Nucleophilic Isomerization of Epoxides by Pincer-Rhodium Catalysts: Activity Increase and Mechanistic Insights

Herein, we present the efficient isomerization of epoxides into methyl ketones with a novel pincer-rhodium complex under very mild conditions. The catalyst system has an excellent functional group tolerance and a wide array of epoxides was tested. The corresponding methyl ketones were obtained in very high yields with excellent chemo- and regioselectivity. In addition, we investigated mechanistic details like the isomerization of the catalyst, and we obtained evidence that the catalytic cycle follows a beta-hydride elimination-reductive elimination pathway after the nucleophilic ring opening of the epoxide.