Insights into the Activation Mode of α-Carbonyl Sulfoxonium Ylides in Rhodium-Catalyzed C-H Activation: A Theoretical Study.

ABSTRACT: 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.

SUBMITTER: Zhang D 

PROVIDER: S-EPMC9278107 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature