Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 9, Pages 3322-3330Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b12768
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Funding
- NIHGMS [R01 GM-103558-05]
- NIH [F32 GM119362-01A1]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM103558, F32GM119362] Funding Source: NIH RePORTER
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Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated spin-center shift (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective alpha-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.
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