Ni(0)-Catalyzed conjugate addition of Me3SiCN to ynones: a-bromo-b-cyano tetrasubstituted enones.

[摘要]：Conjugate addn. of Me3SiCN to ynones is smoothly catalyzed by Ni(cod)2 to give the b-cyanosilyloxyallene quant. Further reaction of the silyloxyallenes with NBS provides the tetrasubstituted a-bromo-b-cyano enones in high yields (up to 95%) with excellent Z-selectivity (E/Z = up to >1/99). X-ray crystallog. anal. showed a bent structure of the a-bromo-b-cyano enone due to a deconjugation of the p-bond and carbonyl group.

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