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

• DOI: 10.1021/jacs.0c03184
• Publication Date: 2020-06-01T14:02:37Z
• Authors: Benjamin N. Bhawal; Julia C. Reisenbauer; Christian Ehinger; Bill Morandi
• Keywords: Hydrocyanation; Reductive elimination; Kinetic resolution

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