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The ortho ‐Difluoroalkylation of Aryliodanes with Enol Silyl Ethers: Rearrangement Enabled by a Fluorine Effect
Author(s) -
Huang Xin,
Zhang Yage,
Zhang Chaoshen,
Zhang Lei,
Xu Ying,
Kong Lichun,
Wang ZhiXiang,
Peng Bo
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201900745
Subject(s) - silylation , chemistry , enol , fluorine , nucleophile , silyl enol ether , medicinal chemistry , photochemistry , organic chemistry , catalysis
Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox‐neutral manner to afford ortho ‐iodo difluoroalkylated arenes. The remaining iodide group provides a versatile platform for converting the products into various valuable difluoroalkylated arenes. The reaction shows excellent functional‐group compatibility and broad substrate scope. A DFT mechanistic study suggests that the fluorine effect facilitates a subtle nucleophilic attack of the oxygen atom of enol silyl ethers onto aryliodanes, therefore leading to a rearrangement.