Abstract
Allylic carbonates are cyanated in high yields to β,γ-unsaturated carbonitriles using trimethylsilyl cyanide in the presence of a catalytic amount (5 mol %) of Pd(PPh3)4 in THF under reflux. In the reaction, cinnnamyl methyl carbonate affords cinnamyl cyanide in 98% yield. Allylic acetates also provide the corresponding carbonitriles, but often in lower yields. The cyanations of several cis- and trans-alicyclic substrates proceed cleanly (stereoselectivity > 99%) with overall retention. Characterization and reaction of palladium complexes relevant to the present catalysis indicate that transmetalation of an η3-allyl palladium complex with trimethylsilyl cyanide is facile, while the resulting cyano(η3-allyl)palladium complexes afford the corresponding allylic cyanides only when excess trimethylsilyl cyanide is present. Stereochemistry of the product indicates that the CN attacks the η3-allyl moieties from the palladium side.
Published Version
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