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C(sp 3 )−H Cyanation Promoted by Visible‐Light Photoredox/Phosphate Hybrid Catalysis
Author(s) -
Wakaki Takayuki,
Sakai Kentaro,
Enomoto Takafumi,
Kondo Mio,
Masaoka Shigeyuki,
Oisaki Kounosuke,
Kanai Motomu
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801746
Subject(s) - cyanation , radical , chemistry , catalysis , photochemistry , phosphate , dissociation (chemistry) , photoredox catalysis , bond cleavage , nucleophile , visible spectrum , combinatorial chemistry , photocatalysis , organic chemistry , materials science , optoelectronics
Abstract Inspired by the reaction mechanism of photo‐induced DNA cleavage in nature, a C(sp 3 )−H cyanation reaction promoted by visible‐light photoredox/phosphate hybrid catalysis was developed. Phosphate radicals, generated by one‐electron photooxidation of phosphate salt, functioned as a hydrogen‐atom‐transfer catalyst to produce nucleophilic carbon radicals from C(sp 3 )−H bonds with a high bond‐dissociation energy. The resulting carbon radicals were trapped by a cyano radical source (TsCN) to produce the C−H cyanation products. Due to the high functional‐group tolerance and versatility of the cyano group, the reaction will be useful for realizing streamlined building block syntheses and late‐stage functionalization of drug‐like molecules.