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

preprint
submitted on 04.03.2020, 10:35 and posted on 04.03.2020, 13:19 by Benjamin N. Bhawal, Julia C. Reisenbauer, Christian Ehinger, Bill Morandi

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.

Funding

EU/ERC Horizon 2020 (ShuttleCat 757608)

ETH Zurich

Max-Planck-Society

Leverhulme Trust

Stipendienfonds Schweizerische Chemische Industrie (SSCI)

History

Email Address of Submitting Author

morandib@ethz.ch

Institution

ETH Zurich

Country

Switzerland

ORCID For Submitting Author

0000-0003-3968-1424

Declaration of Conflict of Interest

A patent application for transfer hydrocyanation has been filed (US2019031602 (A1))

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