Kinetic Resolution of α-Tertiary Propargylic Amines through Asymmetric Remote Aminations of Anilines

Pan, Yongkai; Wang, Donglei; Chen, Yunrong; Zhang, Dekun; Liu, Wei; Yang, Xiaoyu

doi:10.1021/acscatal.1c02331

Cited by 28 publications

(3 citation statements)

References 63 publications

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“…Encouraged by the high performance for KR of 2,2disubstituted hydroquinolines via asymmetric C-H aminations, recently our group extended this approach to the KR of more challenging acyclic -tertiary propargylic amines (Scheme 45). 75 A wide range of aryl and alkyl groups at the -position, as well as the alkynyl and N-aryl variants of the propargylic amines 133 were well compatible with this reaction, providing excellent KR performances (with s-factors up to 111). More encouragingly, KR reaction of -tertiary amine bearing an -cyano group 135 (the Strecker reaction product) could also be readily fulfilled using this method, which provided both recovered (S)-135 and the amination product 136 with high enantioselectivities.…”

Section: Scheme 44 Kr Of Hydroquinolines With -Disubstitution Via C...mentioning

confidence: 95%

Catalytic Kinetic Resolution and Desymmetrization of Amines

Liu¹,

Wang²,

Zhang³

et al. 2022

Synlett

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Optically active amines represent critically important subunits in bioactive natural products and pharmaceuticals, as well as key scaffolds in chiral catalysts and ligands. Kinetic resolution of racemic amines and enantioselective desymmetrization of prochiral amines have proved to be efficient methods to access enantioenriched amines, especially when the racemic or prochiral amines were easy to prepare while the chiral ones are difficult to be accessed directly. In this review, we systematically summarized the development of kinetic resolution and desymmetrization of amines through nonenzymatic asymmetric catalytic approaches in the last two decades.

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Section: Scheme 44 Kr Of Hydroquinolines With -Disubstitution Via C...mentioning

confidence: 95%

Catalytic Kinetic Resolution and Desymmetrization of Amines

Liu¹,

Wang²,

Zhang³

et al. 2022

Synlett

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“…and propargylic tertiary C-H bonds (3l, 120 TTN, 67% e.e.). The absolute stereochemistry for enzymatic product 3f was assigned as S by comparing the elution order of the two enantiomers with a literature report 40 and through X-ray crystallography (see SI, Section 8). The other α-tertiary primary amines 3 were assigned by analogy.…”

Section: Substrate Scope Study Of Tertiary C-h Primary Aminase P411-t...mentioning

confidence: 99%

Biocatalytic, Enantioenriched Primary Amination of Tertiary C–H Bonds

Mao,

Gao,

Qin

et al. 2023

Preprint

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Intermolecular functionalization of tertiary C–H bonds to construct fully substituted stereogenic carbon centers represents a formidable challenge: without the assistance of directing groups, the state-of-the-art catalysts struggle to introduce chirality to racemic tertiary sp3-carbon centers. Direct asymmetric functionalization of such centers is a worthy reactivity and selectivity goal for modern biocatalysis. Here we present an engineered nitrene transferase (P411-TEA-5274), derived from a bacterial cytochrome P450, that is capable of aminating tertiary C–H bonds to provide chiral α-tertiary primary amines with high efficiency (up to 2300 total turnovers) and selectivity (up to >99% enantiomeric excess (e.e.)). The construction of fully substituted stereocenters with methyl and ethyl groups underscores the enzyme’s remarkable selectivity. A comprehensive substrate scope study demonstrates the biocatalyst’s compatibility with diverse functional groups and tertiary C–H bonds. Mechanistic studies, incorporating both experimental and computational data, elucidate how active-site residues distinguish between the enantiomers and enable the enzyme to perform this transformation with excellent enantioselectivity.

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“…Recently, our group has developed a highly efficient kinetic resolution method for arylamines bearing central [41][42][43] or axial chirality 44,45 , by the utilization of chiral phosphoric acid [46][47][48][49] (CPA) catalyzed asymmetric amination reaction with commercially available azodicarboxylates 50,51 . Herein, we report on the efficient and versatile KR of a variety of substituted amido[2.2]paracyclophanes, including those with pseudo-geminal, pseudo-ortho, pseudo-meta and pseudopara disubstitutions, through the CPA-catalyzed asymmetric amination protocol, in which both enantiomers of the substituted amido [2.2] paracyclophanes could be readily afforded by the facile derivatization of the C-H amination products (Fig.…”

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confidence: 99%

Kinetic resolution of substituted amido[2.2]paracyclophanes via asymmetric electrophilic amination

Yu,

Bao,

Zhang

et al. 2023

Nat Commun

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Planar chiral [2.2]paracyclophane derivatives are a type of structurally intriguing and practically useful chiral molecules, which have found a range of important applications in the field of asymmetric catalysis and material science. However, access to enantioenriched [2.2]paracyclophanes represents a longstanding challenge in organic synthesis due to their unique structures, which are still highly dependent on the chiral chromatography separation technique and classical chemical resolution strategy to date. In this work, we report on an efficient and versatile kinetic resolution protocol for various substituted amido[2.2]paracyclophanes, including those with pseudo-geminal, pseudo-ortho, pseudo-meta and pseudo-para disubstitutions, using chiral phosphoric acid (CPA)-catalyzed asymmetric amination reaction, which was also applicable to the enantioselective desymmetrization of an achiral diamido[2.2]paracyclophane. Detailed experimental studies shed light on a new reaction mechanism for the electrophilic aromatic C-H amination, which proceeded through sequential triazane formation and N[1,5]-rearrangement. The facile large-scale kinetic resolution reaction and diverse derivatizations of both the recovered chiral starting materials and the C-H amination products showcased the potential of this method.

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Kinetic Resolution of α-Tertiary Propargylic Amines through Asymmetric Remote Aminations of Anilines

Cited by 28 publications

References 63 publications

Catalytic Kinetic Resolution and Desymmetrization of Amines

Catalytic Kinetic Resolution and Desymmetrization of Amines

Biocatalytic, Enantioenriched Primary Amination of Tertiary C–H Bonds

Kinetic resolution of substituted amido[2.2]paracyclophanes via asymmetric electrophilic amination

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