From Development of Catalysts for Alkyne and Alkyne/Nitrile [2 + 2 + 2] Cycloaddition Reactions to Their Use in Polymerization Reaction
From Development of Catalysts for Alkyne and Alkyne/Nitrile [2 + 2 + 2] Cycloaddition Reactions to Their Use in Polymerization Reaction
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从炔烃和炔烃/腈 [2 2 2] 环加成反应催化剂的开发到其在聚合反应中的应用
作者：
折原賢祐;菅野廉太郎;曽明爍;西山義剛;熊崎太信;谷村瞬;岩坪威;富田泰輔;横島聡;福山透;西山義剛;西山義剛;岡本専太郎
已经开发了由配体、金属化合物和锌组成的几种体系作为用于炔环加成反应和炔-腈共环加成反应的催化剂。N-杂环卡宾（NHC）-氯化铁（III）-锌、NHC-氯化钴（II）-锌和2-{[（2，6-二异丙基苯基）亚氨基]甲基}吡啶（dipimp）-六水合氯化铁（III）-锌体系催化了炔的分子内环三聚反应。dipimp-氯化钴（II）六水合物-锌系统催化环加成反应的各种炔在分子内，部分分子内，和完全分子间的方式。乙烷-1，2-二基双（二苯基膦）-六水合氯化钴（II）-锌体系能有效催化二炔与腈的[2 + 2 + 2]共环加成反应。镍配合物与离子液体标记的配体转化为相应的环辛四烯在甲苯-离子液体两相系统中，在锌的存在下，1，6-二炔。dipimp-nickel（II）chloride hexahydrate-zinc催化剂聚合1，6-diynes形成共轭多烯环状聚合物。本文介绍了这些结果及其在合成中的应用，包括可控聚合反应。1引言2炔[2+2+2]环加成反应2.1 N-杂环卡宾-钴或铁化合物-锌催化体系的发展2.2 2-{[2+2 + 2]环加成反应的发展（2，6-二异丙基苯基）亚氨基]甲基}吡啶-钴或铁盐-锌催化剂体系2.2.1 2-{[（2，6-二异丙基苯基）亚氨基]甲基}吡啶的开发（2，6-二异丙基苯基）亚氨基]甲基}吡啶-氯化铁-锌催化体系（2，6-二异丙基苯基）亚氨基]甲基}吡啶-六水合氯化铁-锌催化体系2.3（二、6-二异丙基苯基）亚氨基]甲基}吡啶-氯化钴（II）六水合物-锌催化剂体系2.3.1反应性和官能团亲和性2.3.2催化剂活化3炔腈[2+2+2] Co-环加成4应用4.1在有机合成中的用途4.2用作聚合物合成的方法4.2.1各种可聚合分子的制备（一个MPEG4库）4.2.2在聚合物官能化中的用途4.2.3用作聚合反应5其它反应5.1镍催化[2+2+2+2] 1，6-二炔的环加成和环加成聚合5.2内炔的氢炔化反应6结论
Several systems consisting of a ligand, a metal compound, and zinc have been developed as catalysts for alkyne cycloaddition reactions and alkyne–nitrile co-cycloaddition reactions. N-Heterocyclic carbene (NHC)–iron(III) chloride–zinc, NHC–cobalt(II) chloride-zinc, and 2-{[(2,6-diisopropylphenyl)imino]methyl}pyridine (dipimp)–iron(III) chloride hexahydrate–zinc systems catalyzed intramolecular cyclotrimerization reactions of alkynes. The dipimp–cobalt(II) chloride hexahydrate–zinc system catalyzed cycloaddition reactions of a variety of alkynes in intramolecular, partially intramolecular, and fully intermolecular fashions. The ethane-1,2-diylbis(diphenylphosphine)–cobalt(II) chloride hexahydrate–zinc system was effective in catalyzing the [2 + 2 + 2] co-cycloaddition of diynes with nitriles. Nickel complexes with an ionic liquid-tagged ligand converted 1,6-diynes into the corresponding cyclooctatetraenes in a toluene–ionic liquid biphasic system in the presence of zinc. The dipimp–nickel(II) chloride hexahydrate–zinc catalyst polymerized 1,6-diynes to form conjugated polyene cyclic polymers. These results and their applications in synthesis, including controlled polymerization reactions, are described.1 Introduction2 Alkyne [2+2+2] Cycloaddition2.1 Development of N-Heterocyclic Carbene–Cobalt or Iron Compound–Zinc Catalyst Systems2.2 Development of 2-{[(2,6-Diisopropylphenyl)imino]methyl}pyridine–Cobalt or Iron Salt–Zinc Catalyst Systems2.2.1 Development of 2-{[(2,6-Diisopropylphenyl)imino]methyl}pyridine–Iron Chloride–Zinc Catalyst Systems2.2.2 Development of the 2-{[(2,6-Diisopropylphenyl)imino]methyl}pyridine–Iron Chloride Hexahydrate–Zinc Catalyst System2.3 The 2-{[(2,6-Diisopropylphenyl)imino]methyl}pyridine–Cobalt(II) Chloride Hexahydrate–Zinc Catalyst System2.3.1 Reactivity and Functional Group Compatibility2.3.2 Catalyst Activation3 Alkyne–Nitrile [2+2+2] Co-cycloaddition4 Applications4.1 Uses in Organic Synthesis4.2 Use as a Method for Polymer Synthesis4.2.1 Preparation of Diverse Polymerizable Molecules (a Monomer Library)4.2.2 Use in Polymer Functionalization4.2.3 Use as a Polymerization Reaction5 Other Reactions5.1 Nickel-Catalyzed [2+2+2+2] Cycloaddition and Cycloaddition Polymerization of 1,6-Diynes5.2 Hydroalkynylation of Internal Alkynes6 Conclusion