Theoretical investigation on the palladium-catalyzed diastereoselective oxidative carbocyclization of enallenes assisted by hydroxyl group

The reaction mechanisms on the palladium-catalyzed oxidative carbocyclization of enallenes assisted by weak coordination hydroxyl groups have been computationally investigated by employing density functional theory (DFT) calculations. The allyl C-H activation is the rate-determining step and the olefin insertion is the diastereoselectivity-determining step. The calculated results can explain the lower diastereoselectivity obtained in the experiment when the OH group was replaced by OAc or OMe.