Alkynylcyanation of alkynes and dienes catalyzed by nickel

作者：Hirata Yasuhiro; Tanaka Masaaki; Yada Akira; Nakao Yoshiaki^*; Hiyarna Tamejiro

来源：Tetrahedron, 2009, 65(26): 5037-5050.

DOI：10.1016/j.tet.2009.03.079

• Nickel
• Lewis acid
• Carbocyanation
• C-C bond activation
• Alkyne
• Diene

Alkynyl cyanides are found to add across alkynes and 1,2-dienes in the presence of a catalyst prepared in situ from Ni(cod)(2), xantphos, and BPh(3). A range of functionalized conjugated cis-enynes are obtained with high regioselectivity. The addition reaction across norbornadiene proceeds in the absence of BPh(3) to give exo-cis adduct exclusively. A stoichiometric reaction of ail alkynyl cyanide, Ni(cod)2, xantphos, and BPh(3) gives trans-(xantphos)Ni(CNBPh(3))(C CSiMe(2)t-Bu), which is suggested to be a plausible reaction intermediate of the alkynylcyanation reaction.

• 出版日期2009-6-27