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Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination

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Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States
*[email protected]
Cite this: J. Am. Chem. Soc. 2015, 137, 30, 9716–9721
Publication Date (Web):July 5, 2015
https://doi.org/10.1021/jacs.5b05446

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Abstract

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The CuH-catalyzed hydroamination of alkenes and alkynes using a silane and an amine transfer reagent represents a simple strategy to access chiral amine products. We have recently reported methods to prepare chiral amines with high efficiency and stereoselectivity using this approach. However, the current technology is limited to the synthesis of trialkylamines from dialkylamine transfer reagents (R2NOBz). When monoalkylamine transfer reagents [RN(H)OBz] were used for the synthesis of chiral secondary amines, competitive, nonproductive consumption of these reagents by the CuH species resulted in poor yields. In this paper, we report the design of a modified type of amine transfer reagent that addresses this limitation. This effort has enabled us to develop a CuH-catalyzed synthesis of chiral secondary amines using a variety of amine coupling partners, including those derived from amino acid esters, carbohydrates, and steroids. Mechanistic investigations indicated that the modified amine transfer reagents are less susceptible to direct reaction with CuH.

Introduction

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Chiral amines are ubiquitous structural motifs found in many pharmaceutical agents, natural products, and catalysts for asymmetric synthesis (see Figure 1 for selected examples). As a result, general and selective methods for their synthesis have long been pursued. (1) Methodologies using resolution (2) or chiral auxiliaries (3) have been established as reliable ways to procure these compounds. Significant progress has also been made in the development of catalytic, asymmetric methods for their preparation. Many of these reported catalytic methods are based on asymmetric transformations of imine, enamine, or enamide intermediates. (4) Other strategies, such as asymmetric allylation of amine nucleophiles (5) and direct C–H bond insertion by a nitrenoid species, (6) are important alternatives.

Figure 1

Figure 1. Representative natural products and pharmaceutical agents that feature a chiral amine motif.

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Asymmetric hydroamination, (7) the net stereoselective addition of a hydrogen atom and an amino group directly across a double bond, represents a particularly appealing strategy to prepare chiral amines. Typically, a hydroamination reaction entails the direct union of an alkene 1 with a primary or secondary amine nucleophile 2 in the presence of a catalyst (Figure 2a). (7) Based on catalytic copper(I) hydride chemistry (8) and recent developments in the copper-mediated amination of carbon-based nucleophiles, (9) our group recently reported a mechanistically distinct approach toward asymmetric hydroamination (10) (Figure 2b). In this technique, an olefin first undergoes asymmetric hydrocupration to provide an alkylcopper intermediate, which is then intercepted by a suitable electrophilic amine transfer reagent. Our laboratory has applied this hydroamination strategy to the synthesis of chiral tertiary alkylamines from styrenes, (10a) 1,1-disubstituted alkenes, (10b) vinylsilanes, (10c) and alkynes. (10d) Independently, Miura and co-workers have reported a similar approach for the hydroamination of styrenes (11a) and strained internal alkenes. (11b)

Figure 2

Figure 2. Hydroamination approaches to make α-chiral amines.

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To date, this approach to hydroamination (10, 11) has been limited to the synthesis of tertiary alkylamines with O-benzoyl-N,N-dialkylhydroxylamines (R2NOBz, R = alkyl) as the dialkylamine transfer reagents. The expansion of this method to monoalkylamine transfer reagents to allow the direct preparation of chiral secondary amines would be of considerable interest. Herein we report the development of a copper-catalyzed hydroamination process to directly generate chiral, branched secondary amines 8 from styrenes (Figure 2c). One key factor in the development of this method is the design and use of a modified class of amine transfer reagents 7, which improved the efficiency and generality of the transformation. Mechanistic studies indicate that use of the modified amine transfer reagent suppresses nonproductive consumption of the reagent by the copper hydride intermediate.

Results and Discussion

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We began our work by studying the reaction between styrene (9a) and O-benzoyl-N-benzylhydroxylamine (12) [BnN(H)OBz, 10a] utilizing our previously reported conditions (10, 13) (Figure 3a). It was found that the desired secondary amine 11a was produced in moderate yield (60%) and excellent enantioselectivity. This result suggested the compatibility between the copper hydride and alkylcopper species with the N–H bond contained in both the amine transfer reagent 10a and the secondary amine product 11a. However, we found that this transformation had a limited substrate scope: either ortho- or β-substitution on the styrene substrate led to a dramatic drop in reaction efficiency (11b and 11c, 25 and <10% yield, respectively). We reasoned that the poor yields of 11b and 11c might be caused by the more challenging hydrocupration of the substituted styrenes (9b and 9c). In these cases, the (relatively rapid) nonproductive consumption of amine transfer reagent 10a by LCuH (Figure 3b, red arrow) would diminish the overall yields of the respective secondary amine products.

Figure 3

Figure 3. CuH-catalyzed hydroamination of styrenes for the formation of chiral secondary amines. aYields are determined using GC with dodecane as an internal standard; unless otherwise noted, CuH solution used in this study was prepared in a nitrogen-filled glovebox. bIsolated yields on 1 mmol scale (average of two runs); enantiomeric excesses (ee) were determined by chiral HPLC analysis; see Supporting Information for experimental details. cThree equivalents of HSi(OEt)2Me was used, and 10e was added over 1.5 h.

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We postulated that the use of an amine transfer reagent that is less susceptible to direct reaction with LCuH 5 would change the relative rates of the desired (hydrocupration) versus the undesired [BnN(H)OBz decomposition] pathway, thus expanding the substrate scope for the synthesis of secondary amines. We hypothesized that perturbation of the electronic properties of the benzoyl group of the electrophilic amine source 10 might lead to such an effect. (14) Thus, we prepared amine transfer reagents 10b–e (Figure 3c) by coupling commercially available N-benzyl hydroxylamine hydrochloride with various carboxylic acids and tested these new amine transfer reagents for the hydroamination of styrenes 9b and 9c under the same conditions as depicted in Figure 3a. As summarized in Figure 3c, we found that the use of more electron-rich amine transfer reagents 10c–e was beneficial to the reaction efficiency. Specifically, the use of 10e, an amine transfer reagent bearing a 4-(dimethylamino)benzoate group, provided the highest yields of 11b and 11c. In contrast, 10b, bearing the electron-deficient 4-(trifluoromethyl)benzoate group, gave poorer yields than the parent benzoate 10a. (15)
With 4-(dimethylamino)benzoate 10e as the amine transfer reagent, we found that a variety of styrene derivatives could be converted to the corresponding chiral secondary amines in good to excellent yield and with excellent enantioselectivity (Figure 3d). All these reactions proceeded to completion within 5 h at 40 °C or 16 h at room temperature under the reaction conditions shown in Figure 3a. For example, β-substituted styrenes and styrenes with ortho-substitution are suitable substrates (11b–e). (16) Additionally, styrenes bearing both electron-donating and electron-withdrawing substituents are tolerated as well (11f–g), and the reaction efficiency is not reduced when performed on a 5 mmol scale (11f). Further, styrenes containing heterocyclic rings are effective reaction partners (11h–j). Use of 4-fluorostyrene yielded 11k, which resembles the core structure of PF-05105679 (Figure 1), in 92% yield and 95% ee. Lastly, this process also permits the preparation of 11l–n, which contain synthetically versatile aryl bromide. The successful formation of 11l was somewhat surprising since related alkylcopper intermediates had been shown to undergo rearrangement to afford the arylcopper species. (17)
We next investigated the scope of the amine transfer reagents that could be employed (Table 1). The amine transfer agents used in this study were prepared from the corresponding primary hydroxylamine 15 and 4-(dimethylamino)benzoic acid via condensation effected by 1,1′-carbonyldiimidazole (CDI). (18) As summarized in Table 1, amine transfer reagents with secondary or tertiary alkyl group substituents are competent substrates, delivering products 17a–d in high yields and enantioselectivities. The use of chiral amine transfer agents afforded products with a high level of diastereoselectivity. The configuration of the newly generated stereocenter was determined by ligand employed (17c and 17d). When either racemic ligand or racemic electrophile was used, a near unity ratio of diastereomers was formed (see Supporting Information). These results are consistent with the diastereoselectivity of the hydroamination process being under catalyst control.
Table 1. Scope of Amine Transfer Reagents in Hydroamination Reactionsa
Table a

Reactions performed on 1 mmol scale for 17a–d and 0.5 mmol scale for 17e–l. Isolated yields are reported (average of two runs). Enantiomeric excesses (ee) were determined by chiral HPLC analysis or 1H NMR analysis. Diastereomeric ratios (dr) were determined by 1H NMR or gas chromatography analysis.

Table b

Toluene was used as the solvent, and amine transfer reagent with a pivolate leaving group was used as the substrate (see Supporting Information).

We found that amine transfer reagents prepared from α-amino esters (19) were competent substrates as well, and gave the N-monoalkylated amino esters with high levels of stereocontrol (17e–l, Table 1). Amino esters spanning a range of steric and electronic properties could be utilized (17e–j). Importantly, the protecting groups on the amino esters could be methyl (17e,f and 17j), benzyl (17g), or tert-butyl (17h,i), allowing a variety of choices for the selection of downstream deprotection methods. No epimerization of the labile stereocenter adjacent to the carbonyl group was observed, reflecting the overall mildness of the reaction system. Not surprisingly, use of different enantiomers of the ligand led to the formation of different diastereomers (17h and 17i), again supporting a catalyst-controlled stereodetermining step. Furthermore, an amine transfer reagent derived from a quaternary α-amino ester could also be employed, giving 17j in excellent yield and enantioselectivity. This method could also transform a vinylsilane (10c) to the α-aminosilane (17k), a class of building blocks often employed for the synthesis of peptidomimetics. (20) Finally, this hydroamination reaction can be integrated into a cascade sequence, delivering cyclic product 17l after in situ alkylation of the intermediate secondary amine.
To further demonstrate the utility of this methodology, we applied it in the context of drug molecule synthesis (Scheme 1). For example, this method was applied to the synthesis of Sensipar (21), a drug used to treat secondary hyperparathyroidism. Commercially available aldehyde 18 was converted to amine transfer reagent 19 and then subjected to hydroamination conditions in the presence of 1-vinylnaphthalene (20) to give 21 in 81% yield and 89% ee (Scheme 1a). This methodology was also applied to the derivatization of commercial pharmaceuticals. For instance, chlorpromazine (22), an antipsychotic, could be converted to vinylarene 23, (21) which then underwent hydroamination with l-valine-derived amine transfer reagent 24 to yield 25 (Scheme 1b). In a similar fashion, loratadine (26), an antihistamine drug, could be converted to 27 and then coupled with 29, an amine transfer reagent derived from an estrone derivative 28, to afford the conjugated product 30 in 85% yield and >20:1 dr (Scheme 1c). Lastly, vinylarene 32 made from tufnil (31), a nonsteroid anti-inflammatory drug, could successfully couple with 34, an amine transfer reagent prepared from a glucose derivative 33, to afford 35 in 73% yield and 17:1 dr (Scheme 1d).

Scheme 1

Scheme 1. Hydroamination Reaction in the Synthesis and Derivatization of Drugsa
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Scheme aReactions performed on 0.5 mmol scale. Isolated yields are reported (average of two runs). Enantioselectivities and diastereoselectivities were determined by chiral HPLC or 1H NMR analysis. Conditions A: (1) NH2OH·HCl, pyridine; (2) NaBH3CN, HCl in MeOH, MeOH/THF; (3) 4-(dimethylamino)benzoic acid, CDI, CH2Cl2. Conditions B: Pd(OAc)2, SPhos, potassium vinyltrifluoroborate, K2CO3, dioxane/H2O.

Mechanistic Studies

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Competition experiments were performed to investigate the role of the modified amine transfer reagents used in this study. We had hypothesized that the narrow substrate scope of the CuH-catalyzed hydroamination reaction using monoalkylamine transfer agents [e.g., BnN(H)OBz] was due to the susceptibility of these reagents toward direct, nonproductive reduction by LCuH. To address this, we conducted a competition experiment by exposing a 1:1 mixture of a pair of mono- and dialkylamine transfer reagents, 10a and 36, to HSi(OEt)2Me and copper catalyst in THF-d8in the absence of styrene and monitored the consumption of these two reagents by 1H NMR spectroscopy (Figure 4a). We found that LCuH was capable of directly reacting with the amine transfer reagents, and over 80% of the monoalkylamine transfer agent 10a was consumed within 1 h to give BnNH2 and the corresponding silylated benzoyl ester (37). (22) In contrast, only a trace (<5%) of the dialkylamine transfer agent 36 was consumed during the same period of time. (23) We then subjected a 1:1 mixture of a pair of monoalkylamine transfer reagents, 10a (parent benzoate) and 10e [4-(dimethylamino)benzoate], to identical conditions as described above (Figure 4b). In this case, both 10a and 10e were gradually consumed in the reaction system, giving the corresponding silylated esters (37 and 38) as products. Importantly, we found that the modified amine transfer reagent 10e was consumed at a considerably slower rate than was 10a. The higher stability of the modified monoalkylamine transfer reagents toward direct reaction with LCuH reaction is consistent with the increased substrate scope seen using the 4-(dimethylamino)benzoate-derived amine transfer reagents.

Figure 4

Figure 4. Relative rates of the reactions between LCuH and different amine transfer agents. Si* = Si(OEt)2Me. Conditions A: a 0.6 mL of a stock solution made from Cu(OAc)2 (3.6 mg), (R)-DTBM-SEGPHOS (26 mg), PPh3 (11.6 mg), HSi(OEt)2Me (0.32 mL, 2.0 mmol), and THF-d8 (1.0 mL) is used. The progress of these experiments was monitored by 1H NMR.

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Conclusion

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In conclusion, we have designed a new type of amine transfer reagent that possesses a 4-(dimethylamino)benzoate group. The use of these reagents enabled the development of a general method to directly convert styrenes to chiral secondary amines. This process was applicable to mono- and disubstituted styrenes and allowed the use of a variety of functionalized, structurally diverse amine transfer reagents, including those derived from carbohydrates, steroids, and amino acid esters. The utility of this reaction was highlighted by its application to the synthesis of pharmaceutically important drugs as well as the conjugation of other ones. Competition experiments have revealed that, relative to the corresponding O-benzoyl-N-alkyl hydroxylamines, the modified amine transfer reagents (O-[4-(dimethylamino)benzoyl]-N-alkyl hydroxylamines) are less susceptible to direct reaction with LCuH. The information gained from this study should prove useful in the design and development of other CuH-catalyzed processes. (24)

Supporting Information

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Experimental procedures and characterization data for all compounds. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b05446.

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.

Author Information

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  • Corresponding Author
    • Stephen L. Buchwald - Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States;  Email: [email protected]
  • Author
    • Dawen Niu - Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

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The authors acknowledge the National Institutes of Health for financial support (GM58160). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. We thank Dr. M.T. Pirnot and Dr. Y. Wang for assistance in the preparation of this manuscript.

References

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    Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution
    Hartwig, John F.; Stanley, Levi M.
    Accounts of Chemical Research (2010), 43 (12), 1461-1475CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. Enantioselective allylic substitution reactions comprise some of the most versatile methods for prepg. enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon-nitrogen, carbon-oxygen, carbon-carbon, and carbon-sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsym. allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, the authors describe the combination of an iridium precursor and a phosphoramidite ligand that catalyzes enantioselective allylic substitution reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or sep. in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prep. intermediates contg. allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from lab. on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields, with high branched-to-linear ratios and high enantioselectivities. Parallel mechanistic studies had revealed the metallacyclic structure of the active catalyst, and subsequent expts. with the purposefully formed metallacycle increased the reaction scope dramatically. Arom. amines, azoles, ammonia, and amides and carbamates as ammonia equiv. all reacted with high selectivities and yields. Also, weakly basic enolates (such as silyl enol ethers) and enolate equiv. (such as enamines) also reacted, and other research groups used this catalyst to conduct reactions of stabilized carbon nucleophiles in the absence of addnl. base. One hallmark of the reactions catalyzed by this iridium system is the invariably high enantioselectivity, which reflects a high stereoselectivity for formation of the allyl intermediate. Enantioselectivity typically exceeds 95%, regioselectivity for formation of branched over linear products is usually near 20:1, and yields generally exceed 75% and are often >90%. Thus, the development of iridium catalysts for enantioselective allylic substitution shows how studies of reaction mechanism can lead to a particularly active and a remarkably general system for an enantioselective process. In this case, a readily accessible catalyst effects allylic substitution, with high enantioselectivity and regioselectivity complementary to that of the venerable palladium systems.
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    Recent advances and applications of iridium-catalysed asymmetric allylic substitution
    Tosatti, Paolo; Nelson, Adam; Marsden, Stephen P.
    Organic & Biomolecular Chemistry (2012), 10 (16), 3147-3163CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
    A review was given on the development of iridium catalysts derived from an Ir salt and a chiral phosphoramidite and their application to the enantioselective synthesis of natural products and biol. relevant compds. Since their discovery in 1997, iridium-catalyzed asym. allylic substitutions were developed into a broadly applicable tool for the synthesis of chiral building blocks via C-C and C-heteroatom bond formation. The remarkable generality of these reactions and the high levels of regio- and enantioselectivity that are usually obtained in favor of the branched products have been made possible by a thorough investigation of the catalyst system and its mode of action. Therefore, today the Ir-catalyzed asym. allylic substitution is a powerful reaction in the org. chemist's repertoire and has been used extensively for several applications.
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  6. 6
    (a) Roizen, J. L.; Harvey, M. E.; Du Bois, J. Acc. Chem. Res. 2012, 45, 911 DOI: 10.1021/ar200318q
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    6a
    Metal-Catalyzed Nitrogen-Atom Transfer Methods for the Oxidation of Aliphatic C-H Bonds
    Roizen, Jennifer L.; Harvey, Mark Edwin; Du Bois, J.
    Accounts of Chemical Research (2012), 45 (6), 911-922CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review. For more than a century, chemists have endeavored to discover and develop reaction processes that enable the selective oxidn. of hydrocarbons. In the 1970s, Abramovitch and Yamada described the synthesis and electrophilic reactivity of sulfonyliminoiodinanes (RSO2N=IPh), demonstrating the utility of this new class of reagents to function as nitrene equiv. Subsequent investigations by Breslow, Mansuy, and Mueller would show such oxidants to be competent for alkene and satd. hydrocarbon functionalization when combined with transition metal salts or metal complexes, namely those of Mn, Fe, and Rh. Here, we trace our own studies to develop N-atom transfer technologies for C-H and π-bond oxidn. This Account discusses advances in both intra- and intermol. amination processes mediated by dirhodium and diruthenium complexes, as well as the mechanistic foundations of catalyst reactivity and arrest. Explicit ref. is given to questions that remain unanswered and to problem areas that are rich for discovery. A fundamental advance in amination technol. has been the recognition that iminoiodinane oxidants can be generated in situ in the presence of a metal catalyst that elicits subsequent N-atom transfer. Under these conditions, both dirhodium and diruthenium lantern complexes function as competent catalysts for C-H bond oxidn. with a range of nitrogen sources (e.g., carbamates, sulfamates, sulfamides, etc.), many of which will not form isolable iminoiodinane equiv. Practical synthetic methods and applications thereof have evolved in parallel with inquiries into the operative reaction mechanism(s). For the intramol. dirhodium-catalyzed process, the body of exptl. and computational data is consistent with a concerted asynchronous C-H insertion pathway, analogous to the consensus mechanism for Rh-carbene transfer. Other studies reveal that the bridging tetracarboxylate ligand groups, which shroud the dirhodium core, are labile to exchange under std. reaction conditions. This information has led to the generation of chelating dicarboxylate dinuclear rhodium complexes, exemplified by Rh2(esp)2. The performance of this catalyst system is unmatched by other dirhodium complexes in both intra- and intermol. C-H amination reactions. Tetra-bridged, mixed-valent diruthenium complexes function as effective promoters of sulfamate ester oxidative cyclization. These catalysts can be crafted with ligand sets other than carboxylates and are more resistant to oxidn. than their dirhodium counterparts. A range of exptl. and computational mechanistic data amassed with the tetra-2-oxypyridinate diruthenium chloride complex, [Ru2(hp)4Cl], has established the insertion event as a stepwise pathway involving a discrete radical intermediate. These data contrast dirhodium-catalyzed C-H amination and offer a cogent model for understanding the divergent chemoselectivity trends obsd. between the two catalyst types. This work constitutes an important step toward the ultimate goal of achieving predictable, reagent-level control over product selectivity.
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    Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion
    Davies, Huw M. L.; Manning, James R.
    Nature (London, United Kingdom) (2008), 451 (7177), 417-424CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
    A review. Novel reactions that can selectively functionalize carbon-hydrogen bonds are of intense interest to the chem. community because they offer new strategic approaches for synthesis. A very promising 'carbon-hydrogen functionalization' method involves the insertion of metal carbenes and nitrenes into C-H bonds. This area has experienced considerable growth in the past decade, particularly in the area of enantioselective intermol. reactions. Here we discuss several facets of these kinds of C-H functionalization reactions and provide a perspective on how this methodol. has affected the synthesis of complex natural products and potential pharmaceutical agents.
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    Enantioselective Catalytic Aziridinations and Asymmetric Nitrene Insertions into CH Bonds
    Mueller, Paul; Fruit, Corinne
    Chemical Reviews (Washington, DC, United States) (2003), 103 (8), 2905-2919CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review.
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  7. 7
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    Organolanthanide-Catalyzed Hydroamination
    Hong, Sukwon; Marks, Tobin J.
    Accounts of Chemical Research (2004), 37 (9), 673-686CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
    A review; organolanthanides are highly efficient catalysts for inter- and intramol. hydroamination of various C-C unsaturations such as alkenes, alkynes, allenes, and dienes. Attractive features of organolanthanide catalysts include very high turnover frequencies and excellent stereoselectivities, rendering this methodol. applicable to concise synthesis of naturally occurring alkaloids and other polycyclic azacycles. The general hydroamination mechanism involves turnover-limiting C-C multiple bond insertion into the Ln-N bond, followed by rapid protonolysis by other amine substrates. Sterically less encumbered ligand designs have been developed to improve reaction rates, and metallocene and nonmetallocene chiral lanthanide complexes have been synthesized for enantioselective hydroamination.
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    Catalytic Markovnikov and anti-Markovnikov functionalization of alkenes and alkynes. Recent developments and trends
    Beller, Matthias; Seayad, Jayasree; Tillack, Annegret; Jiao, Haijun
    Angewandte Chemie, International Edition (2004), 43 (26), 3368-3398CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. The regioselective functionalization of terminal alkenes and alkynes is of utmost importance for the synthesis of a wide variety of org. products. Based on the original observation by Vladimir Markovnikov - the pioneer of this field of research - in the 19th century, the possible regioisomeric products are classified as Markovnikov or anti-Markovnikov products. Contrary to traditional belief, it is nowadays possible to control the regiochem. of various addns. of nucleophiles to alkenes and alkynes by applying different transition-metal catalysts. Recent developments in this area of selective functionalization of alkenes and alkynes are reviewed.
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    Hydroamination: direct addition of amines to alkenes and alkynes
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    Late Transition Metal-Catalyzed Hydroamination and Hydroamidation
    Huang, Liangbin; Arndt, Matthias; Goossen, Kaethe; Heydt, Heinrich; Goossen, Lukas J.
    Chemical Reviews (Washington, DC, United States) (2015), 115 (7), 2596-2697CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
    A review. This review examines recent developments in late transition metal-catalyzed hydroamination and -amidation reactions. In this review, usage of the term hydroamidation is not limited to the substrate classes of amides, sulfonamides, and phosphonamides, but extended to structurally related compds. with a similar pKa range and reactivity, such as carbamates, lactams, ureas, amidines, guanidines, etc.
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  8. 8
    (a) Appella, D. H.; Moritani, Y.; Shintani, R.; Ferreira, E. M.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9473 DOI: 10.1021/ja992366l
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    Asymmetric conjugate reduction of α,β-unsaturated esters using a chiral phosphine-copper catalyst
    Appella, Daniel H.; Moritani, Yasunori; Shintani, Ryo; Ferreira, Eric M.; Buchwald, Stephen L.
    Journal of the American Chemical Society (1999), 121 (40), 9473-9474CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A catalyst formed from (S)-p-tol-BINAP, CuCl, and NaOCMe3effects the asym. conjugate redn. of α,β-unsatd. esters in the presence of 4 equiv. of polymethylhydrosiloxane (PMHS). Thus, redn. of (E)-PhCMe:CHCO2Et in toluene under air-free conditions gave (S)-PhCHMeCH2CO2Et in 84% yield with 90% ee. (E)- and (Z)-stereoisomers of α,β-unsatd. esters give enantiomeric β-substituted esters; e.g., Et (E)-geranate Me2C:CHCH2CH2C(Me):CHCO2Et gives Et (R)-citronellate in 85% ee, while Et (Z)-geranate gives Et (S)-citronellate in 80% ee.
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    (a) Berman, A. M.; Johnson, J. S. J. Am. Chem. Soc. 2004, 126, 5680 DOI: 10.1021/ja049474e
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    Copper-catalyzed electrophilic amination of diorganozinc reagents
    Berman, Ashley M.; Johnson, Jeffrey S.
    Journal of the American Chemical Society (2004), 126 (18), 5680-5681CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The copper-catalyzed electrophilic amination of diorganozinc reagents, employing O-acyl N,N-dialkyl hydroxylamines, e.g., I, as aminating agents, is described. This reaction offered a general method for the prepn. of tertiary amines, e.g., II, in high yields, and easy product isolation (acid/base extractive workup).
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    Mechanistic Studies of the Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents and Development of a Zinc-Free Protocol
    Campbell, Matthew J.; Johnson, Jeffrey S.
    Organic Letters (2007), 9 (8), 1521-1524CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)
    An SN2 mechanism for the copper-catalyzed amination of diorganozinc reagents by O-benzoyl-N,N-dialkylhydroxylamines is supported by following stereochem. defined organometallics through the reaction and by employing the endocyclic restriction test. A copper-catalyzed electrophilic amination of organomagnesium compds. is also described in which the use of zinc halides has been eliminated.
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    Synthesis of Hindered Anilines: Copper-Catalyzed Electrophilic Amination of Aryl Boronic Esters
    Rucker, Richard P.; Whittaker, Aaron M.; Dang, Hester; Lalic, Gojko
    Angewandte Chemie, International Edition (2012), 51 (16), 3953-3956, S3953/1-S3953/108CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The authors have developed a mild copper-catalyzed electrophilic amination reaction for the synthesis of sterically-hindered anilines from aryl and heteroaryl boronic esters. The new method is compatible with a wide range of functionalities, including chloro, bromo, iodo, carbomethoxy, nitro, hydroxyl, formyl, and methoxy groups. Overall, an exceptionally broad scope and reliability of this new procedure, together with the availability of a wide variety of aryl boronic esters, make it a significant addn. to the existing methods for aniline synthesis.
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    Recent progress in copper-catalyzed electrophilic amination
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    A review. Copper-catalyzed coupling reactions have been recognized as one of the most useful strategies for the formation of C-N bonds. This perspective gives an overview of the recent developments in copper-catalyzed electrophilic amination for the construction of various amines and their derivs., including the electrophilic amination of various organometallic reagents and direct C-H bonds as well as the annulative electrophilic amination of o-alkynylphenols and o-alkynylanilines.
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    A review with 209 refs. The amination reagents are: amines, N-haloamines, O-substituted hydroxylamines, azides, oximes, arenediazonium salts, and dialkyl azodicarboxylates.
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    (a) 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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    Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of 1,1-Disubstituted Alkenes
    Zhu, Shaolin; Buchwald, Stephen L.
    Journal of the American Chemical Society (2014), 136 (45), 15913-15916CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Enantioselective synthesis of β-chiral amines has been achieved via copper-catalyzed hydroamination of 1,1-disubstituted alkenes with hydroxylamine esters in the presence of a hydrosilane. This mild process affords a range of structurally diverse β-chiral amines, including β-deuterated amines, in excellent yields with high enantioselectivities. Furthermore, catalyst loading as low as 0.4 mol% could be employed to deliver product in undiminished yield and selectivity, demonstrating the practicality of this method for large-scale synthesis.
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    The synthesis of α-aminosilanes by a highly enantio- and regioselective copper-catalyzed hydroamination of vinylsilanes is reported. The system employs Cu-DTBM-SEGPHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O-benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thus providing access to amino acid mimics and other valuable chiral organosilicon compds.
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    The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a long-standing goal of chem. research. Despite the centrality of amines in a no. of important research areas, including medicinal chem., total synthesis and materials science, a general, selective and step-efficient synthesis of amines is still needed. Here, the authors describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct prepn. of three distinct and important amine classes (enamines, α-chiral branched alkylamines and linear alkylamines) from readily available alkyne starting materials with high levels of chemoselectivity, regioselectivity and stereoselectivity. This method was applied to the asym. synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine and tolterodine. Under optimized conditions the synthesis of the target compds. was achieved using copper(II) acetate as a catalyst and 1,1'-(4R)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] as a catalyst-ligand combination. Alkyne starting materials included 1,1'-(1,2-ethynediyl)bis[benzene], (1-hexynyl)benzene, 1-chloro-3-(ethynyl)benzene, 3-(ethynyl)pyridine, 5-ethynyl-1-[(4-methylphenyl)sulfonyl]-1H-indole, (3,3-diethoxy-1-propyn-1-yl)benzene (acetal). Amine starting materials included N-(benzoyloxy)-N-(phenylmethyl)benzenemethanamine, benzoic acid 2,2,6,6-tetramethyl-1-piperidinyl ester, benzoic acid 4-morpholinyl ester. 3-[[(Trifluoromethyl)sulfonyl]oxy]estra-1,3,5(10)-trien-17-one cyclic 1,2-ethanediyl acetal was also used as a starting material. The title compds. thus formed included N-(ethyl)-N-(methyl)carbamic acid 3-[(1S)-1-(dimethylamino)ethyl]phenyl ester [i.e., (S)-Rivastigmine] and 2-[3-[bis(1-methylethyl)amino]-1-phenylpropyl]-4-(methyl)phenol [i.e., (±)-tolterodine formal synthesis].
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    Organic Letters (2014), 16 (5), 1498-1501CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
    A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addn. of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbornanylamines in good yields and good enantiomeric ratios. Thus, e.g., treatment of oxabenzonorbornadiene with morpholino benzoate in presence of CuCl/(R,R)-Ph-BPE, LiO-t-Bu and PMHS in DME afforded aminated product I in 81% yield, 99:1 er.
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    In contrast to the large number of successful examples using dialkylamine transfer reagents (R2NOBz, R ≠ H) in copper-mediated amination reactions, use of the analogous monoalkylamine transfer reagents [RN(H)OBz] remains underdeveloped. For representative examples, see ref 9b and

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    The C-H amination of electron-deficient arenes such as polyfluoroarenes and azole compds. with O-acylated hydroxylamines effectively proceeds in the presence of a copper catalyst even at room temp. to provide the corresponding anilines and aminoazoles in good yields.
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    Highly Diastereo- and Enantioselective CuH-Catalyzed Synthesis of 2,3-Disubstituted Indolines
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    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)

    PPh3 is used as a secondary ligand due to the observed beneficial effects it has on CuH-catalyzed reactions. This concept was developed by Lipshutz:

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    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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    Attempts to modify the properties of dialkylamine transfer reagents by adjusting the benzoate group have been reported by Johnson. (9c)

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    (a)

    Alkyl carboxylate-based amine transfer reagents 13 and 14 were also tested. Reagent 14 containing a bulky adamantyl group provided yields of 11b and 11c similar to that of 4-(dimethylamino)benzoate 10e. Due to the availability of the 4-(dimethylamino)benzoic acid and its ease of removal after reaction, (15b) 4-(dimethylamino)benzoates were used for most of this work

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    4-(Dimethylamino)benzoic acid is sparingly soluble in Et2O, EtOAc, or CH2Cl2 but readily soluble in 2 M aqueous K2CO3.

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    Attempts to use 10e in the hydroamination of β,β-disubstituted styrenes or terminal unactivated alkenes gave low yields of secondary amine products.

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    Formation of BnNH2 and the silylated ester 37 could be detected by GC/MS and 1H NMR analysis.

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    Reduction of the dialkylamine transfer agent 36 is much slower. Approximately, 60% of 36 was consumed after 20 h under described conditions.

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  • Abstract

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    Figure 1

    Figure 1. Representative natural products and pharmaceutical agents that feature a chiral amine motif.

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    Figure 2

    Figure 2. Hydroamination approaches to make α-chiral amines.

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    Figure 3

    Figure 3. CuH-catalyzed hydroamination of styrenes for the formation of chiral secondary amines. aYields are determined using GC with dodecane as an internal standard; unless otherwise noted, CuH solution used in this study was prepared in a nitrogen-filled glovebox. bIsolated yields on 1 mmol scale (average of two runs); enantiomeric excesses (ee) were determined by chiral HPLC analysis; see Supporting Information for experimental details. cThree equivalents of HSi(OEt)2Me was used, and 10e was added over 1.5 h.

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    Scheme 1

    Scheme 1. Hydroamination Reaction in the Synthesis and Derivatization of Drugsa
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    Scheme aReactions performed on 0.5 mmol scale. Isolated yields are reported (average of two runs). Enantioselectivities and diastereoselectivities were determined by chiral HPLC or 1H NMR analysis. Conditions A: (1) NH2OH·HCl, pyridine; (2) NaBH3CN, HCl in MeOH, MeOH/THF; (3) 4-(dimethylamino)benzoic acid, CDI, CH2Cl2. Conditions B: Pd(OAc)2, SPhos, potassium vinyltrifluoroborate, K2CO3, dioxane/H2O.

    Figure 4

    Figure 4. Relative rates of the reactions between LCuH and different amine transfer agents. Si* = Si(OEt)2Me. Conditions A: a 0.6 mL of a stock solution made from Cu(OAc)2 (3.6 mg), (R)-DTBM-SEGPHOS (26 mg), PPh3 (11.6 mg), HSi(OEt)2Me (0.32 mL, 2.0 mmol), and THF-d8 (1.0 mL) is used. The progress of these experiments was monitored by 1H NMR.

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      This review is intended to provide an overview of the transition metal-catalyzed enantioselective hydrogenation of enamines and imines for the synthesis of chiral amines. The focus of this review is on the development of chiral metal catalysts for these transformations emphasizing rhodium, ruthenium, iridium, titanium, and palladium catalysts. For the hydrogenation of N-acetyl enamines, the chiral rhodium complexes bearing diphosphine ligands were efficient chiral catalysts. However, in the hydrogenation of N-alkyl/aryl imines, the chiral iridium catalysts contg. phosphine oxazoline ligands exhibit outstanding performance. Furthermore, the highly efficient catalysts for activated imines hydrogenation were dominated by palladium complexes of chiral diphosphine ligands.
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      Chemical Reviews (Washington, D. C.) (1999), 99 (5), 1069-1094CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      Review with 125 refs. on reductive amination via imines and C-C bond-formation of imines.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXisVaqt7o%253D&md5=e0e8bbe7e9a18a538a9e5f02262c4a94
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      A review. Methods for enantioselective C-C bond constructions via addns. to imines and related compds. are reviewed, with an emphasis on the most recent efforts involving asym. catalysis. Selected seminal examples are provided in order to place the recent developments in context (e.g., asym. addn. of organometallic nucleophiles, asym. Mannich reactions, Strecker reactions, etc.).
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      Chemical Reviews (Washington, DC, United States) (2011), 111 (4), 2626-2704CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review was given covering the period from the end of 1998 to the beginning of 2009 and surveying the literature on the addn. of C nucleophiles to imines and hydrazones under the influence of metallic and non-metallic promoters and substoichiometric quantities of a chiral source.
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      Yus, Miguel; Gonzalez-Gomez, Jose C.; Foubelo, Francisco
      Chemical Reviews (Washington, DC, United States) (2011), 111 (12), 7774-7854CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Methodologies on the catalytic enantioselective addn. of allylic nucleophiles to carbonyl compds., imines (mostly with N-allyl, -aryl, -benzyl, and -sulfonyl substituents), and imine derivs. (hydrazones) will be considered, paying special attention to the most useful reactions from a synthetic point of view.
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      Complete Field Guide to Asymmetric BINOL-Phosphate Derived Bronsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Bronsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates
      Parmar, Dixit; Sugiono, Erli; Raja, Sadiya; Rueping, Magnus
      Chemical Reviews (Washington, DC, United States) (2014), 114 (18), 9047-9153CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. Chiral BINOL-derived Broensted acids have shown themselves to be highly efficient catalysts for a huge plethora of transformations and allow the end user to form C-C, C-H, and a variety of C-X bonds in a highly enantioselective fashion. Although within this category phosphoric acids are strongly known for activating imine substrates, stronger acids in the form of N-triflyl phosphoramides have bridged the gap somewhat to accessing previously thought out-of-reach substrates. Their utility in synthesis however is not solely limited to their acidic character, and more recently they have become extremely powerful chiral counterions for an increasing list of reactions. Furthermore, they can be combined with metal catalysts to create a synergistic effect, which has opened new reaction modes previously not possible with the individual catalysts themselves. Improved understanding of the mechanisms and interactions assocd. between the catalyst and the substrates has allowed research groups to develop highly powerful methodologies. Unfortunately, our understanding is still far from complete, and currently we have a crude understanding of how the catalysts function, but detailed exptl. and computational studies are still required for further progress in the field.
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    5. 5
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      Allylic Amination
      Johannsen, Mogens; Jorgensen, Karl Anker
      Chemical Reviews (Washington, D. C.) (1998), 98 (4), 1689-1708CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review with 165 refs. on the amination of functionalized and nonfunctionalized alkenes.
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      (b) Helmchen, G. Iridium-Catalyzed Asymmetric Allylic Substitutions. In Iridium Complexes in Organic Synthesis; Oro, L. A.; Claver, C., Eds.; Wiley-VCH: Weinheim, Germany, 2009; pp 211– 250.
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      Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution
      Hartwig, John F.; Stanley, Levi M.
      Accounts of Chemical Research (2010), 43 (12), 1461-1475CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Enantioselective allylic substitution reactions comprise some of the most versatile methods for prepg. enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon-nitrogen, carbon-oxygen, carbon-carbon, and carbon-sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsym. allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, the authors describe the combination of an iridium precursor and a phosphoramidite ligand that catalyzes enantioselective allylic substitution reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or sep. in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prep. intermediates contg. allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from lab. on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields, with high branched-to-linear ratios and high enantioselectivities. Parallel mechanistic studies had revealed the metallacyclic structure of the active catalyst, and subsequent expts. with the purposefully formed metallacycle increased the reaction scope dramatically. Arom. amines, azoles, ammonia, and amides and carbamates as ammonia equiv. all reacted with high selectivities and yields. Also, weakly basic enolates (such as silyl enol ethers) and enolate equiv. (such as enamines) also reacted, and other research groups used this catalyst to conduct reactions of stabilized carbon nucleophiles in the absence of addnl. base. One hallmark of the reactions catalyzed by this iridium system is the invariably high enantioselectivity, which reflects a high stereoselectivity for formation of the allyl intermediate. Enantioselectivity typically exceeds 95%, regioselectivity for formation of branched over linear products is usually near 20:1, and yields generally exceed 75% and are often >90%. Thus, the development of iridium catalysts for enantioselective allylic substitution shows how studies of reaction mechanism can lead to a particularly active and a remarkably general system for an enantioselective process. In this case, a readily accessible catalyst effects allylic substitution, with high enantioselectivity and regioselectivity complementary to that of the venerable palladium systems.
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      Recent advances and applications of iridium-catalysed asymmetric allylic substitution
      Tosatti, Paolo; Nelson, Adam; Marsden, Stephen P.
      Organic & Biomolecular Chemistry (2012), 10 (16), 3147-3163CODEN: OBCRAK; ISSN:1477-0520. (Royal Society of Chemistry)
      A review was given on the development of iridium catalysts derived from an Ir salt and a chiral phosphoramidite and their application to the enantioselective synthesis of natural products and biol. relevant compds. Since their discovery in 1997, iridium-catalyzed asym. allylic substitutions were developed into a broadly applicable tool for the synthesis of chiral building blocks via C-C and C-heteroatom bond formation. The remarkable generality of these reactions and the high levels of regio- and enantioselectivity that are usually obtained in favor of the branched products have been made possible by a thorough investigation of the catalyst system and its mode of action. Therefore, today the Ir-catalyzed asym. allylic substitution is a powerful reaction in the org. chemist's repertoire and has been used extensively for several applications.
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    6. 6
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      Metal-Catalyzed Nitrogen-Atom Transfer Methods for the Oxidation of Aliphatic C-H Bonds
      Roizen, Jennifer L.; Harvey, Mark Edwin; Du Bois, J.
      Accounts of Chemical Research (2012), 45 (6), 911-922CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. For more than a century, chemists have endeavored to discover and develop reaction processes that enable the selective oxidn. of hydrocarbons. In the 1970s, Abramovitch and Yamada described the synthesis and electrophilic reactivity of sulfonyliminoiodinanes (RSO2N=IPh), demonstrating the utility of this new class of reagents to function as nitrene equiv. Subsequent investigations by Breslow, Mansuy, and Mueller would show such oxidants to be competent for alkene and satd. hydrocarbon functionalization when combined with transition metal salts or metal complexes, namely those of Mn, Fe, and Rh. Here, we trace our own studies to develop N-atom transfer technologies for C-H and π-bond oxidn. This Account discusses advances in both intra- and intermol. amination processes mediated by dirhodium and diruthenium complexes, as well as the mechanistic foundations of catalyst reactivity and arrest. Explicit ref. is given to questions that remain unanswered and to problem areas that are rich for discovery. A fundamental advance in amination technol. has been the recognition that iminoiodinane oxidants can be generated in situ in the presence of a metal catalyst that elicits subsequent N-atom transfer. Under these conditions, both dirhodium and diruthenium lantern complexes function as competent catalysts for C-H bond oxidn. with a range of nitrogen sources (e.g., carbamates, sulfamates, sulfamides, etc.), many of which will not form isolable iminoiodinane equiv. Practical synthetic methods and applications thereof have evolved in parallel with inquiries into the operative reaction mechanism(s). For the intramol. dirhodium-catalyzed process, the body of exptl. and computational data is consistent with a concerted asynchronous C-H insertion pathway, analogous to the consensus mechanism for Rh-carbene transfer. Other studies reveal that the bridging tetracarboxylate ligand groups, which shroud the dirhodium core, are labile to exchange under std. reaction conditions. This information has led to the generation of chelating dicarboxylate dinuclear rhodium complexes, exemplified by Rh2(esp)2. The performance of this catalyst system is unmatched by other dirhodium complexes in both intra- and intermol. C-H amination reactions. Tetra-bridged, mixed-valent diruthenium complexes function as effective promoters of sulfamate ester oxidative cyclization. These catalysts can be crafted with ligand sets other than carboxylates and are more resistant to oxidn. than their dirhodium counterparts. A range of exptl. and computational mechanistic data amassed with the tetra-2-oxypyridinate diruthenium chloride complex, [Ru2(hp)4Cl], has established the insertion event as a stepwise pathway involving a discrete radical intermediate. These data contrast dirhodium-catalyzed C-H amination and offer a cogent model for understanding the divergent chemoselectivity trends obsd. between the two catalyst types. This work constitutes an important step toward the ultimate goal of achieving predictable, reagent-level control over product selectivity.
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      Davies, Huw M. L.; Manning, James R.
      Nature (London, United Kingdom) (2008), 451 (7177), 417-424CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)
      A review. Novel reactions that can selectively functionalize carbon-hydrogen bonds are of intense interest to the chem. community because they offer new strategic approaches for synthesis. A very promising 'carbon-hydrogen functionalization' method involves the insertion of metal carbenes and nitrenes into C-H bonds. This area has experienced considerable growth in the past decade, particularly in the area of enantioselective intermol. reactions. Here we discuss several facets of these kinds of C-H functionalization reactions and provide a perspective on how this methodol. has affected the synthesis of complex natural products and potential pharmaceutical agents.
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      Enantioselective Catalytic Aziridinations and Asymmetric Nitrene Insertions into CH Bonds
      Mueller, Paul; Fruit, Corinne
      Chemical Reviews (Washington, DC, United States) (2003), 103 (8), 2905-2919CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review.
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    7. 7
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      Organolanthanide-Catalyzed Hydroamination
      Hong, Sukwon; Marks, Tobin J.
      Accounts of Chemical Research (2004), 37 (9), 673-686CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review; organolanthanides are highly efficient catalysts for inter- and intramol. hydroamination of various C-C unsaturations such as alkenes, alkynes, allenes, and dienes. Attractive features of organolanthanide catalysts include very high turnover frequencies and excellent stereoselectivities, rendering this methodol. applicable to concise synthesis of naturally occurring alkaloids and other polycyclic azacycles. The general hydroamination mechanism involves turnover-limiting C-C multiple bond insertion into the Ln-N bond, followed by rapid protonolysis by other amine substrates. Sterically less encumbered ligand designs have been developed to improve reaction rates, and metallocene and nonmetallocene chiral lanthanide complexes have been synthesized for enantioselective hydroamination.
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      Catalytic Markovnikov and anti-Markovnikov functionalization of alkenes and alkynes. Recent developments and trends
      Beller, Matthias; Seayad, Jayasree; Tillack, Annegret; Jiao, Haijun
      Angewandte Chemie, International Edition (2004), 43 (26), 3368-3398CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. The regioselective functionalization of terminal alkenes and alkynes is of utmost importance for the synthesis of a wide variety of org. products. Based on the original observation by Vladimir Markovnikov - the pioneer of this field of research - in the 19th century, the possible regioisomeric products are classified as Markovnikov or anti-Markovnikov products. Contrary to traditional belief, it is nowadays possible to control the regiochem. of various addns. of nucleophiles to alkenes and alkynes by applying different transition-metal catalysts. Recent developments in this area of selective functionalization of alkenes and alkynes are reviewed.
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      Hydroamination: direct addition of amines to alkenes and alkynes
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      Late Transition Metal-Catalyzed Hydroamination and Hydroamidation
      Huang, Liangbin; Arndt, Matthias; Goossen, Kaethe; Heydt, Heinrich; Goossen, Lukas J.
      Chemical Reviews (Washington, DC, United States) (2015), 115 (7), 2596-2697CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. This review examines recent developments in late transition metal-catalyzed hydroamination and -amidation reactions. In this review, usage of the term hydroamidation is not limited to the substrate classes of amides, sulfonamides, and phosphonamides, but extended to structurally related compds. with a similar pKa range and reactivity, such as carbamates, lactams, ureas, amidines, guanidines, etc.
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    8. 8
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      Asymmetric conjugate reduction of α,β-unsaturated esters using a chiral phosphine-copper catalyst
      Appella, Daniel H.; Moritani, Yasunori; Shintani, Ryo; Ferreira, Eric M.; Buchwald, Stephen L.
      Journal of the American Chemical Society (1999), 121 (40), 9473-9474CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A catalyst formed from (S)-p-tol-BINAP, CuCl, and NaOCMe3effects the asym. conjugate redn. of α,β-unsatd. esters in the presence of 4 equiv. of polymethylhydrosiloxane (PMHS). Thus, redn. of (E)-PhCMe:CHCO2Et in toluene under air-free conditions gave (S)-PhCHMeCH2CO2Et in 84% yield with 90% ee. (E)- and (Z)-stereoisomers of α,β-unsatd. esters give enantiomeric β-substituted esters; e.g., Et (E)-geranate Me2C:CHCH2CH2C(Me):CHCO2Et gives Et (R)-citronellate in 85% ee, while Et (Z)-geranate gives Et (S)-citronellate in 80% ee.
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      (a) Berman, A. M.; Johnson, J. S. J. Am. Chem. Soc. 2004, 126, 5680 DOI: 10.1021/ja049474e
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      9a
      Copper-catalyzed electrophilic amination of diorganozinc reagents
      Berman, Ashley M.; Johnson, Jeffrey S.
      Journal of the American Chemical Society (2004), 126 (18), 5680-5681CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The copper-catalyzed electrophilic amination of diorganozinc reagents, employing O-acyl N,N-dialkyl hydroxylamines, e.g., I, as aminating agents, is described. This reaction offered a general method for the prepn. of tertiary amines, e.g., II, in high yields, and easy product isolation (acid/base extractive workup).
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      Mechanistic Studies of the Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents and Development of a Zinc-Free Protocol
      Campbell, Matthew J.; Johnson, Jeffrey S.
      Organic Letters (2007), 9 (8), 1521-1524CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)
      An SN2 mechanism for the copper-catalyzed amination of diorganozinc reagents by O-benzoyl-N,N-dialkylhydroxylamines is supported by following stereochem. defined organometallics through the reaction and by employing the endocyclic restriction test. A copper-catalyzed electrophilic amination of organomagnesium compds. is also described in which the use of zinc halides has been eliminated.
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      9d
      Synthesis of Hindered Anilines: Copper-Catalyzed Electrophilic Amination of Aryl Boronic Esters
      Rucker, Richard P.; Whittaker, Aaron M.; Dang, Hester; Lalic, Gojko
      Angewandte Chemie, International Edition (2012), 51 (16), 3953-3956, S3953/1-S3953/108CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The authors have developed a mild copper-catalyzed electrophilic amination reaction for the synthesis of sterically-hindered anilines from aryl and heteroaryl boronic esters. The new method is compatible with a wide range of functionalities, including chloro, bromo, iodo, carbomethoxy, nitro, hydroxyl, formyl, and methoxy groups. Overall, an exceptionally broad scope and reliability of this new procedure, together with the availability of a wide variety of aryl boronic esters, make it a significant addn. to the existing methods for aniline synthesis.
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      Recent progress in copper-catalyzed electrophilic amination
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      Catalysis Science & Technology (2014), 4 (12), 4169-4177CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      A review. Copper-catalyzed coupling reactions have been recognized as one of the most useful strategies for the formation of C-N bonds. This perspective gives an overview of the recent developments in copper-catalyzed electrophilic amination for the construction of various amines and their derivs., including the electrophilic amination of various organometallic reagents and direct C-H bonds as well as the annulative electrophilic amination of o-alkynylphenols and o-alkynylanilines.
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      A review with 209 refs. The amination reagents are: amines, N-haloamines, O-substituted hydroxylamines, azides, oximes, arenediazonium salts, and dialkyl azodicarboxylates.
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    10. 10
      (a) Zhu, S.; Niljianskul, N.; Buchwald, S. L. J. Am. Chem. Soc. 2013, 135, 15746 DOI: 10.1021/ja4092819
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      10a
      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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      10b
      Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of 1,1-Disubstituted Alkenes
      Zhu, Shaolin; Buchwald, Stephen L.
      Journal of the American Chemical Society (2014), 136 (45), 15913-15916CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Enantioselective synthesis of β-chiral amines has been achieved via copper-catalyzed hydroamination of 1,1-disubstituted alkenes with hydroxylamine esters in the presence of a hydrosilane. This mild process affords a range of structurally diverse β-chiral amines, including β-deuterated amines, in excellent yields with high enantioselectivities. Furthermore, catalyst loading as low as 0.4 mol% could be employed to deliver product in undiminished yield and selectivity, demonstrating the practicality of this method for large-scale synthesis.
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      10c
      Enantioselective synthesis of α-aminosilanes by copper-catalyzed hydroamination of vinylsilanes
      Niljianskul, Nootaree; Zhu, Shaolin; Buchwald, Stephen L.
      Angewandte Chemie, International Edition (2015), 54 (5), 1638-1641CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The synthesis of α-aminosilanes by a highly enantio- and regioselective copper-catalyzed hydroamination of vinylsilanes is reported. The system employs Cu-DTBM-SEGPHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O-benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thus providing access to amino acid mimics and other valuable chiral organosilicon compds.
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      (d) Shi, S.; Buchwald, S. L. Nat. Chem. 2015, 7, 38 DOI: 10.1038/nchem.2131
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      10d
      Copper-catalyzed selective hydroamination reactions of alkynes
      Shi, Shi-Liang; Buchwald, Stephen L.
      Nature Chemistry (2015), 7 (1), 38-44CODEN: NCAHBB; ISSN:1755-4330. (Nature Publishing Group)
      The development of selective reactions that utilize easily available and abundant precursors for the efficient synthesis of amines is a long-standing goal of chem. research. Despite the centrality of amines in a no. of important research areas, including medicinal chem., total synthesis and materials science, a general, selective and step-efficient synthesis of amines is still needed. Here, the authors describe a set of mild catalytic conditions utilizing a single copper-based catalyst that enables the direct prepn. of three distinct and important amine classes (enamines, α-chiral branched alkylamines and linear alkylamines) from readily available alkyne starting materials with high levels of chemoselectivity, regioselectivity and stereoselectivity. This method was applied to the asym. synthesis of rivastigmine and the formal synthesis of several other pharmaceutical agents, including duloxetine, atomoxetine, fluoxetine and tolterodine. Under optimized conditions the synthesis of the target compds. was achieved using copper(II) acetate as a catalyst and 1,1'-(4R)-[4,4'-bi-1,3-benzodioxole]-5,5'-diylbis[1,1-bis[3,5-bis(1,1-dimethylethyl)-4-methoxyphenyl]phosphine] as a catalyst-ligand combination. Alkyne starting materials included 1,1'-(1,2-ethynediyl)bis[benzene], (1-hexynyl)benzene, 1-chloro-3-(ethynyl)benzene, 3-(ethynyl)pyridine, 5-ethynyl-1-[(4-methylphenyl)sulfonyl]-1H-indole, (3,3-diethoxy-1-propyn-1-yl)benzene (acetal). Amine starting materials included N-(benzoyloxy)-N-(phenylmethyl)benzenemethanamine, benzoic acid 2,2,6,6-tetramethyl-1-piperidinyl ester, benzoic acid 4-morpholinyl ester. 3-[[(Trifluoromethyl)sulfonyl]oxy]estra-1,3,5(10)-trien-17-one cyclic 1,2-ethanediyl acetal was also used as a starting material. The title compds. thus formed included N-(ethyl)-N-(methyl)carbamic acid 3-[(1S)-1-(dimethylamino)ethyl]phenyl ester [i.e., (S)-Rivastigmine] and 2-[3-[bis(1-methylethyl)amino]-1-phenylpropyl]-4-(methyl)phenol [i.e., (±)-tolterodine formal synthesis].
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    11. 11
      (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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      11a
      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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      11b
      Copper-Catalyzed Enantioselective Formal Hydroamination of Oxa- and Azabicyclic Alkenes with Hydrosilanes and Hydroxylamines
      Miki, Yuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro
      Organic Letters (2014), 16 (5), 1498-1501CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addn. of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbornanylamines in good yields and good enantiomeric ratios. Thus, e.g., treatment of oxabenzonorbornadiene with morpholino benzoate in presence of CuCl/(R,R)-Ph-BPE, LiO-t-Bu and PMHS in DME afforded aminated product I in 81% yield, 99:1 er.
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    12. 12

      In contrast to the large number of successful examples using dialkylamine transfer reagents (R2NOBz, R ≠ H) in copper-mediated amination reactions, use of the analogous monoalkylamine transfer reagents [RN(H)OBz] remains underdeveloped. For representative examples, see ref 9b and

      (a) Yotphan, S.; Beukeaw, D.; Reutrakul, V. Tetrahedron 2013, 69, 6627 DOI: 10.1016/j.tet.2013.05.127
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      Synthesis of 2-aminobenzoxazoles via copper-catalyzed electrophilic amination of benzoxazoles with O-benzoyl hydroxylamines
      Yotphan, Sirilata; Beukeaw, Danupat; Reutrakul, Vichai
      Tetrahedron (2013), 69 (32), 6627-6633CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)
      An efficient copper-catalyzed electrophilic amination of benzoxazoles with O-benzoyl hydroxylamines is described, employing CuCl catalyst, PPh3 ligand, and LiOtBu base. This simple air-stable copper catalysis enables the prepn. of various 2-aminobenzoxazole derivs. e. g., I at room temp. in good yields.
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      12b
      Copper-Catalyzed α-Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α-Amino Phosphonic Acids and Derivatives
      McDonald, Stacey L.; Wang, Qiu
      Angewandte Chemie, International Edition (2014), 53 (7), 1867-1871CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A direct approach to important α-amino phosphonic acids and its derivs. was developed by using Cu-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the 1st example of C-N bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temp. with ≥0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope.
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      12c
      Copper-Catalyzed Direct Amination of Electron-Deficient Arenes with Hydroxylamines
      Matsuda, Naoki; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro
      Organic Letters (2011), 13 (11), 2860-2863CODEN: ORLEF7; ISSN:1523-7052. (American Chemical Society)
      The C-H amination of electron-deficient arenes such as polyfluoroarenes and azole compds. with O-acylated hydroxylamines effectively proceeds in the presence of a copper catalyst even at room temp. to provide the corresponding anilines and aminoazoles in good yields.
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    13. 13
      (a) Ascic, E.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137, 4666– 4669 DOI: 10.1021/jacs.5b02316
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      13a
      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)

      PPh3 is used as a secondary ligand due to the observed beneficial effects it has on CuH-catalyzed reactions. This concept was developed by Lipshutz:

      Lipshutz, B. H.; Noson, K.; Chrisman, W.; Lower, A. J. Am. Chem. Soc. 2003, 125, 8779 DOI: 10.1021/ja021391f
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      13b
      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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    14. 14

      Attempts to modify the properties of dialkylamine transfer reagents by adjusting the benzoate group have been reported by Johnson. (9c)

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    15. 15
      (a)

      Alkyl carboxylate-based amine transfer reagents 13 and 14 were also tested. Reagent 14 containing a bulky adamantyl group provided yields of 11b and 11c similar to that of 4-(dimethylamino)benzoate 10e. Due to the availability of the 4-(dimethylamino)benzoic acid and its ease of removal after reaction, (15b) 4-(dimethylamino)benzoates were used for most of this work

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      (b)

      4-(Dimethylamino)benzoic acid is sparingly soluble in Et2O, EtOAc, or CH2Cl2 but readily soluble in 2 M aqueous K2CO3.

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    16. 16

      Attempts to use 10e in the hydroamination of β,β-disubstituted styrenes or terminal unactivated alkenes gave low yields of secondary amine products.

      There is no corresponding record for this reference.
    17. 17
      (a) Grigg, R. D.; Van Hoveln, R.; Schomaker, J. M. J. Am. Chem. Soc. 2012, 134, 16131 DOI: 10.1021/ja306446m
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      Several methodologies have been developed to convert α-amino acid esters into the corresponding primary N-hydroxylamines. For references, see:

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    22. 22

      Formation of BnNH2 and the silylated ester 37 could be detected by GC/MS and 1H NMR analysis.

      There is no corresponding record for this reference.
    23. 23

      Reduction of the dialkylamine transfer agent 36 is much slower. Approximately, 60% of 36 was consumed after 20 h under described conditions.

      There is no corresponding record for this reference.
    24. 24

      A manuscript detailing the use of related modified amine transfer reagents to effect hydroamination of unactivated internal alkenes is in press.

      There is no corresponding record for this reference.

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    Experimental procedures and characterization data for all compounds. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b05446.


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    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.

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