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A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines.

ABSTRACT: A long-standing challenge within radical chemistry is that of controlling the absolute stereochemistry of the products. Here, we report the stereocontrolled addition of α-amino radicals reductively generated from imines via visible-light-mediated photoredox-catalysis to alkenes, giving rise to enantioenriched α-trialkyl-α-tertiary amines. This process exploits a commercially available phenylglycinol derivative as a source of both nitrogen and chiral information. DFT studies support a stereochemical model whereby an intramolecular H-bond rigidifies the transition state of the enantiodetermining step.

SUBMITTER: Harris GR

PROVIDER: S-EPMC9926512 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines.

Harris Georgia R GR Trowbridge Aaron D AD Gaunt Matthew J MJ

Organic letters 20230201 5

A long-standing challenge within radical chemistry is that of controlling the absolute stereochemistry of the products. Here, we report the stereocontrolled addition of α-amino radicals reductively generated from imines via visible-light-mediated photoredox-catalysis to alkenes, giving rise to enantioenriched α-trialkyl-α-tertiary amines. This process exploits a commercially available phenylglycinol derivative as a source of both nitrogen and chiral information. DFT studies support a stereochemi ...[more]

PMID: 36724345

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