Insights into the Activation Mode of α‐Carbonyl Sulfoxonium Ylides in Rhodium‐Catalyzed C−H Activation: A Theoretical Study
Dianmin Zhang,
Xiaofang He,
Tao Yang,
Dr. Song Liu
Affiliations
Dianmin Zhang
Chongqing Key Laboratory of Environmental Materials and Remediation Technologies College of Chemistry and Environmental Engineering Chongqing University of Arts and Sciences Chongqing 402160 China
Xiaofang He
Chongqing Key Laboratory of Environmental Materials and Remediation Technologies College of Chemistry and Environmental Engineering Chongqing University of Arts and Sciences Chongqing 402160 China
Tao Yang
Chongqing Key Laboratory of Environmental Materials and Remediation Technologies College of Chemistry and Environmental Engineering Chongqing University of Arts and Sciences Chongqing 402160 China
Dr. Song Liu
Chongqing Key Laboratory of Environmental Materials and Remediation Technologies College of Chemistry and Environmental Engineering Chongqing University of Arts and Sciences Chongqing 402160 China
Abstract A computational study has been performed to investigate the mechanism of RhIII‐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.
