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Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me 3 SiCF 2 H
Author(s) -
Chen Dingben,
Ni Chuanfa,
Zhao Yanchuan,
Cai Xian,
Li Xinjin,
Xiao Pan,
Hu Jinbo
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201605280
Subject(s) - nucleophile , chemistry , catalysis , reactivity (psychology) , alkali metal , salt (chemistry) , nucleophilic addition , 18 crown 6 , ion , medicinal chemistry , metal , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology
A pentacoordinate bis(difluoromethyl)silicate anion, [Me 3 Si(CF 2 H) 2 ] − , is observed for the first time by the activation of Me 3 SiCF 2 H with a nucleophilic alkali‐metal salt and 18‐crown‐6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me 3 SiCF 2 H by using a combination of CsF and 18‐crown‐6 as the initiation system. Mechanistic investigations demonstrate that [(18‐crown‐6)Cs] + [Me 3 Si(CF 2 H) 2 ] − is a key intermediate in this catalytic reaction.