Overcoming Selectivity Issues in Reversible Catalysis – A Transfer Hydrocyanation Exhibiting High Kinetic Control

Typically, reversible catalytic reactions operate under thermodynamic control and thus establishing a selective catalytic system poses a considerable challenge. In this manuscript, we report a reversible yet kinetically selective transfer hydrocyanation protocol. Selectivity is achieved by exploiting the lower barrier for C–CN oxidative addition and reductive elimination at benzylic positions in the absence of co-catalytic Lewis acid. The design of a novel type of HCN donor was crucial to realizing this practical, branched-selective, HCN-free transfer hydrocyanation. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.