Open AccessInsights into the Activation Mode of α‐Carbonyl Sulfoxonium Ylides in Rhodium‐Catalyzed C−H Activation: A Theoretical Study
Author(s) -
Zhang Dianmin,
He Xiaofang,
Yang Tao,
Liu Song
Publication year - 2022
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202100254
Subject(s) - carbene , chemistry , protonation , catalysis , substituent , rhodium , yield (engineering) , density functional theory , stepwise reaction , activation energy , medicinal chemistry , computational chemistry , transition state , photochemistry , organic chemistry , reaction rate constant , materials science , order of reaction , kinetics , ion , physics , quantum mechanics , metallurgy
A computational study has been performed to investigate the mechanism of Rh III ‐catalyzed C−H bond activation using sulfoxonium ylides as a carbene precursor. The stepwise and concerted activation modes for sulfoxonium ylides were investigated. Detailed theoretical results showed that the favored stepwise pathway involves C−H bond activation, carbonization, carbene insertion, and protonation. The free energy profiles for dialkylation of 2‐phenylpyridine were also calculated to account for the low yield of this reaction. Furthermore, the substituent effect was elucidated by comparing the energy barriers for the protonation of meta ‐ and para ‐substituted sulfoxonium ylides calculated by density functional theory.