Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control
Open access
Date
2020-06-24Type
- Journal Article
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. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000424373Publication status
publishedExternal links
Journal / series
Journal of the American Chemical SocietyVolume
Pages / Article No.
Publisher
American Chemical SocietyOrganisational unit
09634 - Morandi, Bill / Morandi, Bill
Funding
757608 - Shuttle Catalysis for Reversible Molecular Construction (EC)
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