Asymmetric Hydrogenation of Imines

Li, Wei; Zhang, Xumu

doi:10.1007/128_2013_483

Cited by 35 publications

(22 citation statements)

References 142 publications

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“…Enantiomerically pure amines are frequently encountered in natural products, pharmaceuticals, and agrochemicals (Figure A) . They are also important building blocks and chiral auxiliaries in asymmetric synthesis.…”

Section: Introductionmentioning

confidence: 99%

Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates

2021

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Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enecarbamates (N-Cbz-protected enamines) and alkyl halides with high regio-and enantioselectivity. The method works for both nonactivated and activated alkyl halides and is able to produce enantiomerically enriched amines with two minimally differentiated α-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the postproduct functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bioactive compounds.

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Section: Introductionmentioning

confidence: 99%

Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates

2021

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“…Due to their importance and ubiquity, significant efforts have been made toward the construction of enantioenriched amines. 1 Hydroamination, the formal addition of a nitrogen and hydrogen atom across a carbon–carbon π-bond, represents a particularly attractive and direct method for appending amino groups onto a molecule. Although significant progress has been achieved in this regard using late transition metal catalysis, a number of drawbacks have limited the utilization of these methodologies.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins

2015

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Enantioselective copper(I) hydride (CuH)-catalyzed hydroamination has undergone significant development over the past several years. To gain a general understanding of the factors governing these reactions, kinetic and spectroscopic studies were performed on the CuH-catalyzed hydroamination of styrene. Reaction profile analysis, rate order assessment, and Hammett studies indicate that the turnover-limiting step is regeneration of the CuH catalyst by reaction with a silane, with a phosphine-ligated copper(I) benzoate as the catalyst resting state. Spectroscopic, electrospray ionization mass spectrometry, and nonlinear effect studies are consistent with a monomeric active catalyst. With this insight, targeted reagent optimization led to the development of an optimized protocol with an operationally simple setup (ligated copper(II) precatalyst, open to air) and short reaction times (<30 min). This improved protocol is amenable to a diverse range of alkene and alkyne substrate classes.

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“…Chiral, nonracemic amines are exceedingly important compounds that find use in a myriad of research areas and commercial settings . They are often obtained by resolution or chiral auxiliary chemistry, and catalytic enantioselective methods for their preparation have proven challenging, especially when the stereocenter bears two nearly equivalent alkyl groups, as observed in 3 and 4 . , Recently, very nice examples of enantioselective intermolecular hydroamination have appeared . These reactions employ symmetrical olefin starting materials or directing groups to control regioselectivity.…”

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confidence: 99%

Catalytic Enantioselective Synthesis of Amino Skipped Diynes

2016

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The Cu-catalyzed synthesis of nonracemic 3-amino skipped diynes via an enantiodetermining C-C bond formation is described using StackPhos as ligand. Despite challenging issues of reactivity and stereoselectivity inherent to these chiral skipped diynes, the reaction tolerates an extremely broad substrate scope with respect to all components and provides the title compounds in excellent enantiomeric excess. The alkyne moieties are demonstrated here to be useful synthetic handles, and 3-amino skipped diynes are convenient building blocks for enantioselective synthesis.

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Asymmetric Hydrogenation of Imines

Cited by 35 publications

References 142 publications

Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates

Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates

Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins

Catalytic Enantioselective Synthesis of Amino Skipped Diynes

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