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Chiral Brønsted Acid Catalyzed Enantioconvergent Propargylic Substitution Reaction of Racemic Secondary Propargylic Alcohols with Thiols
Author(s) -
Kikuchi Jun,
Takano Kyohei,
Ota Yusuke,
Umemiya Shigenobu,
Terada Masahiro
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001609
Subject(s) - enantioselective synthesis , chemistry , stereocenter , catalysis , organic chemistry , nucleophile , brønsted–lowry acid–base theory , nucleophilic substitution , substitution reaction , electrophile , chirality (physics) , medicinal chemistry , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model
Despite the significant progress of the enantioselective reaction using chiral catalysts, the enantioselective nucleophilic substitution reaction at the chiral sp 3 ‐hybridized carbon atom of a racemic electrophile has not been largely explored. Herein, we report the enantioconvergent propargylic substitution reaction of racemic propargylic alcohols with thiols using chiral bis‐phosphoric acid as the chiral Brønsted acid catalyst. The substitution products were formed in high yields with high enantioselectivities in most cases. The cation‐stabilizing effect of the sulfur functional group introduced at the alkynyl terminus is the key to achieving the efficient enantioconvergent process, in which chiral information originating from not only the racemic stereogenic center but also the formed contact ion pair is completely eliminated from the present system.