Design of Organocatalysts for Asymmetric Propargylations through Computational ScreeningClick to copy article linkArticle link copied!
Abstract
The development of asymmetric catalysts is typically driven by the experimental screening of potential catalyst designs. Herein, we demonstrate the design of asymmetric propargylation catalysts through computational screening. This was done using our computational toolkit AARON (automated alkylation reaction optimizer for N-oxides), which automates the prediction of enantioselectivities for bidentate Lewis base catalyzed alkylation reactions. A systematic screening of 59 potential catalysts built on 6 bipyridine N,N′-dioxide-derived scaffolds results in predicted ee values for the propargylation of benzaldehyde ranging from 45% (S) to 99% (R), with 12 ee values exceeding 95%. These data provide a broad set of experimentally testable predictions. Moreover, the associated data revealed key details regarding the role of stabilizing electrostatic interactions in asymmetric propargylations, which were harnessed in the design of a propargylation catalyst for which the predicted ee exceeds 99%.
I Introduction
Scheme 1
Scheme 2
Figure 1
Figure 1. Five distinct ligand configurations for C2-symmetric bidentate Lewis base catalyzed alkylation reactions, where Nu is the alkyl nucleophile.
II Theoretical Methods
III Results and Discussion

R = H, except where noted. Positive ee values correspond to excess (R)-alcohol formation, whereas negative values indicate excess (S)-alcohol. These ee values are based on relative energy barriers. Values based on relative enthalpy and free energy barriers are available in Table S2 in the Supporting Information.
Experimental ee 52%. (9b)
Catalyst 3g is too sterically encumbered to be viable.
Figure 2
Figure 2. B97-D/TZV(2d,2p) predicted relative energies (kcal mol–1) of the thermodynamically accessible TS structures for catalysts 1a–6j (N.B.: for 2a–j, there are multiple low-lying conformers for some of the TS structures corresponding to different orientations of the phenyl rings).
Figure 3
Figure 3. Key TS structures for catalysts 1a along with relative energies in kcal mol–1. Also displayed are the ESPs of the catalyst in the plane of the formyl group (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Figure 4
Figure 4. Key TS structures for catalysts 1g,j and 2j along with relative energies in kcal mol–1. BP1(R), which is low-lying for 1g, is not pictured.
Figure 5
Figure 5. Key TS structures for catalysts 1b,e along with relative energies in kcal mol–1. For 1e, the electrostatic potential of the catalyst in the plane of the formyl group of benzaldehyde is also plotted (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Figure 6
Figure 6. Key TS structures for catalysts 1h,i along with relative energies in kcal mol–1. The electrostatic potential of the catalyst in the plane of the formyl group of benzaldehyde is also plotted (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Additional Catalyst Design
Figure 7
Figure 7. Catalyst 7 along with the key (R)- and (S)-transition states and relative energies in kcal mol–1.
IV Summary and Concluding Remarks
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.6b02366.
Additional data, absolute electronic energies, enthalpies, and free energies, and optimized Cartesian coordinates (PDF)
Cartesian coordinates of the calculated structures (XYZ)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgment
This work was supported by The Welch Foundation (Grant A-1775) and the National Science Foundation (Grant CHE-1266022). Portions of this research were conducted with high-performance research computing resources provided by Texas A&M University (http://hprc.tamu.edu).
References
This article references 28 other publications.
- 1(a) Lam, Y.; Grayson, M. N.; Holland, M. C.; Simon, A.; Houk, K. N. Acc. Chem. Res. 2016, 49, 750– 762 DOI: 10.1021/acs.accounts.6b00006Google Scholar1ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjvV2lsrc%253D&md5=53e388add531aca3cbba99c4e966ce4fTheory and Modeling of Asymmetric Catalytic ReactionsLam, Yu-hong; Grayson, Matthew N.; Holland, Mareike C.; Simon, Adam; Houk, K. N.Accounts of Chemical Research (2016), 49 (4), 750-762CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)Modern d. functional theory and powerful contemporary computers have made it possible to explore complex reactions of value in org. synthesis. We describe recent explorations of mechanisms and origins of stereoselectivities with d. functional theory calcns. The specific functionals and basis sets that are routinely used in computational studies of stereoselectivities of org. and organometallic reactions in our group are described, followed by our recent studies that uncovered the origins of stereocontrol in reactions catalyzed by (1) vicinal diamines, including cinchona alkaloid-derived primary amines, (2) vicinal amidophosphines, and (3) organo-transition-metal complexes. Two common cyclic models account for the stereoselectivity of aldol reactions of metal enolates (Zimmerman-Traxler) or those catalyzed by the organocatalyst proline (Houk-List). Three other models were derived from computational studies described in this Account.Cinchona alkaloid-derived primary amines and other vicinal diamines are venerable asym. organocatalysts. For α-fluorinations and a variety of aldol reactions, vicinal diamines form enamines at one terminal amine and activate electrophilically with NH+ or NF+ at the other. We found that the stereocontrolling transition states are cyclic and that their conformational preferences are responsible for the obsd. stereoselectivity. In fluorinations, the chair seven-membered cyclic transition states is highly favored, just as the Zimmerman-Traxler chair six-membered aldol transition state controls stereoselectivity. In aldol reactions with vicinal diamine catalysts, the crown transition states are favored, both in the prototype and in an exptl. example, shown in the graphic. We found that low-energy conformations of cyclic transition states occur and control stereoselectivities in these reactions. Another class of bifunctional organocatalysts, the vicinal amidophosphines, catalyzes the (3 + 2) annulation reaction of allenes with activated olefins. Stereocontrol here is due to an intermol. hydrogen bond that activates the electrophilic partner in this reaction. We have also studied complex organometallic catalysts. Krische's ruthenium-catalyzed asym. hydrohydroxyalkylation of butadiene involves two chiral ligands at Ru, a chiral diphosphine and a chiral phosphate. The size of this combination strains the limits of modern computations with over 160 atoms, multiple significant steps, and a variety of ligand coordinations and conformations possible. We found that carbon-carbon bond formation occurs via a chair Zimmerman-Traxler-type transition structure and that a formyl CH···O hydrogen bond from aldehyde CH to phosphate oxygen, as well as steric interactions of the two chiral ligands, control the stereoselectivity.(b) Halskov, K. S.; Donslund, B. S.; Paz, B. M.; Jørgensen, K. A. Acc. Chem. Res. 2016, 49, 974– 986 DOI: 10.1021/acs.accounts.6b00008Google ScholarThere is no corresponding record for this reference.(c) Sunoj, R. B. Acc. Chem. Res. 2016, 49, 1019– 1028 DOI: 10.1021/acs.accounts.6b00053Google ScholarThere is no corresponding record for this reference.(d) Reid, J. P.; Simón, L.; Goodman, J. M. Acc. Chem. Res. 2016, 49, 1029– 1041 DOI: 10.1021/acs.accounts.6b00052Google ScholarThere is no corresponding record for this reference.(e) Peng, Q.; Paton, R. S. Acc. Chem. Res. 2016, 49, 1042– 1051 DOI: 10.1021/acs.accounts.6b00084Google Scholar1ehttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XntVShsLw%253D&md5=3b919d050210c1b0fb472bf5411bc782Catalytic Control in Cyclizations: From Computational Mechanistic Understanding to Selectivity PredictionPeng, Qian; Paton, Robert S.Accounts of Chemical Research (2016), 49 (5), 1042-1051CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. This Account describes the use of quantum-chem. calcns. to elucidate mechanisms and develop catalysts to accomplish highly selective cyclization reactions. Chem. is awash with cyclic mols., and the creation of rings is central to org. synthesis. Cyclization reactions, the formation of rings by the reaction of two ends of a linear precursor, have been instrumental in the development of predictive models for chem. reactivity, from Baldwin's classification and rules for ring closure to the Woodward and Hoffmann rules based on the conservation of orbital symmetry and beyond. Ring formation provides a productive and fertile testing ground for the exploration of catalytic mechanisms and chemo-, regio-, diastereo-, and enantioselectivity using computational and exptl. approaches. This Account is organized around case studies from our lab. and illustrates the ways in which computations provide a deeper understanding of the mechanisms of catalysis in 5-endo cyclizations and how computational predictions can lead to the development of new catalysts for enhanced stereoselectivities in asym. cycloisomerizations. We have explored the extent to which several cation-directed 5-endo ring-closing reactions may be considered as electrocyclic and demonstrated that reaction pathways and magnetic parameters of transition structures computed using quantum chem. are inconsistent with this notion, instead favoring a polar mechanism. A rare example of selectivity in favor of 5-endo-trig ring closure is shown to result from subtle substrate effects that bias the reactant conformation out-of-plane, limiting the involvement of cyclic conjugation. The mode of action of a chiral ammonium counterion was deduced via conformational sampling of the transition state assembly and involves coordination to the substrate via a series of nonclassical hydrogen bonds. We describe how computational mechanistic understanding has led directly to the discovery of new catalyst structures for enantioselective cycloisomerizations. Calcns. have revealed that stepwise C-C bond formation and proton transfer dictate the exclusive endo diastereoselectivity of the intramol. Michael addn. to form 2-azabicyclo[3.3.1]nonane skeletons catalyzed by primary amines. These insights have led to development of a highly enantioselective catalyst with higher atom economy than previous generations. This Account also explores transition-metal-catalyzed cycloisomerizations, where our theor. investigations have uncovered an unexpected reaction pathway in the [5 + 2] cycloisomerization of ynamides. This has led to the design of new phosphoramidite ligands to enable double-stereodifferentiating cycloisomerizations in both matched and mismatched catalyst-substrate settings. Computational understanding of the factors responsible for the regio-, enantio-, and diasterocontrol is shown to generate tangible predictions leading to an acceleration of catalyst development for selective cyclizations.(f) Wheeler, S. E.; Seguin, T. J.; Guan, Y.; Doney, A. C. Acc. Chem. Res. 2016, 49, 1061– 1069 DOI: 10.1021/acs.accounts.6b00096Google Scholar1fhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XmsFCrsLw%253D&md5=4cffcbf91f93ae4ecaf20537c364fcebNoncovalent Interactions in Organocatalysis and the Prospect of Computational Catalyst DesignWheeler, Steven E.; Seguin, Trevor J.; Guan, Yanfei; Doney, Analise C.Accounts of Chemical Research (2016), 49 (5), 1061-1069CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Noncovalent interactions are ubiquitous in org. systems, and can play decisive roles in the outcome of asym. organocatalytic reactions. Their prevalence, combined with the often subtle line sepg. favorable dispersion interactions from unfavorable steric interactions, often complicates the identification of the particular noncovalent interactions responsible for stereoselectivity. Ultimately, the stereoselectivity of most organocatalytic reactions hinges on the balance of both favorable and unfavorable noncovalent interactions in the stereocontrolling transition state (TS). In this Account, we provide an overview of our attempts to understand the role of noncovalent interactions in organocatalyzed reactions and to develop new computational tools for organocatalyst design. Following a brief discussion of noncovalent interactions involving arom. rings and the assocd. challenges capturing these effects computationally, we summarize two examples of chiral phosphoric acid catalyzed reactions in which noncovalent interactions play pivotal, although somewhat unexpected, roles. In the first, List's catalytic asym. Fischer indole reaction, we show that both π-stacking and CH/π interactions of the substrate with the 3,3'-aryl groups of the catalyst impact the stability of the stereocontrolling TS. However, these noncovalent interactions oppose each other, with π-stacking interactions stabilizing the TS leading to one enantiomer and CH/π interactions preferentially stabilizing the competing TS. Ultimately, the CH/π interactions dominate and, when combined with hydrogen bonding interactions, lead to preferential formation of the obsd. product. In the second example, a series of phosphoric acid catalyzed asym. ring openings of meso-epoxides, we show that noncovalent interactions of the substrates with the 3,3'-aryl groups of the catalyst play only an indirect role in stereoselectivity. Instead, the stereoselectivity of these reactions are driven by the electrostatic stabilization of a fleeting partial pos. charge in the SN2-like transition state by the chiral electrostatic environment of the phosphoric acid catalyst. Next, we describe our studies of bipyridine N-oxide and N,N'-dioxide catalyzed alkylation reactions. Based on several examples, we demonstrate that there are many potential arrangements of ligands around a hexacoordinate silicon in the stereocontrolling TS, and one must consider all of these in order to identify the lowest-lying TS structures. We also present a model in which electrostatic interactions between a formyl CH group and a chlorine in these TSs underlie the enantioselectivity of these reactions. Finally, we discuss our efforts to develop computational tools for the screening of potential organocatalyst designs, starting in the context of bipyridine N,N'-dioxide catalyzed alkylation reactions. Our new computational tool kit (AARON) has been used to design highly effective catalysts for the asym. propargylation of benzaldehyde, and is currently being used to screen catalysts for other reactions. We conclude with our views on the potential roles of computational chem. in the future of organocatalyst design.
- 2(a) Fleming, E. M.; Quigley, C.; Rozas, I.; Connon, S. J. J. Org. Chem. 2008, 73, 948– 956 DOI: 10.1021/jo702154mGoogle ScholarThere is no corresponding record for this reference.(b) Houk, K. N.; Cheong, P. H.-Y. Nature 2008, 455, 309– 313 DOI: 10.1038/nature07368Google Scholar2bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtFams7rF&md5=2ce3a7459dd13fb106d6de66878c7b31Computational prediction of small-molecule catalystsHouk, K. N.; Cheong, Paul Ha-YeonNature (London, United Kingdom) (2008), 455 (7211), 309-313CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)A review. Most org. and organometallic catalysts were discovered through serendipity or trial and error, rather than by rational design. Computational methods, however, are rapidly becoming a versatile tool for understanding and predicting the roles of such catalysts in asym. reactions. Such methods should now be regarded as a first line of attack in the design of catalysts.(c) Shinisha, C. B.; Janardanan, D.; Sunoj, R. B. In Challenges and Advances in Computational Chemistry and Physics; Leszczynski, J., Ed.; Springer: New York, 2010.Google ScholarThere is no corresponding record for this reference.(d) Sunoj, R. B. WIREs Comp. Mol. Sci. 2011, 1, 920– 931 DOI: 10.1002/wcms.37Google Scholar2dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFGru7%252FJ&md5=df180d5b04fec2e97248b105ca743f12Proline-derived organocatalysis and synergism between theory and experimentsSunoj, Raghavan B.Wiley Interdisciplinary Reviews: Computational Molecular Science (2011), 1 (6), 920-931CODEN: WIRCAH; ISSN:1759-0884. (Wiley-Blackwell)A review. The ability of proline and its derivs. toward catalyzing asym. org. reactions is highlighted. Illustration of the impact of interdisciplinary efforts between computational and exptl. research is provided through a no. of interesting examples.
- 3Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439– 2461 DOI: 10.1021/cr00023a006Google ScholarThere is no corresponding record for this reference.
- 4(a) Brown, J. M.; Deeth, R. J. Angew. Chem., Int. Ed. 2009, 48, 4476– 4479 DOI: 10.1002/anie.200900697Google ScholarThere is no corresponding record for this reference.(b) Madarász, Á.; Dènes, B.; Paton, R. S. J. Chem. Theory Comput. 2016, 12, 1833– 1844 DOI: 10.1021/acs.jctc.5b01237Google Scholar4bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjtlemtrY%253D&md5=ae407b3e3e294aa4630583e90b134c45Development of a True Transition State Force Field from Quantum Mechanical CalculationsMadarasz, Adam; Berta, Denes; Paton, Robert S.Journal of Chemical Theory and Computation (2016), 12 (4), 1833-1844CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)Transition state force fields (TSFF) treated the TS structure as an artificial min. on the potential energy surface in the past decades. The necessary parameters were developed either manually or by the Quantum-to-mol. mechanics method (Q2MM). In contrast with these approaches, here we propose to model the TS structures as genuine saddle points at the mol. mechanics level. Different methods were tested on small model systems of general chem. reactions such as protonation, nucleophilic attack, and substitution, and the new procedure led to more accurate models than the Q2MM-type parametrization. To demonstrate the practicality of our approach, transferrable parameters have been developed for Mo-catalyzed olefin metathesis using quantum mech. properties as ref. data. Based on the proposed strategy, any force field can be extended with true transition state force field (TTSFF) parameters, and they can be readily applied in several mol. mechanics programs as well.(c) Hansen, E.; Rosales, A. R.; Tutkowski, B.; Norrby, P. O.; Wiest, O. Acc. Chem. Res. 2016, 49, 996– 1005 DOI: 10.1021/acs.accounts.6b00037Google ScholarThere is no corresponding record for this reference.(d) Norrby, P.-O.; Liljefors, T. J. Comput. Chem. 1998, 19, 1146– 1166 DOI: 10.1002/(SICI)1096-987X(19980730)19:10<1146::AID-JCC4>3.0.CO;2-MGoogle ScholarThere is no corresponding record for this reference.(e) Nilsson Lill, S. O.; Forbes, A.; Donoghue, P.; Verdolino, V.; Wiest, O.; Rydberg, P.; Norrby, P.-O. Curr. Org. Chem. 2010, 14, 1629– 1645 DOI: 10.2174/138527210793563224Google ScholarThere is no corresponding record for this reference.(f) Limé, E.; Norrby, P.-O. J. Comput. Chem. 2015, 36, 244– 250 DOI: 10.1002/jcc.23797Google ScholarThere is no corresponding record for this reference.(g) Peña-Cabrera, E.; Norrby, P.-O.; Sjögren, M.; Vitagliano, A.; De Felice, V.; Oslob, J.; Ishii, S.; O’Neill, D.; Åkermark, B.; Helquist, P. J. Am. Chem. Soc. 1996, 118, 4299– 4313 DOI: 10.1021/ja950860tGoogle ScholarThere is no corresponding record for this reference.(h) Norrby, P.-O.; Brandt, P.; Rein, T. J. Org. Chem. 1999, 64, 5845– 5852 DOI: 10.1021/jo990318dGoogle ScholarThere is no corresponding record for this reference.(i) Norrby, P. O.; Rasmussen, T.; Haller, J.; Strassner, T.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 10186– 10192 DOI: 10.1021/ja992023nGoogle ScholarThere is no corresponding record for this reference.(j) Fristrup, P.; Jensen, G. H.; Andersen, M. L. N.; Tanner, D.; Norrby, P.-O. J. Organomet. Chem. 2006, 691, 2182– 2198 DOI: 10.1016/j.jorganchem.2005.11.009Google Scholar4jhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XjvFyrtrg%253D&md5=535cf30994933c5f5aeba23bb5d5d9c5Combining Q2MM modeling and kinetic studies for refinement of the osmium-catalyzed asymmetric dihydroxylation (AD) mnemonicFristrup, Peter; Jensen, Gitte Holm; Andersen, Marie Louise Nygaard; Tanner, David; Norrby, Per-OlaJournal of Organometallic Chemistry (2006), 691 (10), 2182-2198CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)The interactions between the substrate and the ligand in the Sharpless AD reaction have been examd. in detail, using a combination of substrate competition expts. and mol. modeling of transition states. There is a good agreement between computational and exptl. results, in particular for the stereoselectivity of the reaction. The influence of each moiety in the second-generation ligand (DHQD)2PHAL on the rate and selectivity of the reaction has been elucidated in detail.(k) Donoghue, P. J.; Helquist, P.; Norrby, P.-O.; Wiest, O. J. Chem. Theory Comput. 2008, 4, 1313– 1323 DOI: 10.1021/ct800132aGoogle Scholar4khttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXovF2rtLc%253D&md5=486705d3de62f28f9d6dde4b1634309cDevelopment of a Q2MM Force Field for the Asymmetric Rhodium Catalyzed Hydrogenation of EnamidesDonoghue, Patrick J.; Helquist, Paul; Norrby, Per-Ola; Wiest, OlafJournal of Chemical Theory and Computation (2008), 4 (8), 1313-1323CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)The rhodium catalyzed asym. hydrogenation of enamides to generate amino acid products and derivs. is a widely used method to generate unnatural amino acids. The choice of a chiral ligand is of utmost importance in this reaction and is often based on high throughput screening or simply trial and error. A virtual screening method can greatly increase the speed of the ligand screening process by calcg. expected enantiomeric excesses from relative energies of diastereomeric transition states. Utilizing the Q2MM method, new mol. mechanics parameters are derived to model the hydride transfer transition state in the reaction. The new parameters were based off of structures calcd. at the B3LYP/LACVP** level of theory and added to the MM3* force field. The new parameters were validated against a test set of exptl. data utilizing a wide range of bis-phosphine ligands. The computational model agreed with exptl. data well overall, with an unsigned mean error of 0.6 kcal/mol against a set of 18 data points from expt. The major errors in the computational model were due either to large energetic errors at high e.e., still resulting in qual. agreement, or cases where large steric interactions prevent the reaction from proceeding as expected.(l) Donoghue, P. J.; Helquist, P.; Norrby, P.-O.; Wiest, O. J. Am. Chem. Soc. 2009, 131, 410– 411 DOI: 10.1021/ja806246hGoogle ScholarThere is no corresponding record for this reference.(m) Limé, E.; Lundholm, M. D.; Forbes, A.; Wiest, O.; Helquist, P.; Norrby, P.-O. J. Chem. Theory Comput. 2014, 10, 2427– 2435 DOI: 10.1021/ct500178wGoogle Scholar4mhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXotVeltLs%253D&md5=5ff5b87e6ecffc14854cb49a31453d98Stereoselectivity in Asymmetric Catalysis: The Case of Ruthenium-Catalyzed Ketone HydrogenationLime, Elaine; Lundholm, Michelle D.; Forbes, Aaron; Wiest, Olaf; Helquist, Paul; Norrby, Per-OlaJournal of Chemical Theory and Computation (2014), 10 (6), 2427-2435CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)The ruthenium-catalyzed asym. hydrogenation of simple ketones to generate enantiopure alcs. is an important process widely used in the fine chem., pharmaceutical, fragrance, and flavor industries. Chiral diphosphine-RuCl2-1,2-diamine complexes are effective catalysts for the reaction giving high chemo- and enantioselectivity. However, no diphosphine-RuCl2-1,2-diamine complex has yet been discovered that is universal for all kinds of ketone substrates, and the ligands must be carefully chosen for each substrate. The procedure of finding the best ligands for a specific substrate can be facilitated by using virtual screening as a complement to the traditional exptl. screening of catalyst libraries. We have generated a transition state force field (TSFF) for the ruthenium-catalyzed asym. hydrogenation of simple ketones using an improved Q2MM method. The developed TSFF can predict the enantioselectivity for 13 catalytic systems taken from the literature, with a mean unsigned error of 2.7 kJ/mol.
- 5Rooks, B. J.; Wheeler, S. E.AARON:Automated Alkylation Reaction Optimizer for N-Oxides, version 0.72; Texas A&M University, College Station, TX, 2015.Google ScholarThere is no corresponding record for this reference.
- 6Rooks, B. J.; Haas, M. R.; Sepúlveda, D.; Lu, T.; Wheeler, S. E. ACS Catal. 2015, 5, 272– 280 DOI: 10.1021/cs5012553Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvFOht73N&md5=c15bbe8127bbadb0f48aabc18568cfefProspects for the Computational Design of Bipyridine N,N'-Dioxide Catalysts for Asymmetric Propargylation ReactionsRooks, Benjamin J.; Haas, Madison R.; Sepulveda, Diana; Lu, Tongxiang; Wheeler, Steven E.ACS Catalysis (2015), 5 (1), 272-280CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Stereoselectivities were predicted for the allylation of benzaldehyde using allyltrichlorosilanes catalyzed by 18 axially chiral bipyridine N,N'-dioxides. This was facilitated by the computational toolkit AARON (Automated Alkylation Reaction Optimizer for N-oxides), which automates the optimization of all of the required transition-state structures for such reactions. Overall, we were able to predict the sense of stereoinduction for all 18 of the catalysts, with predicted ee's in reasonable agreement with expt. for 15 of the 18 catalysts. Curiously, we find that ee's predicted from relative energy barriers are more reliable than those based on either relative enthalpy or free energy barriers. The ability to correctly predict the stereoselectivities for these allylation catalysts in an automated fashion portends the computational screening of potential organocatalysts for this and related reactions. By studying a large no. of allylation catalysts, we were also able to gain new insight into the origin of stereoselectivity in these reactions, extending our previous model for bipyridine N-oxide-catalyzed alkylation reactions (Org. Letters 2012, 14, 5310). Finally, we assessed the potential performance of these bipyridine N,N'-dioxide catalysts for the propargylation of benzaldehyde using allenyltrichlorosilanes, finding that two of these catalysts should provide reasonable stereoselectivities for this transformation. Most importantly, we show that bipyridine N,N'-dioxides constitute an ideal scaffold for the development of asym. propargylation catalysts and, along with AARON, should enable the rational design of such catalysts purely through computation.
- 7Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620– 6628 DOI: 10.1021/jo00101a021Google ScholarThere is no corresponding record for this reference.
- 8Denmark, S. E.; Coe, D. M.; Pratt, N. E.; Griedel, B. D. J. Org. Chem. 1994, 59, 6161– 6163 DOI: 10.1021/jo00100a013Google ScholarThere is no corresponding record for this reference.
- 9(a) Nakajima, M.; Saito, M.; Shiro, M.; Hashimoto, S.-i. J. Am. Chem. Soc. 1998, 120, 6419– 6420 DOI: 10.1021/ja981091rGoogle Scholar9ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXktFWjurg%253D&md5=101c11844fb72c1be1f8ee009f503735(S)-3,3'-Dimethyl-2,2'-biquinoline N,N'-Dioxide as an Efficient Catalyst for Enantioselective Addition of Allyltrichlorosilanes to AldehydesNakajima, Makoto; Saito, Makoto; Shiro, Motoo; Hashimoto, Shun-ichiJournal of the American Chemical Society (1998), 120 (25), 6419-6420CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Reaction of RCHO [R = Ph, 4-MeOC6H4, 4-F3CC6H4, 2-MeC6H4, 1-naphthyl, (E)-Me(CH2)6CH:CH, (E)-PhCH:CH] with CH2:CHC≡CSiCl3 in presence of the title catalyst gave (R)-HOCHRCH2CH:CH2 in 71-92% ee. Similar results were obtained in the reaction of PhCHO with R1R2C:CR3CH2SiCl3 [R1-R3 = H, Me].(b) Nakajima, M.; Saito, M.; Hashimoto, S. Tetrahedron: Asymmetry 2002, 13, 2449– 2452 DOI: 10.1016/S0957-4166(02)00640-7Google ScholarThere is no corresponding record for this reference.
- 10(a) Malkov, A. V.; Orsini, M.; Pernazza, D.; Muir, K. W.; Langer, V.; Meghani, P.; Kočovský, P. Org. Lett. 2002, 4, 1047– 1049 DOI: 10.1021/ol025654mGoogle ScholarThere is no corresponding record for this reference.(b) Shimada, T.; Kina, A.; Ikeda, S.; Hayashi, T. Org. Lett. 2002, 4, 2799– 2801 DOI: 10.1021/ol026376uGoogle Scholar10bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XltV2mtb8%253D&md5=6e3713b3f7729649866499fb8954d532A Novel Axially Chiral 2,2'-Bipyridine N,N'-Dioxide. Its Preparation and Use for Asymmetric Allylation of Aldehydes with Allyl(trichloro)silane as a Highly Efficient CatalystShimada, Toyoshi; Kina, Asato; Ikeda, Syushiro; Hayashi, TamioOrganic Letters (2002), 4 (16), 2799-2801CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)Novel axially chiral 2,2'-bipyridine N,N'-dioxides I (R1 = H, Me, Me3C, Ph; R2 = H, Me) were obtained by a new method that does not involve any procedures for the sepn. of enantiomers. I (R1 = Ph, R2 = H) exhibited extremely high catalytic activity for the asym. allylation of aldehydes with allyl(trichloro)silane. Thus, the allylation of arom. aldehydes R3CHO (R3 = Ph, 4-MeOC6H4, 4-Me3CC6H4, etc.) proceeded in the presence of 0.01 or 0.1 mol % of the dioxide catalyst I to give the corresponding homoallyl alcs. (S)-R3CH(OH)CH2CH:CH2 with up to 98% ee.(c) Malkov, A. V.; Bell, M.; Orsini, M.; Pernazza, D.; Massa, A.; Herrmann, P.; Meghani, P.; Kočovský, P. J. Org. Chem. 2003, 68, 9659– 9668 DOI: 10.1021/jo035074iGoogle ScholarThere is no corresponding record for this reference.(d) Malkov, A. V.; Kočovský, P. Eur. J. Org. Chem. 2007, 2007, 29– 36 DOI: 10.1002/ejoc.200600474Google ScholarThere is no corresponding record for this reference.(e) Hrdina, R.; Valterová, I.; Hodačová, J.; Císařová, I.; Kotora, M. Adv. Synth. Catal. 2007, 349, 822– 826 DOI: 10.1002/adsc.200600400Google ScholarThere is no corresponding record for this reference.(f) Malkov, A. V.; Ramirez-Lopez, P.; Biedermannova, L.; Rulisek, L.; Dufková, L.; Kotora, M.; Zhu, F.; Kočovky, P. J. Am. Chem. Soc. 2008, 130, 5341– 5348 DOI: 10.1021/ja711338qGoogle ScholarThere is no corresponding record for this reference.(g) Malkov, A. V.; Westwater, M.-M.; Gutnov, A.; Ramírez-López, P.; Friscourt, F.; Kadlčíková, A.; Hodačová, J.; Rankovic, Z.; Kotora, M.; Kočovský, P. Tetrahedron 2008, 64, 11335– 11348 DOI: 10.1016/j.tet.2008.08.084Google Scholar10ghttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtlWltr%252FF&md5=2a56a69084219103c0b1f4a89a6e90bbNew pyridine N-oxides as chiral organocatalysts in the asymmetric allylation of aromatic aldehydesMalkov, Andrei V.; Westwater, Mary-Margaret; Gutnov, Andrey; Ramirez-Lopez, Pedro; Friscourt, Frederic; Kadlcikova, Aneta; Hodacova, Jana; Rankovic, Zoran; Kotora, Martin; Kocovsky, PavelTetrahedron (2008), 64 (49), 11335-11348CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)Asym. allylation of arom. aldehydes with allyltrichlorosilane can be catalyzed by new terpene-derived bipyridine N,N'-dioxides and an axially chiral biisoquinoline dioxide with good enantioselectivities. Dioxides have been found to be more reactive catalysts than their monoxide counterparts.(h) Hrdina, R.; Dračínský, M.; Valterová, I.; Hodačová, J.; Císařová, I.; Kotora, M. Adv. Synth. Catal. 2008, 350, 1449– 1456 DOI: 10.1002/adsc.200800141Google Scholar10hhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXos1Kjtrc%253D&md5=d8575eccebffbb23143e2a514d4686e1New pathway to C2-symmetric atropoisomeric bipyridine N,N'-dioxides and solvent effect in enantioselective allylation of aldehydesHrdina, Radim; Dracinsky, Martin; Valterova, Irena; Hodacova, Jana; Cisarova, Ivana; Kotora, MartinAdvanced Synthesis & Catalysis (2008), 350 (10), 1449-1456CODEN: ASCAF7; ISSN:1615-4150. (Wiley-VCH Verlag GmbH & Co. KGaA)The [2 + 2 + 2]cyclotrimerization of 1,7,9,15-hexadecatetrayne with nitriles catalyzed by dicarbonylcyclopentadienylcobalt(I) opened a new pathway for the synthesis of C2-sym. bis(tetrahydroisoquinolines) that were used as starting material for the prepn. of axially chiral bipyridine N,N'-dioxides. The N,N'-dioxides (1 mol%) were found to be highly catalytically active and enantioselective (up to 83% ee) for the asym. allylation of aldehydes with allyl(trichloro)silane in various solvents. In addn., a dramatic solvent effect was obsd. where the use of different solvents induced opposite chiralities of the product with the same enantiomer of the catalyst, e.g., 65% ee (S) in acetonitrile vs. 82% ee (R) in chlorobenzene.(i) Kadlčíková, A.; Hrdina, R.; Valterová, I.; Kotora, M. Adv. Synth. Catal. 2009, 351, 1279– 1283 DOI: 10.1002/adsc.200900224Google ScholarThere is no corresponding record for this reference.
- 11(a) Lu, T.; Porterfield, M. A.; Wheeler, S. E. Org. Lett. 2012, 14, 5310– 5313 DOI: 10.1021/ol302493dGoogle ScholarThere is no corresponding record for this reference.(b) Chen, J. S.; Captain, B.; Takenaka, N. Org. Lett. 2011, 13, 1654– 1657 DOI: 10.1021/ol200102cGoogle ScholarThere is no corresponding record for this reference.
- 12Sepúlveda, D.; Lu, T.; Wheeler, S. E. Org. Biomol. Chem. 2014, 12, 8346 DOI: 10.1039/C4OB01719FGoogle ScholarThere is no corresponding record for this reference.
- 13Lu, T.; Zhu, R.; An, Y.; Wheeler, S. E. J. Am. Chem. Soc. 2012, 134, 3095– 3102 DOI: 10.1021/ja209241nGoogle ScholarThere is no corresponding record for this reference.
- 14(a) Chelucci, G.; Belmonte, N.; Benaglia, M.; Pignataro, L. Tetrahedron Lett. 2007, 48, 4037– 4041 DOI: 10.1016/j.tetlet.2007.04.028Google ScholarThere is no corresponding record for this reference.(b) Hrdina, R.; Opekar, F.; Roithova, J.; Kotora, M. Chem. Commun. 2009, 2314– 2316 DOI: 10.1039/b819545eGoogle ScholarThere is no corresponding record for this reference.(c) Sereda, O.; Tabassum, S.; Wilhelm, R. Top. Curr. Chem. 2009, 291, 349– 393 DOI: 10.1007/128_2008_17Google ScholarThere is no corresponding record for this reference.
- 15(a) Becke, A. J. Chem. Phys. 1997, 107, 8554– 8560 DOI: 10.1063/1.475007Google Scholar15ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXntFGiuro%253D&md5=e9e466d42d8ea239be08b3a1ede19ae7Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionalsBecke, Axel D.Journal of Chemical Physics (1997), 107 (20), 8554-8560CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A systematic procedure for refining gradient corrections in Kohn-Sham exchange-correlation functionals is presented. The procedure is based on least-squares fitting to accurate thermochem. data. In this first application of the method, we use the G2 test set of Pople and co-workers to generate what we believe to be an optimum GGA/exact-exchange d.-functional theory (i.e., generalized gradient approxn. with mixing of exactly computed exchange).(b) Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829– 5835 DOI: 10.1063/1.467146Google ScholarThere is no corresponding record for this reference.(c) Grimme, S. J. Comput. Chem. 2006, 27, 1787– 1799 DOI: 10.1002/jcc.20495Google Scholar15chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFenu7bO&md5=0b4aa16bebc3a0a2ec175d4b161ab0e4Semiempirical GGA-type density functional constructed with a long-range dispersion correctionGrimme, StefanJournal of Computational Chemistry (2006), 27 (15), 1787-1799CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)A new d. functional (DF) of the generalized gradient approxn. (GGA) type for general chem. applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C6·R-6. A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common d. functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on std. thermochem. benchmark sets, for 40 noncovalently bound complexes, including large stacked arom. mols. and group II element clusters, and for the computation of mol. geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for std. functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean abs. deviation of only 3.8 kcal mol-1. The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the av. CCSD(T) accuracy. The basic strategy in the development to restrict the d. functional description to shorter electron correlation lengths scales and to describe situations with medium to large interat. distances by damped C6·R-6 terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chem. method for large systems where dispersion forces are of general importance.
- 16(a) Cancès, E.; Mennucci, B. J. Math. Chem. 1998, 23, 309– 326 DOI: 10.1023/A:1019133611148Google Scholar16ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXls1Shu7c%253D&md5=43cf1ef267bbe34336ad07031ef9c935New applications of integral equations methods for solvation continuum models: ionic solutions and liquid crystalsCances, Eric; Mennucci, BenedettaJournal of Mathematical Chemistry (1998), 23 (3,4), 309-326CODEN: JMCHEG; ISSN:0259-9791. (Baltzer Science Publishers)We present a new method for solving numerically the equations assocd. with solvation continuum models, which also works when the solvent is an anisotropic dielec. or an ionic soln. This method is based on the integral equation formalism. Its theor. background is set up and some numerical results for simple systems are given. This method is much more effective than three-dimensional methods used so far, like finite elements or finite differences, in terms of both numerical accuracy and computational costs.(b) Cancès, E.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032– 3041 DOI: 10.1063/1.474659Google Scholar16bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXlsVOmtb8%253D&md5=0e2416f84d5f5affc048a6fae1c71b2bA new integral equation formalism for the polarizable continuum model: theoretical background and applications to isotropic and anisotropic dielectricsCances, E.; Mennucci, B.; Tomasi, J.Journal of Chemical Physics (1997), 107 (8), 3032-3041CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The authors present a new integral equation formulation of the polarizable continuum model (PCM) which allows one to treat in a single approach dielecs. of different nature: std. isotropic liqs., intrinsically anisotropic media-like liq. crystals and solid matrixes, or ionic solns. Integral equation methods may be used with success also for the latter cases, which are usually studied with three-dimensional methods, by far less competitive in terms of computational effort. The authors present the theor. bases which underlie the method and some numerical tests which show both a complete equivalence with std. PCM versions for isotropic solvents, and a good efficiency for calcns. with anisotropic dielecs.(c) Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105, 2999– 3093 DOI: 10.1021/cr9904009Google Scholar16chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXmsVynurc%253D&md5=462420dd18b3006ee63d1298b66db247Quantum Mechanical Continuum Solvation ModelsTomasi, Jacopo; Mennucci, Benedetta; Cammi, RobertoChemical Reviews (Washington, DC, United States) (2005), 105 (8), 2999-3093CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review.
- 17Grimme, S. Chem. - Eur. J. 2012, 18, 9955– 9964 DOI: 10.1002/chem.201200497Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XpvFGgsrs%253D&md5=6799a866bf6862f957a4a69b1787c3ffSupramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional TheoryGrimme, StefanChemistry - A European Journal (2012), 18 (32), 9955-9964, S9955/1-S9955/53CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The equil. assocn. free enthalpies ΔGa for typical supramol. complexes in soln. are calcd. by ab initio quantum chem. methods. Ten neutral and three pos. charged complexes with exptl. ΔGa values in the range 0 to -21 kcal mol-1 (on av. -6 kcal mol-1) are investigated. The theor. approach employs a (non-dynamic) single-structure model, but computes the various energy terms accurately without any special empirical adjustments. Dispersion cor. d. functional theory (DFT-D3) with extended basis sets (triple-ζ and quadruple-ζ quality) is used to det. structures and gas-phase interaction energies (ΔE), the COSMO-RS continuum solvation model (based on DFT data) provides solvation free enthalpies and the remaining ro-vibrational enthalpic/entropic contributions are obtained from harmonic frequency calcns. Low-lying vibrational modes are treated by a free-rotor approxn. The accurate account of London dispersion interactions is mandatory with contributions in the range -5 to -60 kcal mol-1 (up to 200% of ΔE). Inclusion of three-body dispersion effects improves the results considerably. A semi-local (TPSS) and a hybrid d. functional (PW6B95) have been tested. Although the ΔGa values result as a sum of individually large terms with opposite sign (ΔE vs. solvation and entropy change), the approach provides unprecedented accuracy for ΔGa values with errors of only 2 kcal mol-1 on av. Relative affinities for different guests inside the same host are always obtained correctly. The procedure is suggested as a predictive tool in supramol. chem. and can be applied routinely to semirigid systems with 300-400 atoms. The various contributions to binding and enthalpy-entropy compensations are discussed.
- 18Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.Gaussian 09, Revision D.01; Gaussian, Inc., Wallingford, CT, 2009.Google ScholarThere is no corresponding record for this reference.
- 20(a) Lehn, J. M.; Pietraszkiewicz, M.; Karpiuk, J. Helv. Chim. Acta 1990, 73, 106– 111 DOI: 10.1002/hlca.19900730111Google Scholar20ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXksFWgtbk%253D&md5=72a98f5e9a2804d0e1bf4b3c71e65fcfSynthesis and properties of acyclic and cryptate europium(III) complexes incorporating the 3,3'-biisoquinoline 2,2'-dioxide unitLehn, Jean Marie; Pietraszkiewicz, Marek; Karpiuk, JerzyHelvetica Chimica Acta (1990), 73 (1), 106-11CODEN: HCACAV; ISSN:0018-019X.[LiL]Br and EuL(ClO4)3 (L = I) were prepd. [Eu(L1)2]Cl3 (L1 = 3,3'-biisoquinoline 2,2'-dioxide) has also been obtained. These Eu(III) complexes present characteristic 1H-NMR spectra contg. markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been detd.(b) Lipkowski, J.; Suwinska, K.; Andreetti, G. D. J. Coord. Chem. 1990, 22, 83– 98 DOI: 10.1080/00958979009410031Google Scholar20bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXitFymu7w%253D&md5=0b3251834de36c32bef367e31fcb3d19Molecular and crystal structure of 1,1'-dimethyl-3,3'-biisoquinoline-N,N'-dioxide and its 2:1 complex with europium trichlorideLipkowski, Janusz; Suwinska, Kinga; Andreetti, Giovanni D.Journal of Coordination Chemistry (1990), 22 (2), 83-98CODEN: JCCMBQ; ISSN:0095-8972.The 1st title compd. is orthorhombic, space group P21212, with a 14.032(4), b 10.605(4), and c 5.242(1) Å; dc = 1.347 for Z = 2. The Eu title compd. is monoclinic, space group P21/c with a 12.829(10), b 17.616(5), c 43.863(7) Å, and β 91.34(4)°; dc = 1.414 for Z = 4 (2 mols./Z). The final R values are 0.035 and 0.072, resp. At. coordinates are given. The complex has a 7-fold coordination for Eu via 3 Cl and 4 O atoms. The coordination polyhedron is a distorted pentagonal bipyramid with 4 O and 1 Cl in the equatorial plane and 2 axial Cl ligands. Packing is of a van der Waals type and includes cocrystd. solvent mols.
- 21Wheeler, S. E.; Houk, K. N. J. Chem. Theory Comput. 2009, 5, 2301– 2312 DOI: 10.1021/ct900344gGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXptVKnu7Y%253D&md5=350e2ff3d9d6087deceea87d5c6f73c5Through-Space Effects of Substituents Dominate Molecular Electrostatic Potentials of Substituted ArenesWheeler, Steven E.; Houk, K. N.Journal of Chemical Theory and Computation (2009), 5 (9), 2301-2312CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)Model systems have been studied using d. functional theory to assess the contributions of π-resonance and through-space effects on electrostatic potentials (ESPs) of substituted arenes. The results contradict the widespread assumption that changes in mol. ESPs reflect only local changes in the electron d. Substituent effects on the ESP above the mol. plane are commonly attributed to changes in the aryl π-system. We show that ESP changes for a collection of substituted benzenes and more complex arom. systems can be accounted for mostly by through-space effects, with no change in the aryl π-electron d. Only when π-resonance effects are substantial do they influence changes to any extent in the ESP above the arom. ring. Examples of substituted arenes studied here are taken from the fields of drug design, host-guest chem., and crystal engineering. These findings emphasize the potential pitfalls of assuming ESP changes reflect changes in the local electron d. Since ESP changes are frequently used to rationalize and predict intermol. interactions, these findings have profound implications for our understanding of substituent effects in countless areas of chem. and mol. biol. Specifically, in many noncovalent interactions there are significant, often neglected, through-space interactions with the substituents. Finally, the present results explain the good performance of many mol. mechanics force-fields when applied to supramol. assembly phenomena, despite the neglect of the polarization of the aryl π-system by substituents.
- 22
The NPA charges on the formyl C and H are approximately +0.25e and +0.20e, respectively, across all TS structures.
There is no corresponding record for this reference. - 23
The lowest-lying TS structure is BP1(R), which is only 0.1 kcal mol–1 lower in energy than BP2(S).
There is no corresponding record for this reference. - 24(a) Wheeler, S. E. Acc. Chem. Res. 2013, 46, 1029– 1038 DOI: 10.1021/ar300109nGoogle Scholar24ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XovFWgu7k%253D&md5=045fc22890c76cf01d324cfcc2e44760Understanding Substituent Effects in Noncovalent Interactions Involving Aromatic RingsWheeler, Steven E.Accounts of Chemical Research (2013), 46 (4), 1029-1038CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Noncovalent interactions involving arom. rings such as π-stacking, cation/π, and anion/π interactions are central to many areas of modern chem. Decades of exptl. studies have provided key insights into the impact of substituents on these interactions, leading to the development of simple intuitive models. However, gas-phase computational studies have raised some doubts about the phys. underpinnings of these widespread models. In this Account we review our recent efforts to unravel the origin of substituent effects in π-stacking and ion/π interactions through computational studies of model noncovalent dimers. First, however, we dispel the notion that so-called arom. interactions depend on the aromaticity of the interacting rings by studying model π-stacked dimers in which the aromaticity of one of the monomers can be "switched off". Somewhat surprisingly, the results show that not only is aromaticity unnecessary for π-stacking interactions, but it actually hinders these interactions to some extent. Consequently, when thinking about π-stacking interactions, researchers should consider broader classes of planar mols., not just arom. systems. Conventional models maintain that substituent effects in π-stacking interactions result from changes in the aryl π-system. This view suggests that π-stacking interactions are maximized when one ring is substituted with electron-withdrawing groups and the other with electron donors. In contrast to these prevailing models, we have shown that substituent effects in π-stacking interactions can be described in terms of direct, local interactions between the substituents and the nearby vertex of the other arene. As a result, in polysubstituted π-stacked dimers the substituents operate independently unless they are in each other's local environment. This means that in π-stacked dimers in which one arene is substituted with electron donors and the other with electron acceptors the interactions will be enhanced only to the extent provided by each substituent on its own, unless the substituents on opposing rings are in close proximity. Overall, this local, direct interaction model predicts that substituent effects in π-stacking interactions will be additive and transferable and will also depend on the relative position of substituents on opposing rings. For cation/π and anion/π interactions, similar π-resonance-based models pervade the literature. Again, computational results indicate that substituent effects in model ion/π complexes can be described primarily in terms of direct interactions between the ion and the substituent. Changes in the aryl π-system do not significantly affect these interactions. We also present a simple electrostatic model that further demonstrates this effect and suggests that the dominant interaction for simple substituents is the interaction of the charged ion with the local dipole assocd. with the substituents. Finally, we discuss substituent effects in electrostatic potentials (ESPs), which are widely used in discussions of noncovalent interactions. In the past, widespread misconceptions have confused the relationship between changes in ESPs and local changes in the electron d. We have shown that computed ESP plots of diverse substituted arenes can be reproduced without altering the aryl π-d. This is because substituent-induced changes in the ESP above the center of aryl rings result primarily from through-space effects of substituents rather than through changes in the distribution of the π-electron d.(b) Wheeler, S. E.; Bloom, J. W. G. J. Phys. Chem. A 2014, 118, 6133– 6147 DOI: 10.1021/jp504415pGoogle Scholar24bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXpvFCns7c%253D&md5=e7cfa276bb23513cba63f0bfd5173282Toward a More Complete Understanding of Noncovalent Interactions Involving Aromatic RingsWheeler, Steven E.; Bloom, Jacob W. G.Journal of Physical Chemistry A (2014), 118 (32), 6133-6147CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)A review. Noncovalent interactions involving arom. rings, which include π-stacking interactions, anion-π interactions, and XH-π interactions, among others, are ubiquitous in chem. and biochem. systems. Despite dramatic advances in our understanding of these interactions over the past decade, many aspects of these noncovalent interactions have only recently been uncovered, with many questions remaining. We summarize our computational studies aimed at understanding the impact of substituents and heteroatoms on these noncovalent interactions. In particular, we discuss our local, direct interaction model of substituent effects in π-stacking interactions. In this model, substituent effects are dominated by electrostatic interactions of the local dipoles assocd. with the substituents and the elec. field of the other ring. The implications of the local nature of substituent effects on π-stacking interactions in larger systems are discussed, with examples given for complexes with carbon nanotubes and a small graphene model, as well as model stacked discotic systems. We also discuss related issues involving the interpretation of electrostatic potential (ESP) maps. Although ESP maps are widely used in discussions of noncovalent interactions, they are often misinterpreted. Next, we provide an alternative explanation for the origin of anion-π interactions involving substituted benzenes and N-heterocycles, and show that these interactions are well-described by simple models based solely on charge-dipole interactions. Finally, we summarize our recent work on the phys. nature of substituent effects in XH-π interactions. Together, these results paint a more complete picture of noncovalent interactions involving arom. rings and provide a firm conceptual foundation for the rational exploitation of these interactions in a myriad of chem. contexts.
- 25Tauer, T.; Sherrill, C. D. J. Phys. Chem. A 2005, 109, 10475– 10478 DOI: 10.1021/jp0553479Google ScholarThere is no corresponding record for this reference.
- 26(a) Seguin, T. J.; Wheeler, S. E. ACS Catal. 2016, 6, 2681– 2688 DOI: 10.1021/acscatal.6b00538Google Scholar26ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XktFejsLw%253D&md5=e34c43ea01cbc3a3c2260003348e9265Electrostatic Basis for Enantioselective Bronsted-Acid-Catalyzed Asymmetric Ring Openings of meso-EpoxidesSeguin, Trevor J.; Wheeler, Steven E.ACS Catalysis (2016), 6 (4), 2681-2688CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Computational studies of three chiral phosphoric-acid-catalyzed asym. ring-openings of meso-epoxides show that the enantioselectivity of these reactions stems from favorable electrostatic interactions of the preferred transition state with the phosphoryl oxygen of the catalyst. The 3,3'-aryl substituents of the catalysts, which are vital for enantioselectivity, serve primarily to create a narrow binding groove that restricts the substrate orientations within the chiral electrostatic environment of the phosphoric acid. This electrostatic, enzyme-like mode of stereoinduction appears to be general for these reactions and suggests a complementary means of achieving stereoinduction in chiral phosphoric acid catalysis. Finally, examn. of the mechanism for subsequent reactions in List's organocatalytic cascade for the synthesis of β-hydroxythiols (Monaco, M. R.; Pr´evost, S.; List, B. J. Am. Chem. Soc. 2014, 136, 16982) explains the requirement for elevated temps. for the latter steps in the cascade sequence, as well as the lack of reactivity of five-membered cyclic epoxides in this transformation.(b) Seguin, T. J.; Lu, T.; Wheeler, S. E. Org. Lett. 2015, 17, 3066– 3069 DOI: 10.1021/acs.orglett.5b01349Google ScholarThere is no corresponding record for this reference.(c) Seguin, T. J.; Wheeler, S. E. ACS Catal. 2016, 6, 7222– 7228 DOI: 10.1021/acscatal.6b01915Google Scholar26chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFamsrjK&md5=b4fdd63c3229a6e97e2ace6768b4204bCompeting Noncovalent Interactions Control the Stereoselectivity of Chiral Phosphoric Acid Catalyzed Ring Openings of 3-Substituted OxetanesSeguin, Trevor J.; Wheeler, Steven E.ACS Catalysis (2016), 6 (10), 7222-7228CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)The noncovalent interactions responsible for enantioselectivity in organo-catalytic oxetane ring openings were quantified using d. functional theory (DFT) computations. Data show that the mode of stereoinduction in these systems differs markedly for different substituted oxetanes, highlighting the challenge of developing general stereochem. models for such reactions. For oxetanes monosubstituted at the 3-position, the enantioselectivity is primarily due to differential CH···π interactions between the mercaptobenzothiazole nucleophile and the arom. backbone of the catalyst. This can be contrasted with 3,3-disubstituted oxetanes, for which interactions between an oxetane substituent and the phosphoric acid functionality and/or the anthryl groups of the catalyst become more important. The former effects are particularly important in the case of 3-OH-substituted oxetanes. Overall, these reactions demonstrate the diversity of competing noncovalent interactions that control the stereoselectivity of many phosphoric acid catalyzed reactions.
- 27
The corresponding energy difference is 1.5 kcal mol–1 for 1c.
There is no corresponding record for this reference. - 28Guan, Y.; Rooks, B. J.; Wheeler, S. E.AARON: An Automated Reaction Optimizer for Non-metal catalyzed reactions, version 0.91; Texas A&M University, College Station, TX, 2016.Google ScholarThere is no corresponding record for this reference.
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(23)
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(21)
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(14)
, 1990-2000. https://doi.org/10.1021/acs.accounts.3c00198
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(15)
, 2616-2621. https://doi.org/10.1021/acs.orglett.3c00590
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(23)
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(17)
, 10923-10932. https://doi.org/10.1021/acscatal.1c02084
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(15)
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(11)
, 4207-4212. https://doi.org/10.1021/acs.orglett.0c01260
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(3)
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(6)
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(4)
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(2)
, 385-399. https://doi.org/10.1021/acs.jpca.8b10007
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(10)
, 5249-5261. https://doi.org/10.1021/acs.jctc.8b00578
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(18)
, 5757-5761. https://doi.org/10.1021/acs.orglett.8b02457
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(7)
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(2)
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(11)
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(42)
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(36)
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(4)
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(4)
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(46)
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(58)
https://doi.org/10.1002/chem.202201570
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(30)
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https://doi.org/10.1002/cmtd.202100107
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(1-4)
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(1-4)
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(24)
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(12)
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(30)
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(4)
https://doi.org/10.1002/wcms.1510
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(20)
, 6879-6889. https://doi.org/10.1039/D1SC00482D
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(6)
, 1584. https://doi.org/10.3390/molecules26061584
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(23)
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(35)
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(24)
, 13431-13439. https://doi.org/10.1039/D0CP01396J
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(20)
, 11529-11536. https://doi.org/10.1039/D0CP00481B
- C. Rose Kennedy, Bo Young Choi, Mary‐Grace R. Reeves, Eric N. Jacobsen. Enantioselective Catalysis of an Anionic Oxy‐Cope Rearrangement Enabled by Synergistic Ion Binding. Israel Journal of Chemistry 2020, 60
(3-4)
, 461-474. https://doi.org/10.1002/ijch.201900168
- Cuihuan Geng, Rongxiu Zhu, Dongju Zhang, Tongxiang Lu, Steven E. Wheeler, Chengbu Liu. Solvent dependence of the stereoselectivity in bipyridine N,N′-dioxide catalyzed allylation of aromatic aldehydes: A computational perspective. Molecular Catalysis 2020, 483 , 110712. https://doi.org/10.1016/j.mcat.2019.110712
- Yangqiu Liu, Xin Yue, Chenguang Luo, Lin Zhang, Ming Lei. Mechanisms of Ketone/Imine Hydrogenation Catalyzed by Transition‐Metal Complexes. ENERGY & ENVIRONMENTAL MATERIALS 2019, 2
(4)
, 292-312. https://doi.org/10.1002/eem2.12050
- Lihan Zhu, Hend Mohamed, Haiyan Yuan, Jingping Zhang. The control effects of different scaffolds in chiral phosphoric acids: a case study of enantioselective asymmetric arylation. Catalysis Science & Technology 2019, 9
(22)
, 6482-6491. https://doi.org/10.1039/C9CY01420A
- Kevin Kang, Jack Fuller, Alexander H. Reath, Joseph W. Ziller, Anastassia N. Alexandrova, Jenny Y. Yang. Installation of internal electric fields by non-redox active cations in transition metal complexes. Chemical Science 2019, 10
(43)
, 10135-10142. https://doi.org/10.1039/C9SC02870F
- Jun Kikuchi, Masahiro Terada. Enantioselective Addition Reaction of Azlactones with Styrene Derivatives Catalyzed by Strong Chiral Brønsted Acids. Angewandte Chemie 2019, 131
(25)
, 8546-8550. https://doi.org/10.1002/ange.201903111
- Jun Kikuchi, Masahiro Terada. Enantioselective Addition Reaction of Azlactones with Styrene Derivatives Catalyzed by Strong Chiral Brønsted Acids. Angewandte Chemie International Edition 2019, 58
(25)
, 8458-8462. https://doi.org/10.1002/anie.201903111
- Jun Kikuchi, Hiromu Aramaki, Hiroshi Okamoto, Masahiro Terada. F
10
BINOL-derived chiral phosphoric acid-catalyzed enantioselective carbonyl-ene reaction: theoretical elucidation of stereochemical outcomes. Chemical Science 2019, 10
(5)
, 1426-1433. https://doi.org/10.1039/C8SC03587C
- Hiroaki Iwamoto, Tsuneo Imamoto, Hajime Ito. Computational design of high-performance ligand for enantioselective Markovnikov hydroboration of aliphatic terminal alkenes. Nature Communications 2018, 9
(1)
https://doi.org/10.1038/s41467-018-04693-9
- Jolene P. Reid, Matthew S. Sigman. Comparing quantitative prediction methods for the discovery of small-molecule chiral catalysts. Nature Reviews Chemistry 2018, 2
(10)
, 290-305. https://doi.org/10.1038/s41570-018-0040-8
- Matthew D. Wodrich, Michael Busch, Clémence Corminboeuf. Expedited Screening of Active and Regioselective Catalysts for the Hydroformylation Reaction. Helvetica Chimica Acta 2018, 101
(9)
https://doi.org/10.1002/hlca.201800107
- Abdulrahiman Nijamudheen, Alexey V. Akimov. Quantum Dynamics Effects in Photocatalysis. 2018, 527-566. https://doi.org/10.1002/9783527808175.ch19
- Matthew D. Wodrich, Boodsarin Sawatlon, Michael Busch, Clémence Corminboeuf. On the Generality of Molecular Volcano Plots. ChemCatChem 2018, 10
(7)
, 1586-1591. https://doi.org/10.1002/cctc.201701709
- Amanda L. Dewyer, Alonso J. Argüelles, Paul M. Zimmerman. Methods for exploring reaction space in molecular systems. WIREs Computational Molecular Science 2018, 8
(2)
https://doi.org/10.1002/wcms.1354
- Toshinobu Korenaga, Ryo Sasaki, Toshihide Takemoto, Toshihisa Yasuda, Masahito Watanabe. Computationally‐Led Ligand Modification using Interplay between Theory and Experiments: Highly Active Chiral Rhodium Catalyst Controlled by Electronic Effects and CH–π Interactions. Advanced Synthesis & Catalysis 2018, 360
(2)
, 322-333. https://doi.org/10.1002/adsc.201701191
- Luis Simón. Enantioselectivity in CPA-catalyzed Friedel–Crafts reaction of indole and
N
-tosylimines: a challenge for guiding models. Organic & Biomolecular Chemistry 2018, 16
(13)
, 2225-2238. https://doi.org/10.1039/C7OB02875J
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(9)
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N
2′ reaction for enantioselective construction of a quaternary stereogenic center. Chemical Science 2018, 9
(26)
, 5747-5757. https://doi.org/10.1039/C8SC01942H
- Yanfei Guan, Steven E. Wheeler. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium‐Catalyzed Asymmetric Hydrogenation. Angewandte Chemie 2017, 129
(31)
, 9229-9233. https://doi.org/10.1002/ange.201704663
- Yanfei Guan, Steven E. Wheeler. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium‐Catalyzed Asymmetric Hydrogenation. Angewandte Chemie International Edition 2017, 56
(31)
, 9101-9105. https://doi.org/10.1002/anie.201704663
- Trevor J. Seguin, Steven E. Wheeler. Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium‐Ion Asymmetric Counteranion‐Directed Catalysis. Angewandte Chemie 2016, 128
(51)
, 16121-16125. https://doi.org/10.1002/ange.201609095
- Trevor J. Seguin, Steven E. Wheeler. Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium‐Ion Asymmetric Counteranion‐Directed Catalysis. Angewandte Chemie International Edition 2016, 55
(51)
, 15889-15893. https://doi.org/10.1002/anie.201609095
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Abstract
Scheme 1
Scheme 1. Asymmetric Propargylation of Benzaldehyde using Allenyltrichlorosilane, along with a Depiction of the Stereocontrolling StepScheme 2
Scheme 2. Library of Catalysts That Were Screened for Reaction 1Figure 1
Figure 1. Five distinct ligand configurations for C2-symmetric bidentate Lewis base catalyzed alkylation reactions, where Nu is the alkyl nucleophile.
Figure 2
Figure 2. B97-D/TZV(2d,2p) predicted relative energies (kcal mol–1) of the thermodynamically accessible TS structures for catalysts 1a–6j (N.B.: for 2a–j, there are multiple low-lying conformers for some of the TS structures corresponding to different orientations of the phenyl rings).
Figure 3
Figure 3. Key TS structures for catalysts 1a along with relative energies in kcal mol–1. Also displayed are the ESPs of the catalyst in the plane of the formyl group (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Figure 4
Figure 4. Key TS structures for catalysts 1g,j and 2j along with relative energies in kcal mol–1. BP1(R), which is low-lying for 1g, is not pictured.
Figure 5
Figure 5. Key TS structures for catalysts 1b,e along with relative energies in kcal mol–1. For 1e, the electrostatic potential of the catalyst in the plane of the formyl group of benzaldehyde is also plotted (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Figure 6
Figure 6. Key TS structures for catalysts 1h,i along with relative energies in kcal mol–1. The electrostatic potential of the catalyst in the plane of the formyl group of benzaldehyde is also plotted (red, −30 kcal mol–1; blue, +30 kcal mol–1; allenyl group removed for clarity).
Figure 7
Figure 7. Catalyst 7 along with the key (R)- and (S)-transition states and relative energies in kcal mol–1.
References
This article references 28 other publications.
- 1(a) Lam, Y.; Grayson, M. N.; Holland, M. C.; Simon, A.; Houk, K. N. Acc. Chem. Res. 2016, 49, 750– 762 DOI: 10.1021/acs.accounts.6b000061ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjvV2lsrc%253D&md5=53e388add531aca3cbba99c4e966ce4fTheory and Modeling of Asymmetric Catalytic ReactionsLam, Yu-hong; Grayson, Matthew N.; Holland, Mareike C.; Simon, Adam; Houk, K. N.Accounts of Chemical Research (2016), 49 (4), 750-762CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)Modern d. functional theory and powerful contemporary computers have made it possible to explore complex reactions of value in org. synthesis. We describe recent explorations of mechanisms and origins of stereoselectivities with d. functional theory calcns. The specific functionals and basis sets that are routinely used in computational studies of stereoselectivities of org. and organometallic reactions in our group are described, followed by our recent studies that uncovered the origins of stereocontrol in reactions catalyzed by (1) vicinal diamines, including cinchona alkaloid-derived primary amines, (2) vicinal amidophosphines, and (3) organo-transition-metal complexes. Two common cyclic models account for the stereoselectivity of aldol reactions of metal enolates (Zimmerman-Traxler) or those catalyzed by the organocatalyst proline (Houk-List). Three other models were derived from computational studies described in this Account.Cinchona alkaloid-derived primary amines and other vicinal diamines are venerable asym. organocatalysts. For α-fluorinations and a variety of aldol reactions, vicinal diamines form enamines at one terminal amine and activate electrophilically with NH+ or NF+ at the other. We found that the stereocontrolling transition states are cyclic and that their conformational preferences are responsible for the obsd. stereoselectivity. In fluorinations, the chair seven-membered cyclic transition states is highly favored, just as the Zimmerman-Traxler chair six-membered aldol transition state controls stereoselectivity. In aldol reactions with vicinal diamine catalysts, the crown transition states are favored, both in the prototype and in an exptl. example, shown in the graphic. We found that low-energy conformations of cyclic transition states occur and control stereoselectivities in these reactions. Another class of bifunctional organocatalysts, the vicinal amidophosphines, catalyzes the (3 + 2) annulation reaction of allenes with activated olefins. Stereocontrol here is due to an intermol. hydrogen bond that activates the electrophilic partner in this reaction. We have also studied complex organometallic catalysts. Krische's ruthenium-catalyzed asym. hydrohydroxyalkylation of butadiene involves two chiral ligands at Ru, a chiral diphosphine and a chiral phosphate. The size of this combination strains the limits of modern computations with over 160 atoms, multiple significant steps, and a variety of ligand coordinations and conformations possible. We found that carbon-carbon bond formation occurs via a chair Zimmerman-Traxler-type transition structure and that a formyl CH···O hydrogen bond from aldehyde CH to phosphate oxygen, as well as steric interactions of the two chiral ligands, control the stereoselectivity.(b) Halskov, K. S.; Donslund, B. S.; Paz, B. M.; Jørgensen, K. A. Acc. Chem. Res. 2016, 49, 974– 986 DOI: 10.1021/acs.accounts.6b00008There is no corresponding record for this reference.(c) Sunoj, R. B. Acc. Chem. Res. 2016, 49, 1019– 1028 DOI: 10.1021/acs.accounts.6b00053There is no corresponding record for this reference.(d) Reid, J. P.; Simón, L.; Goodman, J. M. Acc. Chem. Res. 2016, 49, 1029– 1041 DOI: 10.1021/acs.accounts.6b00052There is no corresponding record for this reference.(e) Peng, Q.; Paton, R. S. Acc. Chem. Res. 2016, 49, 1042– 1051 DOI: 10.1021/acs.accounts.6b000841ehttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XntVShsLw%253D&md5=3b919d050210c1b0fb472bf5411bc782Catalytic Control in Cyclizations: From Computational Mechanistic Understanding to Selectivity PredictionPeng, Qian; Paton, Robert S.Accounts of Chemical Research (2016), 49 (5), 1042-1051CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. This Account describes the use of quantum-chem. calcns. to elucidate mechanisms and develop catalysts to accomplish highly selective cyclization reactions. Chem. is awash with cyclic mols., and the creation of rings is central to org. synthesis. Cyclization reactions, the formation of rings by the reaction of two ends of a linear precursor, have been instrumental in the development of predictive models for chem. reactivity, from Baldwin's classification and rules for ring closure to the Woodward and Hoffmann rules based on the conservation of orbital symmetry and beyond. Ring formation provides a productive and fertile testing ground for the exploration of catalytic mechanisms and chemo-, regio-, diastereo-, and enantioselectivity using computational and exptl. approaches. This Account is organized around case studies from our lab. and illustrates the ways in which computations provide a deeper understanding of the mechanisms of catalysis in 5-endo cyclizations and how computational predictions can lead to the development of new catalysts for enhanced stereoselectivities in asym. cycloisomerizations. We have explored the extent to which several cation-directed 5-endo ring-closing reactions may be considered as electrocyclic and demonstrated that reaction pathways and magnetic parameters of transition structures computed using quantum chem. are inconsistent with this notion, instead favoring a polar mechanism. A rare example of selectivity in favor of 5-endo-trig ring closure is shown to result from subtle substrate effects that bias the reactant conformation out-of-plane, limiting the involvement of cyclic conjugation. The mode of action of a chiral ammonium counterion was deduced via conformational sampling of the transition state assembly and involves coordination to the substrate via a series of nonclassical hydrogen bonds. We describe how computational mechanistic understanding has led directly to the discovery of new catalyst structures for enantioselective cycloisomerizations. Calcns. have revealed that stepwise C-C bond formation and proton transfer dictate the exclusive endo diastereoselectivity of the intramol. Michael addn. to form 2-azabicyclo[3.3.1]nonane skeletons catalyzed by primary amines. These insights have led to development of a highly enantioselective catalyst with higher atom economy than previous generations. This Account also explores transition-metal-catalyzed cycloisomerizations, where our theor. investigations have uncovered an unexpected reaction pathway in the [5 + 2] cycloisomerization of ynamides. This has led to the design of new phosphoramidite ligands to enable double-stereodifferentiating cycloisomerizations in both matched and mismatched catalyst-substrate settings. Computational understanding of the factors responsible for the regio-, enantio-, and diasterocontrol is shown to generate tangible predictions leading to an acceleration of catalyst development for selective cyclizations.(f) Wheeler, S. E.; Seguin, T. J.; Guan, Y.; Doney, A. C. Acc. Chem. Res. 2016, 49, 1061– 1069 DOI: 10.1021/acs.accounts.6b000961fhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XmsFCrsLw%253D&md5=4cffcbf91f93ae4ecaf20537c364fcebNoncovalent Interactions in Organocatalysis and the Prospect of Computational Catalyst DesignWheeler, Steven E.; Seguin, Trevor J.; Guan, Yanfei; Doney, Analise C.Accounts of Chemical Research (2016), 49 (5), 1061-1069CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Noncovalent interactions are ubiquitous in org. systems, and can play decisive roles in the outcome of asym. organocatalytic reactions. Their prevalence, combined with the often subtle line sepg. favorable dispersion interactions from unfavorable steric interactions, often complicates the identification of the particular noncovalent interactions responsible for stereoselectivity. Ultimately, the stereoselectivity of most organocatalytic reactions hinges on the balance of both favorable and unfavorable noncovalent interactions in the stereocontrolling transition state (TS). In this Account, we provide an overview of our attempts to understand the role of noncovalent interactions in organocatalyzed reactions and to develop new computational tools for organocatalyst design. Following a brief discussion of noncovalent interactions involving arom. rings and the assocd. challenges capturing these effects computationally, we summarize two examples of chiral phosphoric acid catalyzed reactions in which noncovalent interactions play pivotal, although somewhat unexpected, roles. In the first, List's catalytic asym. Fischer indole reaction, we show that both π-stacking and CH/π interactions of the substrate with the 3,3'-aryl groups of the catalyst impact the stability of the stereocontrolling TS. However, these noncovalent interactions oppose each other, with π-stacking interactions stabilizing the TS leading to one enantiomer and CH/π interactions preferentially stabilizing the competing TS. Ultimately, the CH/π interactions dominate and, when combined with hydrogen bonding interactions, lead to preferential formation of the obsd. product. In the second example, a series of phosphoric acid catalyzed asym. ring openings of meso-epoxides, we show that noncovalent interactions of the substrates with the 3,3'-aryl groups of the catalyst play only an indirect role in stereoselectivity. Instead, the stereoselectivity of these reactions are driven by the electrostatic stabilization of a fleeting partial pos. charge in the SN2-like transition state by the chiral electrostatic environment of the phosphoric acid catalyst. Next, we describe our studies of bipyridine N-oxide and N,N'-dioxide catalyzed alkylation reactions. Based on several examples, we demonstrate that there are many potential arrangements of ligands around a hexacoordinate silicon in the stereocontrolling TS, and one must consider all of these in order to identify the lowest-lying TS structures. We also present a model in which electrostatic interactions between a formyl CH group and a chlorine in these TSs underlie the enantioselectivity of these reactions. Finally, we discuss our efforts to develop computational tools for the screening of potential organocatalyst designs, starting in the context of bipyridine N,N'-dioxide catalyzed alkylation reactions. Our new computational tool kit (AARON) has been used to design highly effective catalysts for the asym. propargylation of benzaldehyde, and is currently being used to screen catalysts for other reactions. We conclude with our views on the potential roles of computational chem. in the future of organocatalyst design.
- 2(a) Fleming, E. M.; Quigley, C.; Rozas, I.; Connon, S. J. J. Org. Chem. 2008, 73, 948– 956 DOI: 10.1021/jo702154mThere is no corresponding record for this reference.(b) Houk, K. N.; Cheong, P. H.-Y. Nature 2008, 455, 309– 313 DOI: 10.1038/nature073682bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtFams7rF&md5=2ce3a7459dd13fb106d6de66878c7b31Computational prediction of small-molecule catalystsHouk, K. N.; Cheong, Paul Ha-YeonNature (London, United Kingdom) (2008), 455 (7211), 309-313CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)A review. Most org. and organometallic catalysts were discovered through serendipity or trial and error, rather than by rational design. Computational methods, however, are rapidly becoming a versatile tool for understanding and predicting the roles of such catalysts in asym. reactions. Such methods should now be regarded as a first line of attack in the design of catalysts.(c) Shinisha, C. B.; Janardanan, D.; Sunoj, R. B. In Challenges and Advances in Computational Chemistry and Physics; Leszczynski, J., Ed.; Springer: New York, 2010.There is no corresponding record for this reference.(d) Sunoj, R. B. WIREs Comp. Mol. Sci. 2011, 1, 920– 931 DOI: 10.1002/wcms.372dhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsFGru7%252FJ&md5=df180d5b04fec2e97248b105ca743f12Proline-derived organocatalysis and synergism between theory and experimentsSunoj, Raghavan B.Wiley Interdisciplinary Reviews: Computational Molecular Science (2011), 1 (6), 920-931CODEN: WIRCAH; ISSN:1759-0884. (Wiley-Blackwell)A review. The ability of proline and its derivs. toward catalyzing asym. org. reactions is highlighted. Illustration of the impact of interdisciplinary efforts between computational and exptl. research is provided through a no. of interesting examples.
- 3Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439– 2461 DOI: 10.1021/cr00023a006There is no corresponding record for this reference.
- 4(a) Brown, J. M.; Deeth, R. J. Angew. Chem., Int. Ed. 2009, 48, 4476– 4479 DOI: 10.1002/anie.200900697There is no corresponding record for this reference.(b) Madarász, Á.; Dènes, B.; Paton, R. S. J. Chem. Theory Comput. 2016, 12, 1833– 1844 DOI: 10.1021/acs.jctc.5b012374bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjtlemtrY%253D&md5=ae407b3e3e294aa4630583e90b134c45Development of a True Transition State Force Field from Quantum Mechanical CalculationsMadarasz, Adam; Berta, Denes; Paton, Robert S.Journal of Chemical Theory and Computation (2016), 12 (4), 1833-1844CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)Transition state force fields (TSFF) treated the TS structure as an artificial min. on the potential energy surface in the past decades. The necessary parameters were developed either manually or by the Quantum-to-mol. mechanics method (Q2MM). In contrast with these approaches, here we propose to model the TS structures as genuine saddle points at the mol. mechanics level. Different methods were tested on small model systems of general chem. reactions such as protonation, nucleophilic attack, and substitution, and the new procedure led to more accurate models than the Q2MM-type parametrization. To demonstrate the practicality of our approach, transferrable parameters have been developed for Mo-catalyzed olefin metathesis using quantum mech. properties as ref. data. Based on the proposed strategy, any force field can be extended with true transition state force field (TTSFF) parameters, and they can be readily applied in several mol. mechanics programs as well.(c) Hansen, E.; Rosales, A. R.; Tutkowski, B.; Norrby, P. O.; Wiest, O. Acc. Chem. Res. 2016, 49, 996– 1005 DOI: 10.1021/acs.accounts.6b00037There is no corresponding record for this reference.(d) Norrby, P.-O.; Liljefors, T. J. Comput. Chem. 1998, 19, 1146– 1166 DOI: 10.1002/(SICI)1096-987X(19980730)19:10<1146::AID-JCC4>3.0.CO;2-MThere is no corresponding record for this reference.(e) Nilsson Lill, S. O.; Forbes, A.; Donoghue, P.; Verdolino, V.; Wiest, O.; Rydberg, P.; Norrby, P.-O. Curr. Org. Chem. 2010, 14, 1629– 1645 DOI: 10.2174/138527210793563224There is no corresponding record for this reference.(f) Limé, E.; Norrby, P.-O. J. Comput. Chem. 2015, 36, 244– 250 DOI: 10.1002/jcc.23797There is no corresponding record for this reference.(g) Peña-Cabrera, E.; Norrby, P.-O.; Sjögren, M.; Vitagliano, A.; De Felice, V.; Oslob, J.; Ishii, S.; O’Neill, D.; Åkermark, B.; Helquist, P. J. Am. Chem. Soc. 1996, 118, 4299– 4313 DOI: 10.1021/ja950860tThere is no corresponding record for this reference.(h) Norrby, P.-O.; Brandt, P.; Rein, T. J. Org. Chem. 1999, 64, 5845– 5852 DOI: 10.1021/jo990318dThere is no corresponding record for this reference.(i) Norrby, P. O.; Rasmussen, T.; Haller, J.; Strassner, T.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 10186– 10192 DOI: 10.1021/ja992023nThere is no corresponding record for this reference.(j) Fristrup, P.; Jensen, G. H.; Andersen, M. L. N.; Tanner, D.; Norrby, P.-O. J. Organomet. Chem. 2006, 691, 2182– 2198 DOI: 10.1016/j.jorganchem.2005.11.0094jhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XjvFyrtrg%253D&md5=535cf30994933c5f5aeba23bb5d5d9c5Combining Q2MM modeling and kinetic studies for refinement of the osmium-catalyzed asymmetric dihydroxylation (AD) mnemonicFristrup, Peter; Jensen, Gitte Holm; Andersen, Marie Louise Nygaard; Tanner, David; Norrby, Per-OlaJournal of Organometallic Chemistry (2006), 691 (10), 2182-2198CODEN: JORCAI; ISSN:0022-328X. (Elsevier B.V.)The interactions between the substrate and the ligand in the Sharpless AD reaction have been examd. in detail, using a combination of substrate competition expts. and mol. modeling of transition states. There is a good agreement between computational and exptl. results, in particular for the stereoselectivity of the reaction. The influence of each moiety in the second-generation ligand (DHQD)2PHAL on the rate and selectivity of the reaction has been elucidated in detail.(k) Donoghue, P. J.; Helquist, P.; Norrby, P.-O.; Wiest, O. J. Chem. Theory Comput. 2008, 4, 1313– 1323 DOI: 10.1021/ct800132a4khttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXovF2rtLc%253D&md5=486705d3de62f28f9d6dde4b1634309cDevelopment of a Q2MM Force Field for the Asymmetric Rhodium Catalyzed Hydrogenation of EnamidesDonoghue, Patrick J.; Helquist, Paul; Norrby, Per-Ola; Wiest, OlafJournal of Chemical Theory and Computation (2008), 4 (8), 1313-1323CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)The rhodium catalyzed asym. hydrogenation of enamides to generate amino acid products and derivs. is a widely used method to generate unnatural amino acids. The choice of a chiral ligand is of utmost importance in this reaction and is often based on high throughput screening or simply trial and error. A virtual screening method can greatly increase the speed of the ligand screening process by calcg. expected enantiomeric excesses from relative energies of diastereomeric transition states. Utilizing the Q2MM method, new mol. mechanics parameters are derived to model the hydride transfer transition state in the reaction. The new parameters were based off of structures calcd. at the B3LYP/LACVP** level of theory and added to the MM3* force field. The new parameters were validated against a test set of exptl. data utilizing a wide range of bis-phosphine ligands. The computational model agreed with exptl. data well overall, with an unsigned mean error of 0.6 kcal/mol against a set of 18 data points from expt. The major errors in the computational model were due either to large energetic errors at high e.e., still resulting in qual. agreement, or cases where large steric interactions prevent the reaction from proceeding as expected.(l) Donoghue, P. J.; Helquist, P.; Norrby, P.-O.; Wiest, O. J. Am. Chem. Soc. 2009, 131, 410– 411 DOI: 10.1021/ja806246hThere is no corresponding record for this reference.(m) Limé, E.; Lundholm, M. D.; Forbes, A.; Wiest, O.; Helquist, P.; Norrby, P.-O. J. Chem. Theory Comput. 2014, 10, 2427– 2435 DOI: 10.1021/ct500178w4mhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXotVeltLs%253D&md5=5ff5b87e6ecffc14854cb49a31453d98Stereoselectivity in Asymmetric Catalysis: The Case of Ruthenium-Catalyzed Ketone HydrogenationLime, Elaine; Lundholm, Michelle D.; Forbes, Aaron; Wiest, Olaf; Helquist, Paul; Norrby, Per-OlaJournal of Chemical Theory and Computation (2014), 10 (6), 2427-2435CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)The ruthenium-catalyzed asym. hydrogenation of simple ketones to generate enantiopure alcs. is an important process widely used in the fine chem., pharmaceutical, fragrance, and flavor industries. Chiral diphosphine-RuCl2-1,2-diamine complexes are effective catalysts for the reaction giving high chemo- and enantioselectivity. However, no diphosphine-RuCl2-1,2-diamine complex has yet been discovered that is universal for all kinds of ketone substrates, and the ligands must be carefully chosen for each substrate. The procedure of finding the best ligands for a specific substrate can be facilitated by using virtual screening as a complement to the traditional exptl. screening of catalyst libraries. We have generated a transition state force field (TSFF) for the ruthenium-catalyzed asym. hydrogenation of simple ketones using an improved Q2MM method. The developed TSFF can predict the enantioselectivity for 13 catalytic systems taken from the literature, with a mean unsigned error of 2.7 kJ/mol.
- 5Rooks, B. J.; Wheeler, S. E.AARON:Automated Alkylation Reaction Optimizer for N-Oxides, version 0.72; Texas A&M University, College Station, TX, 2015.There is no corresponding record for this reference.
- 6Rooks, B. J.; Haas, M. R.; Sepúlveda, D.; Lu, T.; Wheeler, S. E. ACS Catal. 2015, 5, 272– 280 DOI: 10.1021/cs50125536https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvFOht73N&md5=c15bbe8127bbadb0f48aabc18568cfefProspects for the Computational Design of Bipyridine N,N'-Dioxide Catalysts for Asymmetric Propargylation ReactionsRooks, Benjamin J.; Haas, Madison R.; Sepulveda, Diana; Lu, Tongxiang; Wheeler, Steven E.ACS Catalysis (2015), 5 (1), 272-280CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Stereoselectivities were predicted for the allylation of benzaldehyde using allyltrichlorosilanes catalyzed by 18 axially chiral bipyridine N,N'-dioxides. This was facilitated by the computational toolkit AARON (Automated Alkylation Reaction Optimizer for N-oxides), which automates the optimization of all of the required transition-state structures for such reactions. Overall, we were able to predict the sense of stereoinduction for all 18 of the catalysts, with predicted ee's in reasonable agreement with expt. for 15 of the 18 catalysts. Curiously, we find that ee's predicted from relative energy barriers are more reliable than those based on either relative enthalpy or free energy barriers. The ability to correctly predict the stereoselectivities for these allylation catalysts in an automated fashion portends the computational screening of potential organocatalysts for this and related reactions. By studying a large no. of allylation catalysts, we were also able to gain new insight into the origin of stereoselectivity in these reactions, extending our previous model for bipyridine N-oxide-catalyzed alkylation reactions (Org. Letters 2012, 14, 5310). Finally, we assessed the potential performance of these bipyridine N,N'-dioxide catalysts for the propargylation of benzaldehyde using allenyltrichlorosilanes, finding that two of these catalysts should provide reasonable stereoselectivities for this transformation. Most importantly, we show that bipyridine N,N'-dioxides constitute an ideal scaffold for the development of asym. propargylation catalysts and, along with AARON, should enable the rational design of such catalysts purely through computation.
- 7Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620– 6628 DOI: 10.1021/jo00101a021There is no corresponding record for this reference.
- 8Denmark, S. E.; Coe, D. M.; Pratt, N. E.; Griedel, B. D. J. Org. Chem. 1994, 59, 6161– 6163 DOI: 10.1021/jo00100a013There is no corresponding record for this reference.
- 9(a) Nakajima, M.; Saito, M.; Shiro, M.; Hashimoto, S.-i. J. Am. Chem. Soc. 1998, 120, 6419– 6420 DOI: 10.1021/ja981091r9ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXktFWjurg%253D&md5=101c11844fb72c1be1f8ee009f503735(S)-3,3'-Dimethyl-2,2'-biquinoline N,N'-Dioxide as an Efficient Catalyst for Enantioselective Addition of Allyltrichlorosilanes to AldehydesNakajima, Makoto; Saito, Makoto; Shiro, Motoo; Hashimoto, Shun-ichiJournal of the American Chemical Society (1998), 120 (25), 6419-6420CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Reaction of RCHO [R = Ph, 4-MeOC6H4, 4-F3CC6H4, 2-MeC6H4, 1-naphthyl, (E)-Me(CH2)6CH:CH, (E)-PhCH:CH] with CH2:CHC≡CSiCl3 in presence of the title catalyst gave (R)-HOCHRCH2CH:CH2 in 71-92% ee. Similar results were obtained in the reaction of PhCHO with R1R2C:CR3CH2SiCl3 [R1-R3 = H, Me].(b) Nakajima, M.; Saito, M.; Hashimoto, S. Tetrahedron: Asymmetry 2002, 13, 2449– 2452 DOI: 10.1016/S0957-4166(02)00640-7There is no corresponding record for this reference.
- 10(a) Malkov, A. V.; Orsini, M.; Pernazza, D.; Muir, K. W.; Langer, V.; Meghani, P.; Kočovský, P. Org. Lett. 2002, 4, 1047– 1049 DOI: 10.1021/ol025654mThere is no corresponding record for this reference.(b) Shimada, T.; Kina, A.; Ikeda, S.; Hayashi, T. Org. Lett. 2002, 4, 2799– 2801 DOI: 10.1021/ol026376u10bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XltV2mtb8%253D&md5=6e3713b3f7729649866499fb8954d532A Novel Axially Chiral 2,2'-Bipyridine N,N'-Dioxide. Its Preparation and Use for Asymmetric Allylation of Aldehydes with Allyl(trichloro)silane as a Highly Efficient CatalystShimada, Toyoshi; Kina, Asato; Ikeda, Syushiro; Hayashi, TamioOrganic Letters (2002), 4 (16), 2799-2801CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)Novel axially chiral 2,2'-bipyridine N,N'-dioxides I (R1 = H, Me, Me3C, Ph; R2 = H, Me) were obtained by a new method that does not involve any procedures for the sepn. of enantiomers. I (R1 = Ph, R2 = H) exhibited extremely high catalytic activity for the asym. allylation of aldehydes with allyl(trichloro)silane. Thus, the allylation of arom. aldehydes R3CHO (R3 = Ph, 4-MeOC6H4, 4-Me3CC6H4, etc.) proceeded in the presence of 0.01 or 0.1 mol % of the dioxide catalyst I to give the corresponding homoallyl alcs. (S)-R3CH(OH)CH2CH:CH2 with up to 98% ee.(c) Malkov, A. V.; Bell, M.; Orsini, M.; Pernazza, D.; Massa, A.; Herrmann, P.; Meghani, P.; Kočovský, P. J. Org. Chem. 2003, 68, 9659– 9668 DOI: 10.1021/jo035074iThere is no corresponding record for this reference.(d) Malkov, A. V.; Kočovský, P. Eur. J. Org. Chem. 2007, 2007, 29– 36 DOI: 10.1002/ejoc.200600474There is no corresponding record for this reference.(e) Hrdina, R.; Valterová, I.; Hodačová, J.; Císařová, I.; Kotora, M. Adv. Synth. Catal. 2007, 349, 822– 826 DOI: 10.1002/adsc.200600400There is no corresponding record for this reference.(f) Malkov, A. V.; Ramirez-Lopez, P.; Biedermannova, L.; Rulisek, L.; Dufková, L.; Kotora, M.; Zhu, F.; Kočovky, P. J. Am. Chem. Soc. 2008, 130, 5341– 5348 DOI: 10.1021/ja711338qThere is no corresponding record for this reference.(g) Malkov, A. V.; Westwater, M.-M.; Gutnov, A.; Ramírez-López, P.; Friscourt, F.; Kadlčíková, A.; Hodačová, J.; Rankovic, Z.; Kotora, M.; Kočovský, P. Tetrahedron 2008, 64, 11335– 11348 DOI: 10.1016/j.tet.2008.08.08410ghttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXhtlWltr%252FF&md5=2a56a69084219103c0b1f4a89a6e90bbNew pyridine N-oxides as chiral organocatalysts in the asymmetric allylation of aromatic aldehydesMalkov, Andrei V.; Westwater, Mary-Margaret; Gutnov, Andrey; Ramirez-Lopez, Pedro; Friscourt, Frederic; Kadlcikova, Aneta; Hodacova, Jana; Rankovic, Zoran; Kotora, Martin; Kocovsky, PavelTetrahedron (2008), 64 (49), 11335-11348CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)Asym. allylation of arom. aldehydes with allyltrichlorosilane can be catalyzed by new terpene-derived bipyridine N,N'-dioxides and an axially chiral biisoquinoline dioxide with good enantioselectivities. Dioxides have been found to be more reactive catalysts than their monoxide counterparts.(h) Hrdina, R.; Dračínský, M.; Valterová, I.; Hodačová, J.; Císařová, I.; Kotora, M. Adv. Synth. Catal. 2008, 350, 1449– 1456 DOI: 10.1002/adsc.20080014110hhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXos1Kjtrc%253D&md5=d8575eccebffbb23143e2a514d4686e1New pathway to C2-symmetric atropoisomeric bipyridine N,N'-dioxides and solvent effect in enantioselective allylation of aldehydesHrdina, Radim; Dracinsky, Martin; Valterova, Irena; Hodacova, Jana; Cisarova, Ivana; Kotora, MartinAdvanced Synthesis & Catalysis (2008), 350 (10), 1449-1456CODEN: ASCAF7; ISSN:1615-4150. (Wiley-VCH Verlag GmbH & Co. KGaA)The [2 + 2 + 2]cyclotrimerization of 1,7,9,15-hexadecatetrayne with nitriles catalyzed by dicarbonylcyclopentadienylcobalt(I) opened a new pathway for the synthesis of C2-sym. bis(tetrahydroisoquinolines) that were used as starting material for the prepn. of axially chiral bipyridine N,N'-dioxides. The N,N'-dioxides (1 mol%) were found to be highly catalytically active and enantioselective (up to 83% ee) for the asym. allylation of aldehydes with allyl(trichloro)silane in various solvents. In addn., a dramatic solvent effect was obsd. where the use of different solvents induced opposite chiralities of the product with the same enantiomer of the catalyst, e.g., 65% ee (S) in acetonitrile vs. 82% ee (R) in chlorobenzene.(i) Kadlčíková, A.; Hrdina, R.; Valterová, I.; Kotora, M. Adv. Synth. Catal. 2009, 351, 1279– 1283 DOI: 10.1002/adsc.200900224There is no corresponding record for this reference.
- 11(a) Lu, T.; Porterfield, M. A.; Wheeler, S. E. Org. Lett. 2012, 14, 5310– 5313 DOI: 10.1021/ol302493dThere is no corresponding record for this reference.(b) Chen, J. S.; Captain, B.; Takenaka, N. Org. Lett. 2011, 13, 1654– 1657 DOI: 10.1021/ol200102cThere is no corresponding record for this reference.
- 12Sepúlveda, D.; Lu, T.; Wheeler, S. E. Org. Biomol. Chem. 2014, 12, 8346 DOI: 10.1039/C4OB01719FThere is no corresponding record for this reference.
- 13Lu, T.; Zhu, R.; An, Y.; Wheeler, S. E. J. Am. Chem. Soc. 2012, 134, 3095– 3102 DOI: 10.1021/ja209241nThere is no corresponding record for this reference.
- 14(a) Chelucci, G.; Belmonte, N.; Benaglia, M.; Pignataro, L. Tetrahedron Lett. 2007, 48, 4037– 4041 DOI: 10.1016/j.tetlet.2007.04.028There is no corresponding record for this reference.(b) Hrdina, R.; Opekar, F.; Roithova, J.; Kotora, M. Chem. Commun. 2009, 2314– 2316 DOI: 10.1039/b819545eThere is no corresponding record for this reference.(c) Sereda, O.; Tabassum, S.; Wilhelm, R. Top. Curr. Chem. 2009, 291, 349– 393 DOI: 10.1007/128_2008_17There is no corresponding record for this reference.
- 15(a) Becke, A. J. Chem. Phys. 1997, 107, 8554– 8560 DOI: 10.1063/1.47500715ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXntFGiuro%253D&md5=e9e466d42d8ea239be08b3a1ede19ae7Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionalsBecke, Axel D.Journal of Chemical Physics (1997), 107 (20), 8554-8560CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A systematic procedure for refining gradient corrections in Kohn-Sham exchange-correlation functionals is presented. The procedure is based on least-squares fitting to accurate thermochem. data. In this first application of the method, we use the G2 test set of Pople and co-workers to generate what we believe to be an optimum GGA/exact-exchange d.-functional theory (i.e., generalized gradient approxn. with mixing of exactly computed exchange).(b) Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829– 5835 DOI: 10.1063/1.467146There is no corresponding record for this reference.(c) Grimme, S. J. Comput. Chem. 2006, 27, 1787– 1799 DOI: 10.1002/jcc.2049515chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFenu7bO&md5=0b4aa16bebc3a0a2ec175d4b161ab0e4Semiempirical GGA-type density functional constructed with a long-range dispersion correctionGrimme, StefanJournal of Computational Chemistry (2006), 27 (15), 1787-1799CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)A new d. functional (DF) of the generalized gradient approxn. (GGA) type for general chem. applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C6·R-6. A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common d. functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on std. thermochem. benchmark sets, for 40 noncovalently bound complexes, including large stacked arom. mols. and group II element clusters, and for the computation of mol. geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for std. functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean abs. deviation of only 3.8 kcal mol-1. The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the av. CCSD(T) accuracy. The basic strategy in the development to restrict the d. functional description to shorter electron correlation lengths scales and to describe situations with medium to large interat. distances by damped C6·R-6 terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chem. method for large systems where dispersion forces are of general importance.
- 16(a) Cancès, E.; Mennucci, B. J. Math. Chem. 1998, 23, 309– 326 DOI: 10.1023/A:101913361114816ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1cXls1Shu7c%253D&md5=43cf1ef267bbe34336ad07031ef9c935New applications of integral equations methods for solvation continuum models: ionic solutions and liquid crystalsCances, Eric; Mennucci, BenedettaJournal of Mathematical Chemistry (1998), 23 (3,4), 309-326CODEN: JMCHEG; ISSN:0259-9791. (Baltzer Science Publishers)We present a new method for solving numerically the equations assocd. with solvation continuum models, which also works when the solvent is an anisotropic dielec. or an ionic soln. This method is based on the integral equation formalism. Its theor. background is set up and some numerical results for simple systems are given. This method is much more effective than three-dimensional methods used so far, like finite elements or finite differences, in terms of both numerical accuracy and computational costs.(b) Cancès, E.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032– 3041 DOI: 10.1063/1.47465916bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXlsVOmtb8%253D&md5=0e2416f84d5f5affc048a6fae1c71b2bA new integral equation formalism for the polarizable continuum model: theoretical background and applications to isotropic and anisotropic dielectricsCances, E.; Mennucci, B.; Tomasi, J.Journal of Chemical Physics (1997), 107 (8), 3032-3041CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)The authors present a new integral equation formulation of the polarizable continuum model (PCM) which allows one to treat in a single approach dielecs. of different nature: std. isotropic liqs., intrinsically anisotropic media-like liq. crystals and solid matrixes, or ionic solns. Integral equation methods may be used with success also for the latter cases, which are usually studied with three-dimensional methods, by far less competitive in terms of computational effort. The authors present the theor. bases which underlie the method and some numerical tests which show both a complete equivalence with std. PCM versions for isotropic solvents, and a good efficiency for calcns. with anisotropic dielecs.(c) Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105, 2999– 3093 DOI: 10.1021/cr990400916chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXmsVynurc%253D&md5=462420dd18b3006ee63d1298b66db247Quantum Mechanical Continuum Solvation ModelsTomasi, Jacopo; Mennucci, Benedetta; Cammi, RobertoChemical Reviews (Washington, DC, United States) (2005), 105 (8), 2999-3093CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review.
- 17Grimme, S. Chem. - Eur. J. 2012, 18, 9955– 9964 DOI: 10.1002/chem.20120049717https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XpvFGgsrs%253D&md5=6799a866bf6862f957a4a69b1787c3ffSupramolecular Binding Thermodynamics by Dispersion-Corrected Density Functional TheoryGrimme, StefanChemistry - A European Journal (2012), 18 (32), 9955-9964, S9955/1-S9955/53CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)The equil. assocn. free enthalpies ΔGa for typical supramol. complexes in soln. are calcd. by ab initio quantum chem. methods. Ten neutral and three pos. charged complexes with exptl. ΔGa values in the range 0 to -21 kcal mol-1 (on av. -6 kcal mol-1) are investigated. The theor. approach employs a (non-dynamic) single-structure model, but computes the various energy terms accurately without any special empirical adjustments. Dispersion cor. d. functional theory (DFT-D3) with extended basis sets (triple-ζ and quadruple-ζ quality) is used to det. structures and gas-phase interaction energies (ΔE), the COSMO-RS continuum solvation model (based on DFT data) provides solvation free enthalpies and the remaining ro-vibrational enthalpic/entropic contributions are obtained from harmonic frequency calcns. Low-lying vibrational modes are treated by a free-rotor approxn. The accurate account of London dispersion interactions is mandatory with contributions in the range -5 to -60 kcal mol-1 (up to 200% of ΔE). Inclusion of three-body dispersion effects improves the results considerably. A semi-local (TPSS) and a hybrid d. functional (PW6B95) have been tested. Although the ΔGa values result as a sum of individually large terms with opposite sign (ΔE vs. solvation and entropy change), the approach provides unprecedented accuracy for ΔGa values with errors of only 2 kcal mol-1 on av. Relative affinities for different guests inside the same host are always obtained correctly. The procedure is suggested as a predictive tool in supramol. chem. and can be applied routinely to semirigid systems with 300-400 atoms. The various contributions to binding and enthalpy-entropy compensations are discussed.
- 18Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.Gaussian 09, Revision D.01; Gaussian, Inc., Wallingford, CT, 2009.There is no corresponding record for this reference.
- 20(a) Lehn, J. M.; Pietraszkiewicz, M.; Karpiuk, J. Helv. Chim. Acta 1990, 73, 106– 111 DOI: 10.1002/hlca.1990073011120ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3cXksFWgtbk%253D&md5=72a98f5e9a2804d0e1bf4b3c71e65fcfSynthesis and properties of acyclic and cryptate europium(III) complexes incorporating the 3,3'-biisoquinoline 2,2'-dioxide unitLehn, Jean Marie; Pietraszkiewicz, Marek; Karpiuk, JerzyHelvetica Chimica Acta (1990), 73 (1), 106-11CODEN: HCACAV; ISSN:0018-019X.[LiL]Br and EuL(ClO4)3 (L = I) were prepd. [Eu(L1)2]Cl3 (L1 = 3,3'-biisoquinoline 2,2'-dioxide) has also been obtained. These Eu(III) complexes present characteristic 1H-NMR spectra contg. markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been detd.(b) Lipkowski, J.; Suwinska, K.; Andreetti, G. D. J. Coord. Chem. 1990, 22, 83– 98 DOI: 10.1080/0095897900941003120bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3MXitFymu7w%253D&md5=0b3251834de36c32bef367e31fcb3d19Molecular and crystal structure of 1,1'-dimethyl-3,3'-biisoquinoline-N,N'-dioxide and its 2:1 complex with europium trichlorideLipkowski, Janusz; Suwinska, Kinga; Andreetti, Giovanni D.Journal of Coordination Chemistry (1990), 22 (2), 83-98CODEN: JCCMBQ; ISSN:0095-8972.The 1st title compd. is orthorhombic, space group P21212, with a 14.032(4), b 10.605(4), and c 5.242(1) Å; dc = 1.347 for Z = 2. The Eu title compd. is monoclinic, space group P21/c with a 12.829(10), b 17.616(5), c 43.863(7) Å, and β 91.34(4)°; dc = 1.414 for Z = 4 (2 mols./Z). The final R values are 0.035 and 0.072, resp. At. coordinates are given. The complex has a 7-fold coordination for Eu via 3 Cl and 4 O atoms. The coordination polyhedron is a distorted pentagonal bipyramid with 4 O and 1 Cl in the equatorial plane and 2 axial Cl ligands. Packing is of a van der Waals type and includes cocrystd. solvent mols.
- 21Wheeler, S. E.; Houk, K. N. J. Chem. Theory Comput. 2009, 5, 2301– 2312 DOI: 10.1021/ct900344g21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXptVKnu7Y%253D&md5=350e2ff3d9d6087deceea87d5c6f73c5Through-Space Effects of Substituents Dominate Molecular Electrostatic Potentials of Substituted ArenesWheeler, Steven E.; Houk, K. N.Journal of Chemical Theory and Computation (2009), 5 (9), 2301-2312CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)Model systems have been studied using d. functional theory to assess the contributions of π-resonance and through-space effects on electrostatic potentials (ESPs) of substituted arenes. The results contradict the widespread assumption that changes in mol. ESPs reflect only local changes in the electron d. Substituent effects on the ESP above the mol. plane are commonly attributed to changes in the aryl π-system. We show that ESP changes for a collection of substituted benzenes and more complex arom. systems can be accounted for mostly by through-space effects, with no change in the aryl π-electron d. Only when π-resonance effects are substantial do they influence changes to any extent in the ESP above the arom. ring. Examples of substituted arenes studied here are taken from the fields of drug design, host-guest chem., and crystal engineering. These findings emphasize the potential pitfalls of assuming ESP changes reflect changes in the local electron d. Since ESP changes are frequently used to rationalize and predict intermol. interactions, these findings have profound implications for our understanding of substituent effects in countless areas of chem. and mol. biol. Specifically, in many noncovalent interactions there are significant, often neglected, through-space interactions with the substituents. Finally, the present results explain the good performance of many mol. mechanics force-fields when applied to supramol. assembly phenomena, despite the neglect of the polarization of the aryl π-system by substituents.
- 22
The NPA charges on the formyl C and H are approximately +0.25e and +0.20e, respectively, across all TS structures.
There is no corresponding record for this reference. - 23
The lowest-lying TS structure is BP1(R), which is only 0.1 kcal mol–1 lower in energy than BP2(S).
There is no corresponding record for this reference. - 24(a) Wheeler, S. E. Acc. Chem. Res. 2013, 46, 1029– 1038 DOI: 10.1021/ar300109n24ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XovFWgu7k%253D&md5=045fc22890c76cf01d324cfcc2e44760Understanding Substituent Effects in Noncovalent Interactions Involving Aromatic RingsWheeler, Steven E.Accounts of Chemical Research (2013), 46 (4), 1029-1038CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)A review. Noncovalent interactions involving arom. rings such as π-stacking, cation/π, and anion/π interactions are central to many areas of modern chem. Decades of exptl. studies have provided key insights into the impact of substituents on these interactions, leading to the development of simple intuitive models. However, gas-phase computational studies have raised some doubts about the phys. underpinnings of these widespread models. In this Account we review our recent efforts to unravel the origin of substituent effects in π-stacking and ion/π interactions through computational studies of model noncovalent dimers. First, however, we dispel the notion that so-called arom. interactions depend on the aromaticity of the interacting rings by studying model π-stacked dimers in which the aromaticity of one of the monomers can be "switched off". Somewhat surprisingly, the results show that not only is aromaticity unnecessary for π-stacking interactions, but it actually hinders these interactions to some extent. Consequently, when thinking about π-stacking interactions, researchers should consider broader classes of planar mols., not just arom. systems. Conventional models maintain that substituent effects in π-stacking interactions result from changes in the aryl π-system. This view suggests that π-stacking interactions are maximized when one ring is substituted with electron-withdrawing groups and the other with electron donors. In contrast to these prevailing models, we have shown that substituent effects in π-stacking interactions can be described in terms of direct, local interactions between the substituents and the nearby vertex of the other arene. As a result, in polysubstituted π-stacked dimers the substituents operate independently unless they are in each other's local environment. This means that in π-stacked dimers in which one arene is substituted with electron donors and the other with electron acceptors the interactions will be enhanced only to the extent provided by each substituent on its own, unless the substituents on opposing rings are in close proximity. Overall, this local, direct interaction model predicts that substituent effects in π-stacking interactions will be additive and transferable and will also depend on the relative position of substituents on opposing rings. For cation/π and anion/π interactions, similar π-resonance-based models pervade the literature. Again, computational results indicate that substituent effects in model ion/π complexes can be described primarily in terms of direct interactions between the ion and the substituent. Changes in the aryl π-system do not significantly affect these interactions. We also present a simple electrostatic model that further demonstrates this effect and suggests that the dominant interaction for simple substituents is the interaction of the charged ion with the local dipole assocd. with the substituents. Finally, we discuss substituent effects in electrostatic potentials (ESPs), which are widely used in discussions of noncovalent interactions. In the past, widespread misconceptions have confused the relationship between changes in ESPs and local changes in the electron d. We have shown that computed ESP plots of diverse substituted arenes can be reproduced without altering the aryl π-d. This is because substituent-induced changes in the ESP above the center of aryl rings result primarily from through-space effects of substituents rather than through changes in the distribution of the π-electron d.(b) Wheeler, S. E.; Bloom, J. W. G. J. Phys. Chem. A 2014, 118, 6133– 6147 DOI: 10.1021/jp504415p24bhttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXpvFCns7c%253D&md5=e7cfa276bb23513cba63f0bfd5173282Toward a More Complete Understanding of Noncovalent Interactions Involving Aromatic RingsWheeler, Steven E.; Bloom, Jacob W. G.Journal of Physical Chemistry A (2014), 118 (32), 6133-6147CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)A review. Noncovalent interactions involving arom. rings, which include π-stacking interactions, anion-π interactions, and XH-π interactions, among others, are ubiquitous in chem. and biochem. systems. Despite dramatic advances in our understanding of these interactions over the past decade, many aspects of these noncovalent interactions have only recently been uncovered, with many questions remaining. We summarize our computational studies aimed at understanding the impact of substituents and heteroatoms on these noncovalent interactions. In particular, we discuss our local, direct interaction model of substituent effects in π-stacking interactions. In this model, substituent effects are dominated by electrostatic interactions of the local dipoles assocd. with the substituents and the elec. field of the other ring. The implications of the local nature of substituent effects on π-stacking interactions in larger systems are discussed, with examples given for complexes with carbon nanotubes and a small graphene model, as well as model stacked discotic systems. We also discuss related issues involving the interpretation of electrostatic potential (ESP) maps. Although ESP maps are widely used in discussions of noncovalent interactions, they are often misinterpreted. Next, we provide an alternative explanation for the origin of anion-π interactions involving substituted benzenes and N-heterocycles, and show that these interactions are well-described by simple models based solely on charge-dipole interactions. Finally, we summarize our recent work on the phys. nature of substituent effects in XH-π interactions. Together, these results paint a more complete picture of noncovalent interactions involving arom. rings and provide a firm conceptual foundation for the rational exploitation of these interactions in a myriad of chem. contexts.
- 25Tauer, T.; Sherrill, C. D. J. Phys. Chem. A 2005, 109, 10475– 10478 DOI: 10.1021/jp0553479There is no corresponding record for this reference.
- 26(a) Seguin, T. J.; Wheeler, S. E. ACS Catal. 2016, 6, 2681– 2688 DOI: 10.1021/acscatal.6b0053826ahttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XktFejsLw%253D&md5=e34c43ea01cbc3a3c2260003348e9265Electrostatic Basis for Enantioselective Bronsted-Acid-Catalyzed Asymmetric Ring Openings of meso-EpoxidesSeguin, Trevor J.; Wheeler, Steven E.ACS Catalysis (2016), 6 (4), 2681-2688CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Computational studies of three chiral phosphoric-acid-catalyzed asym. ring-openings of meso-epoxides show that the enantioselectivity of these reactions stems from favorable electrostatic interactions of the preferred transition state with the phosphoryl oxygen of the catalyst. The 3,3'-aryl substituents of the catalysts, which are vital for enantioselectivity, serve primarily to create a narrow binding groove that restricts the substrate orientations within the chiral electrostatic environment of the phosphoric acid. This electrostatic, enzyme-like mode of stereoinduction appears to be general for these reactions and suggests a complementary means of achieving stereoinduction in chiral phosphoric acid catalysis. Finally, examn. of the mechanism for subsequent reactions in List's organocatalytic cascade for the synthesis of β-hydroxythiols (Monaco, M. R.; Pr´evost, S.; List, B. J. Am. Chem. Soc. 2014, 136, 16982) explains the requirement for elevated temps. for the latter steps in the cascade sequence, as well as the lack of reactivity of five-membered cyclic epoxides in this transformation.(b) Seguin, T. J.; Lu, T.; Wheeler, S. E. Org. Lett. 2015, 17, 3066– 3069 DOI: 10.1021/acs.orglett.5b01349There is no corresponding record for this reference.(c) Seguin, T. J.; Wheeler, S. E. ACS Catal. 2016, 6, 7222– 7228 DOI: 10.1021/acscatal.6b0191526chttps://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsFamsrjK&md5=b4fdd63c3229a6e97e2ace6768b4204bCompeting Noncovalent Interactions Control the Stereoselectivity of Chiral Phosphoric Acid Catalyzed Ring Openings of 3-Substituted OxetanesSeguin, Trevor J.; Wheeler, Steven E.ACS Catalysis (2016), 6 (10), 7222-7228CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)The noncovalent interactions responsible for enantioselectivity in organo-catalytic oxetane ring openings were quantified using d. functional theory (DFT) computations. Data show that the mode of stereoinduction in these systems differs markedly for different substituted oxetanes, highlighting the challenge of developing general stereochem. models for such reactions. For oxetanes monosubstituted at the 3-position, the enantioselectivity is primarily due to differential CH···π interactions between the mercaptobenzothiazole nucleophile and the arom. backbone of the catalyst. This can be contrasted with 3,3-disubstituted oxetanes, for which interactions between an oxetane substituent and the phosphoric acid functionality and/or the anthryl groups of the catalyst become more important. The former effects are particularly important in the case of 3-OH-substituted oxetanes. Overall, these reactions demonstrate the diversity of competing noncovalent interactions that control the stereoselectivity of many phosphoric acid catalyzed reactions.
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The corresponding energy difference is 1.5 kcal mol–1 for 1c.
There is no corresponding record for this reference. - 28Guan, Y.; Rooks, B. J.; Wheeler, S. E.AARON: An Automated Reaction Optimizer for Non-metal catalyzed reactions, version 0.91; Texas A&M University, College Station, TX, 2016.There is no corresponding record for this reference.
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Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.6b02366.
Additional data, absolute electronic energies, enthalpies, and free energies, and optimized Cartesian coordinates (PDF)
Cartesian coordinates of the calculated structures (XYZ)
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