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

preprint
submitted on 04.03.2020 and posted on 04.03.2020 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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