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Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers
Author(s) -
Xu Wentao,
Ma Junyang,
Yuan XiangAi,
Dai Jie,
Xie Jin,
Zhu Chengjian
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201805927
Subject(s) - umpolung , chemistry , alkyl , regioselectivity , catalysis , ether , hydrogen bond , molecule , stereochemistry , combinatorial chemistry , organic chemistry , nucleophile
The first transition‐metal‐free, site‐specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp 3 )–SCF 3 coupling under redox‐neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL‐based phosphorothiols can site‐selectively cleave tertiary sp 3 C(sp 3 )–O ether bonds in complex molecules initiated by a polarity‐matching hydrogen‐atom‐transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp 3 )−H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C−O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site‐selective C−O bond functionalization of unsymmetrical tertiary alkyl ethers.