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Nickel‐Catalyzed Electrochemical C(sp 3 )−C(sp 2 ) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides **
Author(s) -
Luo Jian,
Hu Bo,
Wu Wenda,
Hu Maowei,
Liu T. Leo
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202014244
Subject(s) - chemistry , electrophile , electrosynthesis , electrochemistry , catalysis , coupling reaction , nucleophile , aryl , electrolysis , transmetalation , organic synthesis , bromide , halide , inorganic chemistry , combinatorial chemistry , organic chemistry , electrode , electrolyte , alkyl
Reported here is the redox neutral electrochemical C(sp 2 )−C(sp 3 ) cross‐coupling reaction of bench‐stable aryl halides or β‐bromostyrene (electrophiles) and benzylic trifluoroborates (nucleophiles) using nonprecious, bench‐stable NiCl 2 ⋅glyme/polypyridine catalysts in an undivided cell configuration under ambient conditions. The broad reaction scope and good yields of the Ni‐catalyzed electrochemical coupling reactions were confirmed by 50 examples of aryl/β‐styrenyl chloride/bromide and benzylic trifluoroborates. Potential applications were demonstrated by electrosynthesis and late‐stage functionalization of pharmaceuticals and natural amino acid modification, and three reactions were run on gram‐scale in a flow‐cell electrolyzer. The electrochemical C−C cross‐coupling reactions proceed through an unconventional radical transmetalation mechanism. This method is highly productive and expected to find wide‐spread applications in organic synthesis.