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Light‐Driven Carbene Catalysis for the Synthesis of Aliphatic and α‐Amino Ketones
Author(s) -
Bay Anna V.,
Fitzpatrick Keegan P.,
GonzálezMontiel Gisela A.,
Farah Abdikani Omar,
Cheong Paul HaYeon,
Scheidt Karl A.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105354
Subject(s) - carbene , chemistry , steric effects , catalysis , reactivity (psychology) , ketone , substrate (aquarium) , combinatorial chemistry , surface modification , photochemistry , organic chemistry , medicine , oceanography , alternative medicine , pathology , geology
Single‐electron N‐heterocyclic carbene (NHC) catalysis has gained attention recently for the synthesis of C−C bonds. Guided by density functional theory and mechanistic analyses, we report the light‐driven synthesis of aliphatic and α‐amino ketones using single‐electron NHC operators. Computational and experimental results reveal that the reactivity of the key radical intermediate is substrate‐dependent and can be modulated through steric and electronic parameters of the NHC. Catalyst potential is harnessed in the visible‐light driven generation of an acyl azolium radical species that undergoes selective coupling with various radical partners to afford diverse ketone products. This methodology is showcased in the direct late‐stage functionalization of amino acids and pharmaceutical compounds, highlighting the utility of single‐electron NHC operators.