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

[Image: see text] 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, gi...

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Autores principales: Harris, Georgia R., Trowbridge, Aaron D., Gaunt, Matthew J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9926512/
https://www.ncbi.nlm.nih.gov/pubmed/36724345
http://dx.doi.org/10.1021/acs.orglett.2c04308
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author Harris, Georgia R.
Trowbridge, Aaron D.
Gaunt, Matthew J.
author_facet Harris, Georgia R.
Trowbridge, Aaron D.
Gaunt, Matthew J.
author_sort Harris, Georgia R.
collection PubMed
description [Image: see text] 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.
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spelling pubmed-99265122023-02-15 A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines Harris, Georgia R. Trowbridge, Aaron D. Gaunt, Matthew J. Org Lett [Image: see text] 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. American Chemical Society 2023-02-01 /pmc/articles/PMC9926512/ /pubmed/36724345 http://dx.doi.org/10.1021/acs.orglett.2c04308 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Harris, Georgia R.
Trowbridge, Aaron D.
Gaunt, Matthew J.
A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title_full A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title_fullStr A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title_full_unstemmed A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title_short A Chiral Amine Transfer Approach to the Photocatalytic Asymmetric Synthesis of α-Trialkyl-α-tertiary Amines
title_sort chiral amine transfer approach to the photocatalytic asymmetric synthesis of α-trialkyl-α-tertiary amines
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9926512/
https://www.ncbi.nlm.nih.gov/pubmed/36724345
http://dx.doi.org/10.1021/acs.orglett.2c04308
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