Regio- and Enantioselective Allylic Cyanomethylation by Synergistic Rhodium and Silane Catalysis.

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 .