Alkynylcyanation of alkynes and dienes catalyzed by nickel
Alkynylcyanation of alkynes and dienes catalyzed by nickel
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DOI：
10.1016/j.tet.2009.03.079
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发表时间：
2009-06-27
期刊：
影响因子：
2.1
通讯作者：
Hiyama, Tamejiro
中科院分区：
文献类型：
--
作者：
Hirata, Yasuhiro;Tanaka, Masaaki;Hiyama, Tamejiro
在Ni(CoD)(2)、Xantphos和BPh3原位制备的催化剂的存在下，发现炔基氰化物在炔烃和1，2-二烯之间加成。得到了一系列具有高区域选择性的官能化共轭顺式烯炔类化合物。跨降冰片二烯的加成反应在没有BPh3的情况下进行，得到唯一的外加成产物。所有的炔基氰化物、Ni(Cod)2、xantphos和BPh3的化学计量反应生成了反式(Xantphos)Ni(CNBPh3)(C CSiMe(2)t-Bu)，它被认为是炔基氰化反应的一个可能的反应中间体。(C)2009爱思唯尔有限公司。保留所有权利。
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 BPh3. A range of functionalized conjugated cis-enynes are obtained with high regioselectivity. The addition reaction across norbornadiene proceeds in the absence of BPh3 to give exo-cis adduct exclusively. A stoichiometric reaction of ail alkynyl cyanide, Ni(cod)2, xantphos, and BPh3 gives trans-(xantphos)Ni(CNBPh3)(C CSiMe(2)t-Bu), which is suggested to be a plausible reaction intermediate of the alkynylcyanation reaction. (C) 2009 Elsevier Ltd. All rights reserved.