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Copper‐Catalyzed and Proton‐Directed Selective Hydroxymethylation of Alkynes with CO 2
Author(s) -
Wang MeiYan,
Jin Xin,
Wang Xiaofei,
Xia Shumei,
Wang Yue,
Huang Shouying,
Li Ying,
He LiangNian,
Ma Xinbin
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202012768
Subject(s) - protonation , allylic rearrangement , chemistry , catalysis , alkyne , proton , combinatorial chemistry , medicinal chemistry , copper , organic chemistry , physics , ion , quantum mechanics
An intriguing strategy for copper‐catalyzed hydroxymethylation of alkynes with CO 2 and hydrosilane was developed. Switched on/off a proton source, for example, t BuOH, direct hydroxymethylation and reductive hydroxymethylation could be triggered selectively, delivering a series of allylic alcohols and homobenzylic alcohols, respectively, with high levels of Z / E , regio‐ and enantioselectivity. Such a selective synthesis is attributed to the differences in response of vinylcopper intermediate to proton and CO 2 . The protonation of vinylcopper species is demonstrated to be prior to hydroxymethylation, thus allowing a diversion from direct alkyne hydroxymethylation to reductive hydroxymethylation in the presence of suitable proton.