Theoretical Study of Ruthenium(0)-Catalyzed Transfer Hydrogenative Cycloaddition of Cyclohexadiene and Norbornadiene with 1,2-Diols to Form Bridged Carbocycles

The recent success of Krische et al. (Angew. Chem., Int. Ed. 2017, 56, 14667–14671) in achieving a ruthenium(0)-catalyzed transfer hydrogenative cycloaddition of 1,2-diols with cyclohexadiene and norbornadiene in excellent yield with exo- and diastereoselectivity represents an exciting development in the synthesis of bridged carbocycles. In the present work, the possible catalytic mechanisms and origin of the exo- and diastereoselectivity for cyclohexadiene and norbornadiene were studied in detail by density functional theory calculations. The theoretical results indicate that the exoselective pathway for the cyclohexadiene substrate proceeds by a novel two-step successive C–C coupling, while the endoselective pathway undergoes the C–C coupling reaction in a conventional concerted manner. The origin of the preferential chemoselectivity of dione–cyclohexadiene C–C coupling over aromatization to benzene was investigated. Aromatization to benzene is unfavorable because of the large distortion energy of the three-membered ring in the transition state of hydrogen migration. From distortion/interaction analysis, for norbornadiene, the distortion energy plays the main role in determining the exoselectivity.