DFT Studies on the Rh‐Catalyzed Oxidative Coupling Cyclization of 2,3‐Allenols

Abstract The mechanism of the Rh‐catalyzed oxidative coupling cyclization of 2,3‐allenols has been studied by DFT calculations. The whole process of the current reaction involves the nucleophilic cyclic oxyrhodation/ stereodefined carborhodation/ β ‐H elimination/ reductive elimination. Calculated results reveal that the carborhodation step is not only the rate‐limiting step but also determines the stereo‐selectivity.