Overcoming Selectivity Issues in Reversible Catalysis – A Transfer Hydrocyanation Exhibiting High Kinetic Control
Preprints are manuscripts made publicly available before they have been submitted for formal peer review and publication. They might contain new research findings or data. Preprints can be a draft or final version of an author's research but must not have been accepted for publication at the time of submission.
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.
Read the published paper
in Journal of the American Chemical Society