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Mechanistic Investigation of a Synthetic Route to Biaryls by the Sigmatropic Rearrangement of Arylsulfonium Species
Author(s) -
Yanagi Tomoyuki,
Yorimitsu Hideki
Publication year - 2021
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.202101735
Subject(s) - sigmatropic reaction , trifluoroacetic anhydride , chemistry , yield (engineering) , rearrangement reaction , concerted reaction , computational chemistry , aryl , reaction mechanism , claisen rearrangement , cascade , phenols , smiles rearrangement , photochemistry , organic chemistry , physics , catalysis , thermodynamics , alkyl , chromatography
A comprehensive mechanistic investigation was conducted on the coupling reaction of aryl sulfoxides with phenols by using trifluoroacetic anhydride to yield biaryls. NMR experiments revealed that our previously proposed mechanism, which consists of a cascade of an interrupted Pummerer reaction and a rate‐determining [3,3] sigmatropic rearrangement, is reasonable. The electronic effects of the substrates were also evaluated to elucidate the nature of the rearrangement step. Based on experimental observations and theoretical calculations, we conclude that the rearrangement is highly asynchronous and stepwise rather than concerted when electron‐rich phenols are employed for the reaction.