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

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Bhawal,  Benjamin N.
ETH Zürich;
Research Group Morandi, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Reisenbauer,  Julia C.
ETH Zürich;
Research Group Morandi, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons145542

Morandi,  Bill
ETH Zürich;
Research Group Morandi, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Bhawal, B. N., Reisenbauer, J. C., Ehinger, C., & Morandi, B. (2020). Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control. Journal of the American Chemical Society, 142(25), 10914-10920. doi:10.1021/jacs.0c03184.


Cite as: http://hdl.handle.net/21.11116/0000-0006-C65C-4
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.