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Updated: Aug 11, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Regio- and Enantioselective Allylic Cyanomethylation by Synergistic Rhodium and Silane Catalysis
Minghe Sun1, Linsheng Wei1, Changkun Li1
1Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering Frontiers Science Center for Transformative Molecules Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Abstract:
Rh/silane-cocatalyzed regio- and enantioselctive allylic cyanomethylation with inert acetonitrile directly has been developed. Addition of a catalytic amount neutral silane reagent as an acetonitrile anion carrier is essential for the success of this reaction. The synthesis of mono- and bis-allylation products can be switched by adjusting the size of substituents on the silane, ligands, and temperature. Chiral homoallylic nitriles could be synthesized in above 20:1 branch/linear ratio, up to 98% yield and >99% ee.
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