α-Olefins as alkenylmetal equivalents in catalytic conjugate addition reactions
α-Olefins as alkenylmetal equivalents in catalytic conjugate addition reactions
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DOI：
10.1002/anie.200705163
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Jamison, Timothy F.
中科院分区：
文献类型：
--
作者：
Ho, Chun-Yu;Ohmiya, Hirohisa;Jamison, Timothy F.
共轭加成反应最早是在世纪前被记载的，是最常用的有机反应之一。在碳-碳键形成变体中，亲核试剂通常是有机金属的。早期的技术采用烯醇化物、有机锂、格氏试剂或有机铜试剂;最近，有机锌和有机硼化合物显著增强了这种转化。[1，2]尽管官能团耐受性增加，但在这些强大的方法中仍然需要有机金属或类有机化合物。在本文中，我们描述了一种新的共辄加成反应，其中简单的未活化的烯烃（乙烯、α-烯烃或苯乙烯）代替有机金属试剂[Eq.①]。因此，虽然烯烃本身不是烯基金属试剂，但它在碳-碳键形成过程中起作用。烯烃的催化聚合是最重要的工业过程之一[3]，镍催化的双烯烃偶联反应也受到了极大的关注，包括加氢乙烯化反应。[4]蒙哥马利和同事发现，镍配合物催化各种共轭加成反应，[5]但最接近的先例是，
First documented over a century ago, conjugate additions are among the most utilized organic reactions. In carbon–carbon bond-forming variants, the nucleophile is typically organometallic. Earlier technology employed enolate, organolithium, Grignard, or organocopper reagents; more recently, organozinc and organoboron compounds have enhanced this transformation significantly.[1, 2] Despite increased functional group tolerance, an organometallic or an organometalloid compound is nonetheless required in these powerful methods. Herein we describe a novel conjugate addition reaction in which a simple, unactivated alkene (ethylene, an α-olefin, or styrene) takes the place of the organometal reagent [Eq.(1)]. Thus, although an alkene is not an alkenylmetal reagent per se, it functions as one in this carbon–carbon bond-forming process.Catalyzed polymerization of alkenes is one of the most important industrial processes,[3] and Ni-catalyzed two-alkene coupling reactions have also received significant attention, including hydrovinylation.[4] Montgomery and co-workers found that nickel complexes catalyze a wide variety of conjugate addition reactions,[5] but the closest precedent to