Pd-Catalyzed γ-Acetoxylation of Alkylamides: Structural Influence of Directing Groups
Peng‐Yu Liu, Shi‐Chen Zhao, Mingyuan Zhang, Lijuan Song, Caiping Wang, Fang Yu, Qingtao Meng, Zhiqiang Zhang, Yu‐Peng He
Abstract
Although direct acetoxylation and cyclization of alkylamide have been extensively reported, investigation of the structural influence of directing groups on selectivity is limited. Pd-catalyzed 2-methoxyiminoacyl (MIA) assisted γ-acetoxylation of alkylamides has been developed. Further DFT studies have demonstrated that the directing groups have a significant influence on the reductive elimination step. The strong electron-donating effect of the OMe group in MIA leads to the preferential formation of a five-membered cyclopalladium (OAc-Pd-C) complex, which favors the acetoxylation pathway.
Topics & Concepts
ChemistryCatalysisSelectivityMedicinal chemistryReductive eliminationCombinatorial chemistryStereochemistryOrganic chemistryCatalytic C–H Functionalization MethodsOxidative Organic Chemistry ReactionsCatalytic Cross-Coupling Reactions