Mechanism in palladium-catalyzed dearomative allylic reactions of benzyl phosphates with allyl borates: Insights from DFT calculations

Dearomatic reactions are very important to build alicyclic moieties and expand the structural diversity. Muto and Yamaguchi recently investigated the Pd-catalyzed dearomative allylic reactions of allyl borates with benzyl phosphates to give final compounds. Herein, the calculations were conducted to explore the reaction mechanism and selectivity, and the results clarified that the dearomatic product through carbon-carbon bond formation between eta(3)-exo-(naphthyl)methyl para-carbon atom and allyl terminal carbon atom (TS3 = 7.3 kcal/mol) is energetically more favorable than the other carbon-carbon bond formation paths to afford aromatic and dearomatic compounds.