Regio-, diastereo- and enantioselectivity in the photocatalytic generation of carbanions via hydrogen atom transfer and reductive radical-polar crossover

A sequence involving photocatalytic hydrogen atom transfer (HAT), reductive radical-polar crossover (RRPCO), and protonation/deuteration for stereochemical editing at benzylic positions is described. A systematic screening of substrates with benzylic C–H bonds provides trends in reactivity for C–H a...

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Published in:Organic chemistry frontiers an international journal of organic chemistry 2024-10, Vol.11 (20), p.5890-5900
Main Authors: Grotjahn, Sascha, Müller, Lea, Pattanaik, Aryaman, Falk, Alexander, Barison, Giorgia, Bauer, Jonathan O, Rehbein, Julia, Gschwind, Ruth M, König, Burkhard
Format: Article
Language:English
Subjects:
Deuteration
Enantiomers
Hydrogen atoms
Isomerization
Protonation
Radicals
Reagents
Silanes
Substrates
Thiols
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container_issue 20
container_start_page 5890
container_title Organic chemistry frontiers an international journal of organic chemistry
container_volume 11
creator Grotjahn, Sascha
Müller, Lea
Pattanaik, Aryaman
Falk, Alexander
Barison, Giorgia
Bauer, Jonathan O
Rehbein, Julia
Gschwind, Ruth M
König, Burkhard
description A sequence involving photocatalytic hydrogen atom transfer (HAT), reductive radical-polar crossover (RRPCO), and protonation/deuteration for stereochemical editing at benzylic positions is described. A systematic screening of substrates with benzylic C–H bonds provides trends in reactivity for C–H activation by silane thiols. A cis/trans isomerization of dihydrobenzofurans proceeding under kinetic control in the HAT step is presented, and the concept is transferred to a deracemization by chiral silane thiols as HAT reagents in a proof of concept study.
doi_str_mv 10.1039/d4qo01219d
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subjects Deuteration
Enantiomers
Hydrogen atoms
Isomerization
Protonation
Radicals
Reagents
Silanes
Substrates
Thiols
title Regio-, diastereo- and enantioselectivity in the photocatalytic generation of carbanions via hydrogen atom transfer and reductive radical-polar crossover
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