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Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids

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Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
*[email protected]
Cite this: J. Am. Chem. Soc. 2016, 138, 18, 5821–5824
Publication Date (Web):April 27, 2016
https://doi.org/10.1021/jacs.6b03086

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Abstract

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A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance.

The asymmetric construction of chiral ketones and alcohols remains an important area of research in organic synthesis due to the high utility of these functional groups. (1) The reaction of an alkene with an aldehyde, via catalytic hydroacylation or reductive coupling, represents an attractive route to α-chiral ketones and alcohols, respectively. (2, 3) These processes construct a carbon–carbon bond (and corresponding stereogenic center) while obviating the need for stoichiometric preformed organometallic reagents. Impressive developments toward generalizing these transformations have been reported although significant limitations and challenges remain. For example, numerous methods for highly enantioselective intermolecular alkene hydroacylation have been reported; however, a metal-coordinating substituent on either the alkene or aldehyde component is typically required. (4) Pioneering work by Krische has led to numerous methods for the asymmetric reductive coupling of alkenes to carbonyls for relatively activated C–C π-systems, such as electron-deficient alkenes, enynes, dienes, and allenes. (3, 5-7) In contrast, stereoselective catalytic intermolecular reductive coupling of aryl alkenes to carbonyls remains largely undeveloped, likely a consequence of the lower reactivity of these alkenes. (8, 9) Building upon an initial report by Miura, (10) Krische developed a highly efficient Rh-catalyzed coupling of aryl alkenes and anhydride reagents to selectively access branched ketones in a racemic manner (Scheme 1a). (9, 11) We reasoned that using a similar approach, namely, using a carboxylic acid derivative as an aldehyde surrogate, the limitations described above for hydroacylation and reductive coupling could be addressed via copper(I) hydride (CuH) catalysis. We herein report a CuH-catalyzed protocol for the reductive coupling of aryl alkenes to activated carboxylic acids that, depending on the reaction conditions, selectively yields enantioenriched ketones or alcohols (Scheme 1b).

Scheme 1

Scheme 1. (a) Prior Work in Aryl Alkene Reductive Coupling to Acyl Electrophiles; (b) Proposed Access to Chiral Ketones or Alcohols; (c) Proposed Catalytic Cycles
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We, as well as Hirano and Miura, have developed enantioselective CuH-catalyzed hydroamination reactions that proceed through catalytically generated chiral organocopper intermediates that are formed from hydrocupration of an alkene substrate. (12, 13) As an expansion of this work, we recently reported methods for the synthesis of enantioenriched carbo- and heterocycles via intramolecular trapping of a putative organocopper intermediate with alkyl bromides and imines. (14) We reasoned that this strategy could be applied to the intermolecular coupling of an alkene to an appropriately activated carboxylic acid derivative to initially yield an α-chiral ketone, constituting a formal hydroacylation process. (15, 16) Subsequent reduction of the ketone would additionally yield an alcohol containing two stereocenters. The proposed catalytic cycle (Scheme 1c) proceeds via asymmetric Markovnikov hydrocupration of aryl alkene 2 followed by electrophilic interception with an acyl electrophile (1) to deliver enantioenriched ketone (3) and L*CuX (7). (17) σ-Bond metathesis of L*CuX (7) with a hydrosilane is required to regenerate L*CuH (5). Under appropriate conditions, reformed L*CuH (5) could perform a highly diastereoselective 1,2-reduction of ketone 3 in the reduction cycle to produce silyl ether 9. Ideally, these two catalytic processes could be performed in the same reaction vessel with a common electrophile, thus providing either enantioenriched ketone or alcohol products, depending upon the reaction conditions employed.

In the presence of a hydrosilane reductant, phosphine-ligated CuH species are typically very active catalysts for the 1,2-reduction of carbonyl functional groups, such as ketones and aldehydes. (18) This propensity for efficient carbonyl reduction presents a major challenge in the development of the proposed methodology (Scheme 1b), as hydrocupration of an alkene must occur in the presence of a carbonyl electrophile. Variation of the electronic, steric, and coordinating properties of the activating group provides an opportunity to achieve the desired chemoselectivity. A highly stereoselective process is further contingent on avoiding ketone racemization.

We began our studies with an examination of the reductive coupling of styrene (2a) to benzoyl electrophiles to yield chiral alcohol product (4a). Based on our catalyst system for enantioselective hydroamination, we initially employed a mixture of Cu(OAc)2 (2 mol %), (S)-DTBM-SEGPHOS phosphine ligand (L1, 2.2 mol %), and dimethoxymethylsilane (DMMS) in THF. (12) Most of the electrophiles examined (1a–f) failed to react or underwent rapid reduction to form benzyl alcohol (Table 1, entries 1–6). When benzoic anhydride (1g) was used, 25% of the desired product was formed with high selectivity, but benzyl alcohol was still the major product (entry 7). Use of other biaryl-based diphosphine ligands, such as (S)-BINAP (L2), did not yield any product (entry 8), while monoaryl diphoshine (R,R)-Me-DuPhos (L3) increased the yield to 45% with drastically reduced stereoselectivity (entry 9). The trialkyl diphosphine (S,S)-Ph-BPE (L4) proved to be the optimal supporting ligand, increasing the yield to 77% with high selectivity (entry 10). The yield was further increased to 91% when (S,S)-Ph-BPE was used with added PPh3 (2.2 mol %) as a secondary ligand, yielding the desired product in >20:1 dr and 94% ee (entry 11). (19)

Table 1. Optimization of Chiral Alcohol Synthesis via Styrene Reductive Coupling with Benzoyl Electrophilesa
Table a

Yields and dr determined by 1H NMR analysis of crude reaction mixture; enantioselectivity determined of the purified alcohol product after treatment with NH4F in MeOH.

The scope of the optimized coupling process was next explored using symmetrical aryl carboxylic anhydrides (Table 2). Many functional groups, such as esters (4b), nitriles (4c), phenols (4d), substituted alkenes (4e), carbamates (4h), and aryl halides (4k, 4m, and 4n), are compatible with this transformation. With electron-neutral and electron-rich aryl alkenes, alcohol products are typically formed in moderate to good yield (45–88%) with >20:1 dr and >95% ee. However, highly electron-deficient styrenes, such as 4-cyanostyrene (4c), led to products in good yield but with low selectivity, possibly due to racemization of the more acidic ketone intermediate formed upon hydroacylation. ortho- and β-Substitution is tolerated on the aryl alkene component (4i and 4j), but product yields are decreased as direct anhydride reduction competes with hydrocupration of these more encumbered alkene substrates. For the anhydride component, electron-rich (4l), electron-poor (4k), and ortho-substituted (4m) substrates are all competent coupling partners. Furthermore, good yields and selectivities were obtained with a range of substrates containing heterocyclic fragments, including indoles (4f), pyrazoles (4g), piperazines (4h), benzofurans (4o), furans (4p), and thiophenes (4q). Under the current reaction conditions, alkyl carboxylic anhydrides do not engage in the coupling reaction and are instead directly reduced by the CuH catalyst, a current limitation of this system.

Table 2. Alcohol Synthesis Substrate Scopea
Table a

All yields represent average isolated yields of two runs performed with 1 mmol of alkene; dr determined by 1H NMR analysis of crude reaction material.

Table b

Reaction run at ambient temperature.

Table c

2.0 equiv of anhydride used.

Table d

4 mol % catalyst used.

Table e

Bz2O added over 4 h, 1H NMR yield, product isolated and characterized as the acylated alcohol.

A useful feature of this methodology is the ability to selectively access chiral ketones or alcohols by controlling the relative rates of hydroacylation and carbonyl reduction. We have qualitatively observed that 1,2-reduction occurs more slowly than the hydroacylation process, and when the reaction is conducted at a lower temperature, ketone products can be isolated in good yields. (20)Scheme 2a shows several examples of this formal enantioselective hydroacylation protocol. With styrene, ketones are isolated with moderate to good enantioselectivity (77–89% ee) (3a, 3c, and 3d). Employing the more electron-rich 4-acetoxystyrene as a substrate enabled the respective ketone product to be produced with high enantioselectivity (3b, 97% ee).

Scheme 2

Scheme 2. (a) Enantioselective Ketone Synthesis and (b) Reductiona
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Scheme aAll yields represent average isolated yields of two runs performed with 1 mmol of alkene.

Scheme bReaction run at ambient temperature.

At the outset of this project, we questioned whether the chirality of the L*CuH catalyst would be matched for both transformations (hydroacylation and 1,2-reduction). To examine this aspect, chiral ketone 3a, which was produced in 89% ee using (S,S)-Ph-BPE ligand, was reduced under the standard reaction conditions using both antipodes of the Ph-BPE ligand. (21) The (S,S)-Ph-BPE system yielded alcohol in 97:3 dr with 97% ee, while the use of (R,R)-Ph-BPE ligand delivered alcohol in 55:45 dr with 78 and 99% ee, respectively. These results indicate that a matched/mismatched case is evident for ketone reduction and that the ligand used is stereomatched for hydroacylation and reduction. This phenomenon provides an opportunity for further enantioenrichment of the final alcohol product, as demonstrated with the typically high levels of enantiopurity (>90% ee) observed for the alcohol products in Table 2. (22)

In summary, we have developed a new protocol for the enantioselective reductive coupling of aryl alkenes with aryl carboxylic anhydrides for selective access to either chiral ketones or alcohols. This process is enabled through dual catalytic cycles wherein a chiral L*CuH catalyst first promotes enantioselective hydroacylation, while a slower diastereoselective ketone reduction process delivers the alcohol product with further enantioenrichment. A wide range of functional groups and heterocycles are tolerated, and ongoing work is aimed at expanding this methodology to less activated alkenes and aliphatic carboxylic acids.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b03086.

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  • Corresponding Author
    • Stephen L. Buchwald - Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States;  Email: [email protected]
  • Authors
    • Jeffrey S. Bandar - Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
    • Erhad Ascic - Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

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Research reported in this publication was supported by the National Institutes of Health (GM46059). We thank the NIH for a postdoctoral fellowship for J.S.B. (GM112197) and the Danish Council for Independent Research, Technology and Production Sciences for a postdoctoral fellowship for E.A. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We also thank Drs. Michael Pirnot and Yiming Wang for advice on the preparation of this manuscript.

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    (h) Osborne, J. D.; Randell-Sly, H. E.; Currie, G. S.; Cowley, A. R.; Willis, M. C. J. Am. Chem. Soc. 2008, 130, 17232 DOI: 10.1021/ja8069133
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    4h
    Catalytic Enantioselective Intermolecular Hydroacylation: Rhodium-Catalyzed Combination of β-S-Aldehydes and 1,3-Disubstituted Allenes
    Osborne, James D.; Randell-Sly, Helen E.; Currie, Gordon S.; Cowley, Andrew R.; Willis, Michael C.
    Journal of the American Chemical Society (2008), 130 (51), 17232-17233CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A rhodium(I) catalyst incorporating the Me-DuPhos ligand promotes enantioselective intermol. hydroacylation between β-S-aldehydes and 1,3-disubstituted allenes. The nonconjugated enone products are obtained in good yields and with high enantioselectivities.
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  5. 5

    For reviews on reductive aldol, Mannich, and Michael reactions:

    (a) Nishiyama, H.; Shiomi, T. Top. Curr. Chem. 2007, 279, 105 DOI: 10.1007/128_2007_126
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    (b) Guo, H.-C.; Ma, J.-A. Angew. Chem., Int. Ed. 2006, 45, 354 DOI: 10.1002/anie.200500195
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    5b
    Catalytic asymmetric tandem transformations triggered by conjugate additions
    Guo, Hong-Chao; Ma, Jun-An
    Angewandte Chemie, International Edition (2006), 45 (3), 354-366CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. The development of efficient methods to access complex mols. with multistereogenic centers has been a substantial challenge in both academic research and industrial applications. One approach to this challenge is catalytic asym. tandem transformations, which allow a rapid increase in mol. complexity from readily available starting materials to produce enantiopure compds. In recent years, considerable efforts have been directed towards the development of asym. tandem transformations. This Minireview highlights recent developments and the applications of metal-catalyzed and organocatalytic asym. tandem transformations triggered by conjugate addns.
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    (c) Jang, H.-Y.; Krische, M. J. Eur. J. Org. Chem. 2004, 3953 DOI: 10.1002/ejoc.200400270
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    Selected Cu-catalyzed reductive coupling reactions:

    (d) Lipshutz, B. H.; Amorelli, B.; Unger, J. B. J. Am. Chem. Soc. 2008, 130, 14378 DOI: 10.1021/ja8045475
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    5d
    CuH-Catalyzed Enantioselective Intramolecular Reductive Aldol Reactions Generating Three New Contiguous Asymmetric Stereocenters
    Lipshutz, Bruce H.; Amorelli, Benjamin; Unger, John B.
    Journal of the American Chemical Society (2008), 130 (44), 14378-14379CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Treatment of β,β-disubstituted-α,β-unsatd. ketones, e.g., I, bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to cycloalkanols, e.g., II, with three newly created adjacent chiral centers. Excellent de's and ee's are obtained for several examples studied.
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    (e) Zhao, D.; Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 14440 DOI: 10.1021/ja0652565
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    5e
    Dramatic Ligand Effect in Catalytic Asymmetric Reductive Aldol Reaction of Allenic Esters to Ketones
    Zhao, Dongbo; Oisaki, Kounosuke; Kanai, Motomu; Shibasaki, Masakatsu
    Journal of the American Chemical Society (2006), 128 (45), 14440-14441CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A general catalytic asym. reductive aldol reaction of allenic esters H2C:C:CHCO2R1 (R1 = Me, Et) with ketones R2COMe (R2 = Me2CH, n-Bu, H2C:CHCH2CH2, Ph, 4-ClC6H4, PhCH:CH, PhCH2CH2, 2-naphthyl, etc.) is described. Two distinct constitutional isomers were selectively produced depending on the reaction conditions. A combination of CuOAc/(R)-DTBM-SEGPHOS/PCy3 as the catalyst predominantly produced γ-cis-products R2MeC(OH)CH2CH:CHCO2R1 in high yields with excellent enantioselectivity (up to 99% ee). The reaction was applicable to both arom. and aliph. ketones, including unsatd. ketones. On the other hand, CuF-Taniaphos complexes produced α-aldol products R2MeC(OH)CH(CH:CH2)CO2R1 with high diastereo- and enantioselectivity (up to 84% ee). The new Taniaphos deriv., contg. di(3,5-xylyl)phosphine and morpholine units, produced optimum results in the α-selective reaction. The products are versatile chiral building blocks in org. synthesis. Furthermore, the basic reaction pattern (i.e., conjugate addn.-aldol reaction) was extended to a catalytic enantioselective alkylative aldol reaction to ketones using dialkylzinc reagents as the initiator.
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    (f) Deschamp, J.; Chuzel, O.; Hannedouche, J.; Riant, O. Angew. Chem., Int. Ed. 2006, 45, 1292 DOI: 10.1002/anie.200503791
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    5f
    Highly diastereo- and enantioselective copper-catalyzed domino reduction/aldol reaction of ketones with methyl acrylate
    Deschamp, Julia; Chuzel, Olivier; Hannedouche, Jerome; Riant, Olivier
    Angewandte Chemie, International Edition (2006), 45 (8), 1292-1297CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A new catalytic method was found for the construction of stereogenic quaternary carbon centers through a copper-catalyzed domino conjugated redn./aldol reaction of Me acrylate with various alkyl aryl ketones. The proper choice of the chiral diphosphine ligand leads to high chemo-, diastereo-, and enantioselectivity.
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  6. 6

    Selected examples of catalytic asymmetric enyne, diene, and allene reductive couplings:

    (a) Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.; Krische, M. J. Science 2012, 336, 324 DOI: 10.1126/science.1219274
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    6a
    Enantioselective C-H Crotylation of Primary Alcohols via Hydrohydroxyalkylation of Butadiene
    Zbieg, Jason R.; Yamaguchi, Eiji; McInturff, Emma L.; Krische, Michael J.
    Science (Washington, DC, United States) (2012), 336 (6079), 324-327CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    The direct, byproduct-free conversion of basic feedstocks to products of medicinal and agricultural relevance is a broad goal of chem. research. Butadiene is a product of petroleum cracking and is produced on an enormous scale (about 12 × 106 metric tons annually). Here, with the use of a ruthenium catalyst modified by a chiral phosphate counterion, the direct redox-triggered carbon-carbon coupling of alcs. and butadiene is reported to form products of carbonyl crotylation with high levels of anti-diastereoselectivity and enantioselectivity in the absence of stoichiometric byproducts.
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    (b) Han, S. B.; Kim, I. S.; Han, H.; Krische, M. J. J. Am. Chem. Soc. 2009, 131, 6916 DOI: 10.1021/ja902437k
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    (c) Geary, L. M.; Woo, S. K.; Leung, J. C.; Krische, M. J. Angew. Chem., Int. Ed. 2012, 51, 2972 DOI: 10.1002/anie.201200239
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    6c
    Diastereo- and Enantioselective Iridium-Catalyzed Carbonyl Propargylation from the Alcohol or Aldehyde Oxidation Level: 1,3-Enynes as Allenylmetal Equivalents
    Geary, Laina M.; Woo, Sang Kook; Leung, Joyce C.; Krische, Michael J.
    Angewandte Chemie, International Edition (2012), 51 (12), 2972-2976, S2972/1-S2972/61CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Iridium-catalyzed carbonyl propargylation of protected hex-5-en-3-ynes I (R = TBDMS, TIPS) with aldehydes or primary alcs. is described. As an example, using 4-bromobenzyl alc. or 4-bromobenzaldehyde gave II in 87% and 89% yield, with 12:1 and 11:1 diastereomeric ratio (anti:syn), and 89% ee and 87% ee of the major diastereomer, resp. Compd. II was then deprotected in a one-pot procedure, giving III in 86% yield.
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  7. 7

    Selected reviews on alkyne reductive coupling:

    (a) Tanaka, K.; Tajima, Y. Eur. J. Org. Chem. 2012, 3715 DOI: 10.1002/ejoc.201200098
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    (b) Moslin, R. M.; Miller-Moslin, K.; Jamison, T. F. Chem. Commun. 2007, 4441 DOI: 10.1039/b707737h
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    (c) Reichard, H. A.; McLaughlin, M.; Chen, M. Z.; Micalizio, G. C. Eur. J. Org. Chem. 2010, 391 DOI: 10.1002/ejoc.200901094
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    (d) Jackson, E. P.; Malik, H. A.; Sormunen, G. J.; Baxter, R. D.; Liu, P.; Wang, H.; Shareef, A.-R.; Montgomery, J. Acc. Chem. Res. 2015, 48, 1736 DOI: 10.1021/acs.accounts.5b00096
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    7d
    Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings
    Jackson, Evan P.; Malik, Hasnain A.; Sormunen, Grant J.; Baxter, Ryan D.; Liu, Peng; Wang, Hengbin; Shareef, Abdur-Rafay; Montgomery, John
    Accounts of Chemical Research (2015), 48 (6), 1736-1745CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. The control of regiochem. is a considerable challenge in the development of a wide array of catalytic processes. Simple π-components such as alkenes, alkynes, 1,3-dienes, and allenes are among the many classes of substrates that present complexities in regioselective catalysis. Considering an internal alkyne as a representative example, when steric and electronic differences between the two substituents are minimal, differentiating among the two termini of the alkyne presents a great challenge. In cases where the differences between the alkyne substituents are substantial, overcoming those biases to access the regioisomer opposite that favored by substrate biases often presents an even greater challenge. Nickel-catalyzed reductive couplings of unsym. π-components make up a group of reactions where control of regiochem. presents a challenging but important objective. In the course of our studies of aldehyde-alkyne reductive couplings, complementary solns. to challenges in regiocontrol have been developed. Through careful selection of the ligand and reductant, as well as the more subtle reaction variables such as temp. and concn., effective protocols have been established that allow highly selective access to either regiosiomer of the allylic alc. products using a wide range of unsym. alkynes. Computational studies and an evaluation of reaction kinetics have provided an understanding of the origin of the regioselectivity control. Throughout the various procedures described, the development of ligand-substrate interactions plays an essential role, and the overall kinetic descriptions were found to differ between protocols. Rational alteration of the rate-detg. step plays a key role in the regiochem. reversal strategy, and in one instance, the two possible regioisomeric outcomes in a single reaction were found to operate by different kinetic descriptions. With this mechanistic information in hand, the empirical factors that influence regiochem. can be readily understood, and more importantly, the insights suggest simple and predictable exptl. variables to achieving a desired reaction outcome. These studies thus present a detailed picture of the influences that control regioselectivity in a specific catalytic reaction, but they also delineate strategies for regiocontrol that may extend to numerous classes of reactions. The work provides an illustration of how insights into the kinetics and mechanism of a catalytic process can rationalize subtle empirical findings and suggest simple and rational modifications in procedure to access a desirable reaction outcome. Furthermore, these studies present an illustration of how important challenges in org. synthesis can be met by novel reactivity afforded by base metal catalysis. The use of nickel catalysis in this instance not only provides an inexpensive and sustainable method for catalysis but also enables unique reactivity patterns not accessible to other metals.
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  8. 8
    (a) Yamaguchi, E.; Mowat, J.; Luong, T.; Krische, M. J. Angew. Chem., Int. Ed. 2013, 52, 8428 DOI: 10.1002/anie.201303552
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    For the reductive couplings of electron-deficient azaarene alkenes:

    (b) Best, D.; Lam, H. W. J. Org. Chem. 2014, 79, 831 DOI: 10.1021/jo402414k
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    8b
    C=N-Containing Azaarenes as Activating Groups in Enantioselective Catalysis
    Best, Daniel; Lam, Hon Wai
    Journal of Organic Chemistry (2014), 79 (3), 831-845CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
    A review. Nitrogen-contg. arom. heterocycles (azaarenes) are of widespread chem. significance, and chiral compds. contg. azaarenes feature prominently in pharmaceuticals, agrochems., and natural products. This Perspective highlights the use of a relatively underdeveloped strategy to prep. chiral azaarene-contg. compds.: exploitation of the C=N bond embedded within certain azaarenes to activate adjacent functionality in catalytic asym. reactions. Work in this area has resulted in the development of several different types of catalytic enantioselective processes, including redns., nucleophilic addns., and reductive couplings. It is hoped that this Perspective will encourage more researchers to work in this promising area.
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    (c) Saxena, A.; Choi, B.; Lam, H. W. J. Am. Chem. Soc. 2012, 134, 8428 DOI: 10.1021/ja3036916
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    8c
    Enantioselective Copper-Catalyzed Reductive Coupling of Alkenylazaarenes with Ketones
    Saxena, Aakarsh; Choi, Bonnie; Lam, Hon Wai
    Journal of the American Chemical Society (2012), 134 (20), 8428-8431CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Catalytic enantioselective methods for the prepn. of chiral azaarene-contg. compds. are of high value. By combining the utility of copper hydride catalysis with the ability of C=N-contg. azaarenes to activate adjacent alkenes toward nucleophilic addns., the enantioselective reductive coupling of alkenylazaarenes with ketones has been developed. The process is tolerant of a wide variety of azaarenes and ketones, and provides arom. heterocycles bearing tertiary-alc.-contg. side chains with high levels of diastereo- and enantioselectivities.
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  9. 9
    Hong, Y.-T.; Barchuk, A.; Krische, M. J. Angew. Chem., Int. Ed. 2006, 45, 6885 DOI: 10.1002/anie.200602377
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  10. 10
    Kokubo, K.; Miura, M.; Nomura, M. Organometallics 1995, 14, 4521 DOI: 10.1021/om00010a016
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  11. 11

    For additional examples using anhydride and acyl chloride reagents in formal hydroacylation processes, see:

    (a) Fujihara, T.; Tatsumi, K.; Terao, J.; Tsuji, Y. Org. Lett. 2013, 15, 2286 DOI: 10.1021/ol400862k
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    (b) Fujihara, T.; Hosomi, T.; Cong, C.; Hosoki, T.; Terao, J.; Tsuji, Y. Tetrahedron 2015, 71, 4570 DOI: 10.1016/j.tet.2015.01.066
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  12. 12

    For a review:

    (a) Pirnot, M. T.; Wang, Y.-M.; Buchwald, S. L. Angew. Chem., Int. Ed. 2016, 55, 48 DOI: 10.1002/anie.201507594
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    12a
    Copper Hydride-Catalyzed Hydroamination of Alkenes and Alkynes
    Pirnot, Michael T.; Wang, Yi-Ming; Buchwald, Stephen L.
    Angewandte Chemie, International Edition (2016), 55 (1), 48-57CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Over the past few years, CuH-catalyzed hydroamination was discovered and developed as a robust and conceptually novel approach for the synthesis of enantioenriched secondary and tertiary amines. The success in this area of research was made possible through the large body of precedent in copper(I) hydride catalysis and the well-explored use of hydroxylamine esters as electrophilic amine sources in related copper-catalyzed processes. This minireview details the background, advances, and mechanistic studies in CuH-catalyzed hydroamination.
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    For selected individual reports:

    (b) Zhu, S.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013, 135, 15746 DOI: 10.1021/ja4092819
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    12b
    Enantio- and Regioselective CuH-Catalyzed Hydroamination of Alkenes
    Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.
    Journal of the American Chemical Society (2013), 135 (42), 15746-15749CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    In the presence of (R)-DTBM-SEGPHOS and copper(II) acetate and using diethoxymethylsilane as a reducing agent, styrenes underwent regio- and enantioselective hydroamination reactions with O-benzoylhydroxylamines such as (PhCH2)2NOCOPh to give nonracemic aralkylamines such as [(S)-PhCHMe]N(CH2Ph)2 in 77-98% yields and in 86->99% ee; in one case, a trisubstituted aryl alkene underwent hydroamination to give a nonracemic β-alkyl aralkylamine as a single diastereomer in >99% ee. The reaction tolerated a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes, to yield nonracemic α-branched amines. Using racemic DTBM-SEGPHOS and copper(II) acetate and using diethoxymethylsilane as a reducing agent, terminal and 1,1-disubstituted aliph. alkenes such as 4-phenyl-1-butene underwent regioselective hydroamination with O-benzoylhydroxylamines such as (PhCH2)2NOCOPh to give anti-Markovnikov alkylamines such as Ph(CH2)4N(CH2Ph)2 in 80-99% yields.
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    (c) Yang, Y.; Shi, S.-L.; Niu, D.; Liu, P.; Buchwald, S. L. Science 2015, 349, 62 DOI: 10.1126/science.aab3753
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    12c
    Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines
    Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L.
    Science (Washington, DC, United States) (2015), 349 (6243), 62-66CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    A catalytic assembly of enantiopure aliph. amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chem. Here, the authors describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins-an important yet unexploited class of abundant feedstock chems.-into highly enantioenriched α-branched amines (≥96% enantiomeric excess) featuring two minimally differentiated aliph. substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas. Under optimized conditions the synthesis of the target compds. was achieved using copper diacetate and 1,1'-(4S)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] [i.e., (S)-(+)-DTBM-SEGPHOS] as a catalyst-ligand combination. The synthesis of the target compds. was achieved using (4E)-4-octene, (3E)-2,5-dimethyl-3-hexene, (7E)-2,2,3,3,12,12,13,13-octamethyl-4,11-dioxa-3,12-disilatetradec-7-ene, (3E)-3-hexene-1,6-diol, (2E)-4-methyl-2-pentene, (3E)-2,2-dimethyl-3-hexene as alkene starting materials. Hydroxylamine-ester derivs. included N-(benzoyloxy)-N-(phenylmethyl)benzenemethanamine, 4-methoxybenzoic acid bis[(aryl)methyl]azanyl ester derivs. (pyridine, pyrimidine, thiophene, furan, piperidine, piperazine derivs.). The title compds. thus formed included chiral amines, such as N-[(1S)-1-methylpropyl]-N-(phenylmethyl)benzenemethanamine. (αR)-α-methyl-N-[3-[3-(trifluoromethyl)phenyl]propyl]-1-naphthalenemethanamine (i.e., cinacalcet) and (3S,4R)-3-[(1,3-benzodioxol-5-yloxy)methyl]-4-(4-fluorophenyl)piperidine (i.e. paroxetine) were used as starting materials. Opposite enantiomers were obtained using 1,1'-(4R)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] [i.e., (R)-(-)-DTBM-SEGPHOS] as ligand.
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  13. 13
    (a) Miki, Y.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2013, 52, 10830 DOI: 10.1002/anie.201304365
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    13a
    Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines
    Miki, Yuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro
    Angewandte Chemie, International Edition (2013), 52 (41), 10830-10834CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A copper-catalyzed intermol. regioselective hydroamination of arylalkenes R1CH:CHR2 (R1 = Ph, 4-MeOC6H4, 3-ClC6H4, 2-naphthyl, etc.; R2 = H, Me, i-Pr, MeOCH2, AcOCH2) with polymethylhydrosiloxane and O-benzoyl hydroxylamines R3R4NOC(O)Ph [R3 = R4 = Et, H2C:CHCH2, PhCH2; R3 = Me, R4 = PhCH2; R3R4 = (CH2)5, (CH2)6, (CH2)2O(CH2)2; etc.] affording the corresponding aralkyl amines R1CHNR3R4CH2R2 has been developed. Moreover, the chiral biphosphine-ligated copper complex was successfully used for the synthesis of non-racemic aralkyl amines with good enantiomeric ratios.
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    See also:

    (b) Xi, Y.; Butcher, T. W.; Zhang, J.; Hartwig, J. F. Angew. Chem., Int. Ed. 2016, 55, 776 DOI: 10.1002/anie.201509235
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    13b
    Regioselective, Asymmetric Formal Hydroamination of Unactivated Internal Alkenes
    Xi, Yumeng; Butcher, Trevor W.; Zhang, Jing; Hartwig, John F.
    Angewandte Chemie, International Edition (2016), 55 (2), 776-780CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The regioselective and enantioselective formal hydroamination of unsym. internal alkenes catalyzed by a copper catalyst ligated by DTBM-SEGPHOS is reported. The regioselectivity of the reaction is controlled by the electronic effects of ether, ester, and sulfonamide groups in the homoallylic position. The obsd. selectivity underscores the influence of inductive effects of remote substituents on the selectivity of catalytic processes occurring at hydrocarbyl groups, and the method provides direct access to various 1,3-aminoalc. derivs. with high enantioselectivity.
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    For examples of acylation reactions with nucleophilic copper(I) species, see:

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    The proposed catalytic cycle (Scheme 1c) shows a stereoretentive reaction of 6 with 1; however, a stereoinvertive process is also possible.

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  18. 18

    For a review of CuH-catalyzed reactions:

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    CuH-Catalyzed Reactions
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    Lipshutz initially reported PPh3 as a secondary ligand in CuH-catalyzed reactions:

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    Krische has reported a similar temperature-dependent control in diene-carbonyl reductive couplings:

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    Under the conditions of ruthenium-catalyzed transfer hydrogenation, isoprene couples to benzylic and aliph. alcs. RCH2OH (R = n-octyl, 2-MeOC6H4, 4-BrC6H4, 2-thienyl, etc.) to deliver β,γ-unsatd. ketones H2C:C(Me)CHMeCOR in good to excellent isolated yields. Under identical conditions, aldehydes RCHO couple to isoprene to provide an identical set of β,γ-unsatd. ketones in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene, and 1,2-dimethylbutadiene to representative alcs. RCH2OH (R = 3-MeOC6H4, 4-MeOC6H4, 4-BrC6H4), diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsatd. ketones. In all cases, complete branch regioselectivity is obsd., and, with the exception of adduct of 1,3-butadiene and 4-bromobenzyl alc., isomerization to the conjugated enone is not detected. Thus, formal intermol. diene hydroacylation is achieved from the alc. or aldehyde oxidn. level.
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    Reduction of 3a with LiAlH4 at −78 °C has been shown to yield alcohol in >20:1 dr:

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    This phenomenon is related to the Horeau Principle and we thank a reviewer for providing this insight. For additional examples of this effect, see:

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  • Abstract

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    Scheme 1

    Scheme 1. (a) Prior Work in Aryl Alkene Reductive Coupling to Acyl Electrophiles; (b) Proposed Access to Chiral Ketones or Alcohols; (c) Proposed Catalytic Cycles
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    Scheme 2

    Scheme 2. (a) Enantioselective Ketone Synthesis and (b) Reductiona
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    Scheme aAll yields represent average isolated yields of two runs performed with 1 mmol of alkene.

    Scheme bReaction run at ambient temperature.

  • References

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    This article references 22 other publications.

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      Metallacycle-mediated cross-coupling with substituted and electronically unactivated alkenes
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      A review. This perspective surveys the history of - and recent advances in - metallacycle-mediated coupling chem. of substituted alkenes. While the reaction of preformed metal-π complexes with ethylene was reported nearly 30 years ago, the generalization of this mode of bimol. C-C bond formation to the regio- and stereoselective union of complex substrates has only recently begun to emerge. This perspective discusses early observations in this area, the challenges assocd. with controlling such processes, the evolution of a general strategy to overcome these challenges, and a summary of highly regio- and stereoselective convergent coupling reactions that are currently available via metallacycle-mediated cross-coupling of substituted alkenes.
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      For reviews on asymmetric hydroacylation, see:

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      Enantioselective hydroacylation of olefins with rhodium catalysts
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      Chemical Communications (Cambridge, United Kingdom) (2014), 50 (89), 13645-13649CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A review. Over thirty years ago, James and Young reported the first enantioselective olefin hydroacylation by using rhodium catalysts. This viewpoint highlights the advances in this area, including 4-pentenal cyclizations, medium-ring syntheses, and intermol. variants.
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      For selected enantioselective intermolecular hydroacylation reactions, see:

      (c) Liu, F.; Bugaut, X.; Schedler, M.; Fröhlich, R.; Glorius, F. Angew. Chem., Int. Ed. 2011, 50, 12626 DOI: 10.1002/anie.201106155
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      Designing N-Heterocyclic Carbenes: Simultaneous Enhancement of Reactivity and Enantioselectivity in the Asymmetric Hydroacylation of Cyclopropenes
      Liu, Fan; Bugaut, Xavier; Schedler, Michael; Froehlich, Roland; Glorius, Frank
      Angewandte Chemie, International Edition (2011), 50 (52), 12626-12630CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      We have described the first syntheses of ortho,ortho'-disubstituted electron-rich triazolium salts 5a-c (I, R = H (a), R = Me (b), R = Ph (c)) and demonstrated their synthetic utility in the prepn. of enantiomerically enriched acyl cyclopropanes. Preliminary kinetic studies showed that the newly designed catalysts allowed for a simultaneous enhancement of reactivity and selectivity, which is in accordance with previous calcns. We believe that this new 2,6-dimethoxyphenyl unit is an effective addn. to the current spectrum of NHC aryl substituents and has the potential to become a widely employed motif in carbene catalysts. This dramatic effect on reactivity and enantioselectivity is further evidence for the power and potential of NHCs and should find further applications in unexplored territories of organocatalysis.
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      Catalytic Enantioselective Intermolecular Hydroacylation: Rhodium-Catalyzed Combination of β-S-Aldehydes and 1,3-Disubstituted Allenes
      Osborne, James D.; Randell-Sly, Helen E.; Currie, Gordon S.; Cowley, Andrew R.; Willis, Michael C.
      Journal of the American Chemical Society (2008), 130 (51), 17232-17233CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A rhodium(I) catalyst incorporating the Me-DuPhos ligand promotes enantioselective intermol. hydroacylation between β-S-aldehydes and 1,3-disubstituted allenes. The nonconjugated enone products are obtained in good yields and with high enantioselectivities.
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    5. 5

      For reviews on reductive aldol, Mannich, and Michael reactions:

      (a) Nishiyama, H.; Shiomi, T. Top. Curr. Chem. 2007, 279, 105 DOI: 10.1007/128_2007_126
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      Catalytic asymmetric tandem transformations triggered by conjugate additions
      Guo, Hong-Chao; Ma, Jun-An
      Angewandte Chemie, International Edition (2006), 45 (3), 354-366CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. The development of efficient methods to access complex mols. with multistereogenic centers has been a substantial challenge in both academic research and industrial applications. One approach to this challenge is catalytic asym. tandem transformations, which allow a rapid increase in mol. complexity from readily available starting materials to produce enantiopure compds. In recent years, considerable efforts have been directed towards the development of asym. tandem transformations. This Minireview highlights recent developments and the applications of metal-catalyzed and organocatalytic asym. tandem transformations triggered by conjugate addns.
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      Selected Cu-catalyzed reductive coupling reactions:

      (d) Lipshutz, B. H.; Amorelli, B.; Unger, J. B. J. Am. Chem. Soc. 2008, 130, 14378 DOI: 10.1021/ja8045475
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      CuH-Catalyzed Enantioselective Intramolecular Reductive Aldol Reactions Generating Three New Contiguous Asymmetric Stereocenters
      Lipshutz, Bruce H.; Amorelli, Benjamin; Unger, John B.
      Journal of the American Chemical Society (2008), 130 (44), 14378-14379CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Treatment of β,β-disubstituted-α,β-unsatd. ketones, e.g., I, bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to cycloalkanols, e.g., II, with three newly created adjacent chiral centers. Excellent de's and ee's are obtained for several examples studied.
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      Dramatic Ligand Effect in Catalytic Asymmetric Reductive Aldol Reaction of Allenic Esters to Ketones
      Zhao, Dongbo; Oisaki, Kounosuke; Kanai, Motomu; Shibasaki, Masakatsu
      Journal of the American Chemical Society (2006), 128 (45), 14440-14441CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A general catalytic asym. reductive aldol reaction of allenic esters H2C:C:CHCO2R1 (R1 = Me, Et) with ketones R2COMe (R2 = Me2CH, n-Bu, H2C:CHCH2CH2, Ph, 4-ClC6H4, PhCH:CH, PhCH2CH2, 2-naphthyl, etc.) is described. Two distinct constitutional isomers were selectively produced depending on the reaction conditions. A combination of CuOAc/(R)-DTBM-SEGPHOS/PCy3 as the catalyst predominantly produced γ-cis-products R2MeC(OH)CH2CH:CHCO2R1 in high yields with excellent enantioselectivity (up to 99% ee). The reaction was applicable to both arom. and aliph. ketones, including unsatd. ketones. On the other hand, CuF-Taniaphos complexes produced α-aldol products R2MeC(OH)CH(CH:CH2)CO2R1 with high diastereo- and enantioselectivity (up to 84% ee). The new Taniaphos deriv., contg. di(3,5-xylyl)phosphine and morpholine units, produced optimum results in the α-selective reaction. The products are versatile chiral building blocks in org. synthesis. Furthermore, the basic reaction pattern (i.e., conjugate addn.-aldol reaction) was extended to a catalytic enantioselective alkylative aldol reaction to ketones using dialkylzinc reagents as the initiator.
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      Highly diastereo- and enantioselective copper-catalyzed domino reduction/aldol reaction of ketones with methyl acrylate
      Deschamp, Julia; Chuzel, Olivier; Hannedouche, Jerome; Riant, Olivier
      Angewandte Chemie, International Edition (2006), 45 (8), 1292-1297CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A new catalytic method was found for the construction of stereogenic quaternary carbon centers through a copper-catalyzed domino conjugated redn./aldol reaction of Me acrylate with various alkyl aryl ketones. The proper choice of the chiral diphosphine ligand leads to high chemo-, diastereo-, and enantioselectivity.
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    6. 6

      Selected examples of catalytic asymmetric enyne, diene, and allene reductive couplings:

      (a) Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.; Krische, M. J. Science 2012, 336, 324 DOI: 10.1126/science.1219274
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      Enantioselective C-H Crotylation of Primary Alcohols via Hydrohydroxyalkylation of Butadiene
      Zbieg, Jason R.; Yamaguchi, Eiji; McInturff, Emma L.; Krische, Michael J.
      Science (Washington, DC, United States) (2012), 336 (6079), 324-327CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      The direct, byproduct-free conversion of basic feedstocks to products of medicinal and agricultural relevance is a broad goal of chem. research. Butadiene is a product of petroleum cracking and is produced on an enormous scale (about 12 × 106 metric tons annually). Here, with the use of a ruthenium catalyst modified by a chiral phosphate counterion, the direct redox-triggered carbon-carbon coupling of alcs. and butadiene is reported to form products of carbonyl crotylation with high levels of anti-diastereoselectivity and enantioselectivity in the absence of stoichiometric byproducts.
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      (c) Geary, L. M.; Woo, S. K.; Leung, J. C.; Krische, M. J. Angew. Chem., Int. Ed. 2012, 51, 2972 DOI: 10.1002/anie.201200239
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      Diastereo- and Enantioselective Iridium-Catalyzed Carbonyl Propargylation from the Alcohol or Aldehyde Oxidation Level: 1,3-Enynes as Allenylmetal Equivalents
      Geary, Laina M.; Woo, Sang Kook; Leung, Joyce C.; Krische, Michael J.
      Angewandte Chemie, International Edition (2012), 51 (12), 2972-2976, S2972/1-S2972/61CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Iridium-catalyzed carbonyl propargylation of protected hex-5-en-3-ynes I (R = TBDMS, TIPS) with aldehydes or primary alcs. is described. As an example, using 4-bromobenzyl alc. or 4-bromobenzaldehyde gave II in 87% and 89% yield, with 12:1 and 11:1 diastereomeric ratio (anti:syn), and 89% ee and 87% ee of the major diastereomer, resp. Compd. II was then deprotected in a one-pot procedure, giving III in 86% yield.
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    7. 7

      Selected reviews on alkyne reductive coupling:

      (a) Tanaka, K.; Tajima, Y. Eur. J. Org. Chem. 2012, 3715 DOI: 10.1002/ejoc.201200098
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      (d) Jackson, E. P.; Malik, H. A.; Sormunen, G. J.; Baxter, R. D.; Liu, P.; Wang, H.; Shareef, A.-R.; Montgomery, J. Acc. Chem. Res. 2015, 48, 1736 DOI: 10.1021/acs.accounts.5b00096
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      7d
      Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings
      Jackson, Evan P.; Malik, Hasnain A.; Sormunen, Grant J.; Baxter, Ryan D.; Liu, Peng; Wang, Hengbin; Shareef, Abdur-Rafay; Montgomery, John
      Accounts of Chemical Research (2015), 48 (6), 1736-1745CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. The control of regiochem. is a considerable challenge in the development of a wide array of catalytic processes. Simple π-components such as alkenes, alkynes, 1,3-dienes, and allenes are among the many classes of substrates that present complexities in regioselective catalysis. Considering an internal alkyne as a representative example, when steric and electronic differences between the two substituents are minimal, differentiating among the two termini of the alkyne presents a great challenge. In cases where the differences between the alkyne substituents are substantial, overcoming those biases to access the regioisomer opposite that favored by substrate biases often presents an even greater challenge. Nickel-catalyzed reductive couplings of unsym. π-components make up a group of reactions where control of regiochem. presents a challenging but important objective. In the course of our studies of aldehyde-alkyne reductive couplings, complementary solns. to challenges in regiocontrol have been developed. Through careful selection of the ligand and reductant, as well as the more subtle reaction variables such as temp. and concn., effective protocols have been established that allow highly selective access to either regiosiomer of the allylic alc. products using a wide range of unsym. alkynes. Computational studies and an evaluation of reaction kinetics have provided an understanding of the origin of the regioselectivity control. Throughout the various procedures described, the development of ligand-substrate interactions plays an essential role, and the overall kinetic descriptions were found to differ between protocols. Rational alteration of the rate-detg. step plays a key role in the regiochem. reversal strategy, and in one instance, the two possible regioisomeric outcomes in a single reaction were found to operate by different kinetic descriptions. With this mechanistic information in hand, the empirical factors that influence regiochem. can be readily understood, and more importantly, the insights suggest simple and predictable exptl. variables to achieving a desired reaction outcome. These studies thus present a detailed picture of the influences that control regioselectivity in a specific catalytic reaction, but they also delineate strategies for regiocontrol that may extend to numerous classes of reactions. The work provides an illustration of how insights into the kinetics and mechanism of a catalytic process can rationalize subtle empirical findings and suggest simple and rational modifications in procedure to access a desirable reaction outcome. Furthermore, these studies present an illustration of how important challenges in org. synthesis can be met by novel reactivity afforded by base metal catalysis. The use of nickel catalysis in this instance not only provides an inexpensive and sustainable method for catalysis but also enables unique reactivity patterns not accessible to other metals.
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    8. 8
      (a) Yamaguchi, E.; Mowat, J.; Luong, T.; Krische, M. J. Angew. Chem., Int. Ed. 2013, 52, 8428 DOI: 10.1002/anie.201303552
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      For the reductive couplings of electron-deficient azaarene alkenes:

      (b) Best, D.; Lam, H. W. J. Org. Chem. 2014, 79, 831 DOI: 10.1021/jo402414k
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      C=N-Containing Azaarenes as Activating Groups in Enantioselective Catalysis
      Best, Daniel; Lam, Hon Wai
      Journal of Organic Chemistry (2014), 79 (3), 831-845CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)
      A review. Nitrogen-contg. arom. heterocycles (azaarenes) are of widespread chem. significance, and chiral compds. contg. azaarenes feature prominently in pharmaceuticals, agrochems., and natural products. This Perspective highlights the use of a relatively underdeveloped strategy to prep. chiral azaarene-contg. compds.: exploitation of the C=N bond embedded within certain azaarenes to activate adjacent functionality in catalytic asym. reactions. Work in this area has resulted in the development of several different types of catalytic enantioselective processes, including redns., nucleophilic addns., and reductive couplings. It is hoped that this Perspective will encourage more researchers to work in this promising area.
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      Enantioselective Copper-Catalyzed Reductive Coupling of Alkenylazaarenes with Ketones
      Saxena, Aakarsh; Choi, Bonnie; Lam, Hon Wai
      Journal of the American Chemical Society (2012), 134 (20), 8428-8431CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Catalytic enantioselective methods for the prepn. of chiral azaarene-contg. compds. are of high value. By combining the utility of copper hydride catalysis with the ability of C=N-contg. azaarenes to activate adjacent alkenes toward nucleophilic addns., the enantioselective reductive coupling of alkenylazaarenes with ketones has been developed. The process is tolerant of a wide variety of azaarenes and ketones, and provides arom. heterocycles bearing tertiary-alc.-contg. side chains with high levels of diastereo- and enantioselectivities.
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    11. 11

      For additional examples using anhydride and acyl chloride reagents in formal hydroacylation processes, see:

      (a) Fujihara, T.; Tatsumi, K.; Terao, J.; Tsuji, Y. Org. Lett. 2013, 15, 2286 DOI: 10.1021/ol400862k
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    12. 12

      For a review:

      (a) Pirnot, M. T.; Wang, Y.-M.; Buchwald, S. L. Angew. Chem., Int. Ed. 2016, 55, 48 DOI: 10.1002/anie.201507594
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      Copper Hydride-Catalyzed Hydroamination of Alkenes and Alkynes
      Pirnot, Michael T.; Wang, Yi-Ming; Buchwald, Stephen L.
      Angewandte Chemie, International Edition (2016), 55 (1), 48-57CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Over the past few years, CuH-catalyzed hydroamination was discovered and developed as a robust and conceptually novel approach for the synthesis of enantioenriched secondary and tertiary amines. The success in this area of research was made possible through the large body of precedent in copper(I) hydride catalysis and the well-explored use of hydroxylamine esters as electrophilic amine sources in related copper-catalyzed processes. This minireview details the background, advances, and mechanistic studies in CuH-catalyzed hydroamination.
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      For selected individual reports:

      (b) Zhu, S.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013, 135, 15746 DOI: 10.1021/ja4092819
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      Enantio- and Regioselective CuH-Catalyzed Hydroamination of Alkenes
      Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.
      Journal of the American Chemical Society (2013), 135 (42), 15746-15749CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      In the presence of (R)-DTBM-SEGPHOS and copper(II) acetate and using diethoxymethylsilane as a reducing agent, styrenes underwent regio- and enantioselective hydroamination reactions with O-benzoylhydroxylamines such as (PhCH2)2NOCOPh to give nonracemic aralkylamines such as [(S)-PhCHMe]N(CH2Ph)2 in 77-98% yields and in 86->99% ee; in one case, a trisubstituted aryl alkene underwent hydroamination to give a nonracemic β-alkyl aralkylamine as a single diastereomer in >99% ee. The reaction tolerated a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes, to yield nonracemic α-branched amines. Using racemic DTBM-SEGPHOS and copper(II) acetate and using diethoxymethylsilane as a reducing agent, terminal and 1,1-disubstituted aliph. alkenes such as 4-phenyl-1-butene underwent regioselective hydroamination with O-benzoylhydroxylamines such as (PhCH2)2NOCOPh to give anti-Markovnikov alkylamines such as Ph(CH2)4N(CH2Ph)2 in 80-99% yields.
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      (c) Yang, Y.; Shi, S.-L.; Niu, D.; Liu, P.; Buchwald, S. L. Science 2015, 349, 62 DOI: 10.1126/science.aab3753
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      12c
      Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines
      Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L.
      Science (Washington, DC, United States) (2015), 349 (6243), 62-66CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      A catalytic assembly of enantiopure aliph. amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chem. Here, the authors describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins-an important yet unexploited class of abundant feedstock chems.-into highly enantioenriched α-branched amines (≥96% enantiomeric excess) featuring two minimally differentiated aliph. substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas. Under optimized conditions the synthesis of the target compds. was achieved using copper diacetate and 1,1'-(4S)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] [i.e., (S)-(+)-DTBM-SEGPHOS] as a catalyst-ligand combination. The synthesis of the target compds. was achieved using (4E)-4-octene, (3E)-2,5-dimethyl-3-hexene, (7E)-2,2,3,3,12,12,13,13-octamethyl-4,11-dioxa-3,12-disilatetradec-7-ene, (3E)-3-hexene-1,6-diol, (2E)-4-methyl-2-pentene, (3E)-2,2-dimethyl-3-hexene as alkene starting materials. Hydroxylamine-ester derivs. included N-(benzoyloxy)-N-(phenylmethyl)benzenemethanamine, 4-methoxybenzoic acid bis[(aryl)methyl]azanyl ester derivs. (pyridine, pyrimidine, thiophene, furan, piperidine, piperazine derivs.). The title compds. thus formed included chiral amines, such as N-[(1S)-1-methylpropyl]-N-(phenylmethyl)benzenemethanamine. (αR)-α-methyl-N-[3-[3-(trifluoromethyl)phenyl]propyl]-1-naphthalenemethanamine (i.e., cinacalcet) and (3S,4R)-3-[(1,3-benzodioxol-5-yloxy)methyl]-4-(4-fluorophenyl)piperidine (i.e. paroxetine) were used as starting materials. Opposite enantiomers were obtained using 1,1'-(4R)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] [i.e., (R)-(-)-DTBM-SEGPHOS] as ligand.
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    13. 13
      (a) Miki, Y.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2013, 52, 10830 DOI: 10.1002/anie.201304365
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      13a
      Copper-Catalyzed Intermolecular Regioselective Hydroamination of Styrenes with Polymethylhydrosiloxane and Hydroxylamines
      Miki, Yuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro
      Angewandte Chemie, International Edition (2013), 52 (41), 10830-10834CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A copper-catalyzed intermol. regioselective hydroamination of arylalkenes R1CH:CHR2 (R1 = Ph, 4-MeOC6H4, 3-ClC6H4, 2-naphthyl, etc.; R2 = H, Me, i-Pr, MeOCH2, AcOCH2) with polymethylhydrosiloxane and O-benzoyl hydroxylamines R3R4NOC(O)Ph [R3 = R4 = Et, H2C:CHCH2, PhCH2; R3 = Me, R4 = PhCH2; R3R4 = (CH2)5, (CH2)6, (CH2)2O(CH2)2; etc.] affording the corresponding aralkyl amines R1CHNR3R4CH2R2 has been developed. Moreover, the chiral biphosphine-ligated copper complex was successfully used for the synthesis of non-racemic aralkyl amines with good enantiomeric ratios.
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      See also:

      (b) Xi, Y.; Butcher, T. W.; Zhang, J.; Hartwig, J. F. Angew. Chem., Int. Ed. 2016, 55, 776 DOI: 10.1002/anie.201509235
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      13b
      Regioselective, Asymmetric Formal Hydroamination of Unactivated Internal Alkenes
      Xi, Yumeng; Butcher, Trevor W.; Zhang, Jing; Hartwig, John F.
      Angewandte Chemie, International Edition (2016), 55 (2), 776-780CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The regioselective and enantioselective formal hydroamination of unsym. internal alkenes catalyzed by a copper catalyst ligated by DTBM-SEGPHOS is reported. The regioselectivity of the reaction is controlled by the electronic effects of ether, ester, and sulfonamide groups in the homoallylic position. The obsd. selectivity underscores the influence of inductive effects of remote substituents on the selectivity of catalytic processes occurring at hydrocarbyl groups, and the method provides direct access to various 1,3-aminoalc. derivs. with high enantioselectivity.
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    14. 14
      (a) Ascic, E.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137, 4666 DOI: 10.1021/jacs.5b02316
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      14a
      Highly Diastereo- and Enantioselective CuH-Catalyzed Synthesis of 2,3-Disubstituted Indolines
      Ascic, Erhad; Buchwald, Stephen L.
      Journal of the American Chemical Society (2015), 137 (14), 4666-4669CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A diastereo- and enantioselective CuH-catalyzed method for the prepn. of highly functionalized indolines I [R1 = H, 4-Me, 5-OMe, 6-F, etc; R2 = H, Me, CH2OMe; Ar = Ph, 4-OH-C6H4, 2-thiophenyl, etc.] is reported. The mild reaction conditions and high degree of functional group compatibility as demonstrated with substrates bearing heterocycles, olefins, and substituted arom. groups, renders this technique highly valuable for the synthesis of a variety of cis-2,3-disubstituted indolines in high yield and enantioeselectivity.
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      (b) Wang, Y.-M.; Bruno, N. C.; Placeres, Á. L.; Zhu, S.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137, 10524 DOI: 10.1021/jacs.5b07061
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      14b
      Enantioselective Synthesis of Carbo- and Heterocycles through a CuH-Catalyzed Hydroalkylation Approach
      Wang, Yi-Ming; Bruno, Nicholas C.; Placeres, Angel L.; Zhu, Shaolin; Buchwald, Stephen L.
      Journal of the American Chemical Society (2015), 137 (33), 10524-10527CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The enantioselective, intramol. hydroalkylation of halide-tethered styrenes has been achieved through a copper hydride-catalyzed process. This approach allowed for the synthesis of enantioenriched cyclobutanes, cyclopentanes, indanes, and six-membered N- and O-heterocycles. This protocol was applied to the synthesis of the com. serotonin reuptake inhibitor (-)-paroxetine.
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    15. 15

      For selected examples of asymmetric carbonyl additions of catalytically generated olefin-derived Cu(I) species, see:

      (a) Meng, F.; Haeffner, F.; Hoveyda, A. H. J. Am. Chem. Soc. 2014, 136, 11304 DOI: 10.1021/ja5071202
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      15a
      Diastereo- and enantioselective reactions of bis(pinacolato)diboron, 1,3-enynes, and aldehydes catalyzed by an easily accessible bisphosphine-Cu complex
      Meng, Fanke; Haeffner, Fredrik; Hoveyda, Amir H.
      Journal of the American Chemical Society (2014), 136 (32), 11304-11307CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Catalytic enantioselective multicomponent processes involving bis(pinacolato)diboron B2(pin)2, 1,3-enynes RC≡CCH:CH2 (R = Ph, aryl, 3-thienyl, 1-cyclohexenyl, TIPSOCMe2, Et3Si), and aldehydes R1CHO (R1 = aryl, 3-benzo[b]thienyl, cinnamyl, cyclohexenyl, PhCH2CH2) resulting in chiral bis(homopropargyl) diols R1CH(OH)CH(CH2OH)C≡CR are disclosed; the resulting compds. contain a primary C-B(pin) bond, as well as alkyne- and hydroxyl-substituted tertiary carbon stereogenic centers. A crit. feature is the initial enantioselective Cu-B(pin) addn. to an alkyne-substituted terminal alkene. This and other key mechanistic issues have been investigated by DFT calcns. Reactions are promoted by the Cu complex of a com. available enantiomerically pure bis-phosphine and are complete in 8 h at ambient temp.; products are generated in 66-94% yield (after oxidn. or catalytic cross-coupling), 90:10 to >98:2 diastereomeric ratio, and 85:15-99:1 enantiomeric ratio. Aryl-, heteroaryl-, alkenyl-, and alkyl-substituted aldehydes and enynes can be used. Utility is illustrated through catalytic alkylation and arylation of the organoboron products as well as applications to synthesis of fragments of tylonolide and mycinolide IV.
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      (b) Meng, F.; Jang, H.; Jung, B.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2013, 52, 5046 DOI: 10.1002/anie.201301018
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      15b
      Cu-Catalyzed Chemoselective Preparation of 2-(Pinacolato)boron-Substituted Allylcopper Complexes and their In Situ Site-, Diastereo-, and Enantioselective Additions to Aldehydes and Ketones
      Meng, Fanke; Jang, Hwanjong; Jung, Byunghyuck; Hoveyda, Amir H.
      Angewandte Chemie, International Edition (2013), 52 (19), 5046-5051CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A three-component single-vessel Cu-catalyzed method for chemo-, diastereo- and enantioselective reaction of aldehydes or ketones R1C(O)R2 (R1 = Ph, 2-ClC6H4, n-octyl, cyclohexyl, 2-naphthyl, PhCH:CH, etc.; R2 = H, Me, Et, etc.) and monosubstituted allenes R3CH:C:CH2 (R3 = Me, Ph, t-BuSiMe2OCH2CH2) in the presence of bis(pinacolato)diboron is described. The reaction proceeds via the formation of 2-(pinacolatoboron)-substituted allylcopper complexes which undergo addn. to an aldehyde or a ketone affording secondary or tertiary β-hydroxy ketones I (after oxidative work-up) or hydroxy-substituted vinyl bromides II (after bromination with CuBr2).
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      (c) Chikkade, P. K.; Shimizu, Y.; Kanai, M. Chem. Sci. 2014, 5, 1585 DOI: 10.1039/c3sc52803k
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      15c
      Catalytic enantioselective synthesis of 2-(2-hydroxyethyl)indole scaffolds via consecutive intramolecular amido-cupration of allenes and asymmetric addition of carbonyl compounds
      Chikkade, Prasanna Kumara; Shimizu, Yohei; Kanai, Motomu
      Chemical Science (2014), 5 (4), 1585-1590CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      A catalytic enantioselective method for the synthesis of 2-(2-hydroxyethyl)indole scaffolds was developed. The process included catalytic intramol. amido-cupration of an allene to generate a novel allylcopper species, followed by asym. addn. of the thus-generated chiral nucleophile to aldehydes and ketones. This was the first example of catalytic indole formation coupled with asym. C-C bond formation via in situ generation of a reactive chiral allylcopper species.
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    16. 16

      For examples of acylation reactions with nucleophilic copper(I) species, see:

      (a) Cirriez, V.; Rasson, C.; Riant, O. Adv. Synth. Catal. 2013, 355, 3137 DOI: 10.1002/adsc.201300621
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      16a
      Synthesis of Acylsilanes by Copper(I)-Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives
      Cirriez, Virginie; Rasson, Corentin; Riant, Olivier
      Advanced Synthesis & Catalysis (2013), 355 (16), 3137-3140CODEN: ASCAF7; ISSN:1615-4150. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The transition metal-catalyzed transfer of Si nucleophiles onto various electrophiles has recently gained considerable attention, due to the now readily available Si pro-nucleophiles such as silylboronates. The addn. of such species to acid derivs. generates acylsilanes. An efficient method to synthesize these compds., starting from easy-to-form anhydrides, with very good yields is reported. E.g., reaction of 4-methylbenzoic anhydride with dimethyl(phenyl)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane in the presence of 2 mol% CuF(PPh3)3·2MeOH and 1 equiv. of tetrabutylammonium triphenyldifluorosilicate in toluene solvent gave a 98% yield of [dimethyl(phenyl)silyl](p-tolyl)methanone.
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    17. 17

      The proposed catalytic cycle (Scheme 1c) shows a stereoretentive reaction of 6 with 1; however, a stereoinvertive process is also possible.

      There is no corresponding record for this reference.
    18. 18

      For a review of CuH-catalyzed reactions:

      Deutsch, C.; Krause, N.; Lipshutz, B. H. Chem. Rev. 2008, 108, 2916 DOI: 10.1021/cr0684321
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      18
      CuH-Catalyzed Reactions
      Deutsch, Carl; Krause, Norbert; Lipshutz, Bruce H.
      Chemical Reviews (Washington, DC, United States) (2008), 108 (8), 2916-2927CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. During the past decade, copper hydride chem. has evolved dramatically and can nowadays be considered as an integral part of modern org. synthesis. By expanding the diversity of ligands that stabilize copper hydride, from phosphines and their oxides to N-heterocyclic carbenes, new copper hydride systems with unprecedented reactivities have become available. Because of the nucleophilicity of hydride on Cu(I), akin to carbon-based systems, many copper-catalyzed reactions developed in the recent past involving C-C bond formation may well be reinvestigated using an alternative C-H bond construction. The high chemo-, regio- and stereoselectivity of catalytic copper hydride chem. makes it also a highly attractive reagent for applications to target-oriented synthesis. With the advent of new biaryl- and ferrocenyl-based ligands with remarkable innate levels of stereocontrol, hydrosilylations catalyzed by chiral CuH complexes have begun to compete with asym. hydrogenation on several levels.
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    19. 19

      Lipshutz initially reported PPh3 as a secondary ligand in CuH-catalyzed reactions:

      (a) Lipshutz, B. H.; Noson, K.; Chrisman, W.; Lower, A. J. Am. Chem. Soc. 2003, 125, 8779 DOI: 10.1021/ja021391f
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      19a
      Asymmetric Hydrosilylation of Aryl Ketones Catalyzed by Copper Hydride Complexed by Nonracemic Biphenyl Bis-phosphine Ligands
      Lipshutz, Bruce H.; Noson, Kevin; Chrisman, Will; Lower, Asher
      Journal of the American Chemical Society (2003), 125 (29), 8779-8789CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Copper hydride is an extremely reactive catalyst capable of effecting asym. hydrosilylations of arom. ketones at temps. between -50 and -78°, when complexed by chiral diphosphines of the BIPHEP or the SEGPHOS series. Inexpensive silanes serve as stoichiometric sources of hydride. Substrate-to-ligand ratios exceeding 100,000:1 were achieved. The level of induction is usually in the >90% ee category. The nature of the reagent was investigated using spectroscopic and chem. means, although its exact structure remains unclear.
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      (b)

      See also ref 14a

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    20. 20

      Krische has reported a similar temperature-dependent control in diene-carbonyl reductive couplings:

      Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14120 DOI: 10.1021/ja805356j
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      20
      Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium-Catalyzed C-C Bond-Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones
      Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.
      Journal of the American Chemical Society (2008), 130 (43), 14120-14122CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Under the conditions of ruthenium-catalyzed transfer hydrogenation, isoprene couples to benzylic and aliph. alcs. RCH2OH (R = n-octyl, 2-MeOC6H4, 4-BrC6H4, 2-thienyl, etc.) to deliver β,γ-unsatd. ketones H2C:C(Me)CHMeCOR in good to excellent isolated yields. Under identical conditions, aldehydes RCHO couple to isoprene to provide an identical set of β,γ-unsatd. ketones in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene, and 1,2-dimethylbutadiene to representative alcs. RCH2OH (R = 3-MeOC6H4, 4-MeOC6H4, 4-BrC6H4), diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsatd. ketones. In all cases, complete branch regioselectivity is obsd., and, with the exception of adduct of 1,3-butadiene and 4-bromobenzyl alc., isomerization to the conjugated enone is not detected. Thus, formal intermol. diene hydroacylation is achieved from the alc. or aldehyde oxidn. level.
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    21. 21

      Reduction of 3a with LiAlH4 at −78 °C has been shown to yield alcohol in >20:1 dr:

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      This phenomenon is related to the Horeau Principle and we thank a reviewer for providing this insight. For additional examples of this effect, see:

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