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Photoredox‐Catalyzed Site‐Selective α‐C(sp 3 )−H Alkylation of Primary Amine Derivatives
Author(s) -
Ashley Melissa A.,
Yamauchi Chiaki,
Chu John C. K.,
Otsuka Shinya,
Yorimitsu Hideki,
Rovis Tomislav
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201812227
Subject(s) - photoredox catalysis , chemistry , amine gas treating , intramolecular force , alkylation , catalysis , primary (astronomy) , radical , tertiary amine , combinatorial chemistry , intermolecular force , selectivity , photochemistry , intramolecular reaction , amination , stereochemistry , organic chemistry , molecule , photocatalysis , physics , astronomy
The synthetic utility of tertiary amines to oxidatively generate α‐amino radicals is well established, however, primary amines remain challenging because of competitive side reactions. This report describes the site‐selective α‐functionalization of primary amine derivatives through the generation of α‐amino radical intermediates. Employing visible‐light photoredox catalysis, primary sulfonamides are coupled with electron‐deficient alkenes to efficiently and mildly construct C−C bonds. Interestingly, a divergence between intermolecular hydrogen‐atom transfer (HAT) catalysis and intramolecular [1,5] HAT was observed through precise manipulation of the protecting group. This dichotomy was leveraged to achieve excellent α/δ site‐selectivity.