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

Benjamin N. Bhawal, Julia C. Reisenbauer, Christian Ehinger, Bill Morandi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C-CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. 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.

Original languageEnglish
Pages (from-to)10914-10920
Number of pages7
JournalJournal of the American Chemical Society
Volume142
Issue number25
Early online date1 Jun 2020
DOIs
Publication statusPublished - 24 Jun 2020

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