The Catalytic Synthesis of Allyl Derivatives Using Copper(I) Complexies Having Enzymimic Function

本文研究了具有拟酶功能的铜（I）配合物催化合成烯丙基衍生物的反应。烯丙基氯化物的多相催化反应（1-氯-2-丙烯、1-氯-2-丁烯、3-氯-1-丁烯和肉桂酰氯）与抗坏血酸聚合物（聚（甲基丙烯酸甲酯），聚丙烯腈，离子交换树脂和螯合树脂）负载铜（I）作为高分子催化剂这些催化体系表现出很高的催化活性，在催化量的聚合物负载Cu（I）和抗坏血酸的存在下，反应容易进行，得到相应的烯丙基衍生物（1/100摩尔，基于取代基）。在pH4.0的丙酮水溶液中，30 ℃、氩气保护下，以抗坏血酸和光学活性高分子如聚甲基丙烯酸1-薄荷酯（PMnMA）和聚甲基丙烯酸（-）-异丙基酯（PBoMA）为催化剂，负载铜（I），进行1-氯-2-丁烯的非均相不对称羟基化反应，得到光学活性1-丁烯-3-醇。与无聚合物载体的催化体系相比，聚合物催化体系表现出相当高的不对称诱导。这一现象是由于聚合物载体表面的疏水微环境增加了反应底物与光学活性配体之间稳定的相互作用，以及通过π-烯丙基氯化铜中间体的形成而引起的，这些背景信息为烯丙基衍生物的合成提供了一种高实用性的化学工业方法。

This study was investigated on the catalytic synthesis of allyl derivatives using copper(I) complexies having enzymimic function.Heterogeneous catalytic reactions of allyl cholrides(1-chloro-2-propene, 1-chloro-2-butene, 3-chloro-1-butene, and cinnamyl chloride) were carried out with ascorbic acid polymer(poly(methyl methacrylate), polyacrylonitrile, ion exchange resin and chelate resin)-supported copper(I) as a polymeric catalyst(having enzymimic function)in the presence of corresponding nucleophiles under an argon atmosphere at 30ﾟC.These catalytic systems showed very high activity and the reactions proceed easily to give the corresponding allyl derivatives with catalytic amount of polymer-supported Cu(I) and ascorbic acid(1/100 mol based on subsurate)as compared with that in the absence of the polymeric supports. And also heterogeneous asymmetric hydroxylation of 1-chloro-2-butene was carried out with ascorbic acid and optical active polymers such as poly(l-menthyl methacrylate)(PMnMA) and poly((-)-bornyl methacrylate)(PBoMA) which supported coppre(I) as an asymmetric polymer catalyst in aqueous acetone at pH 4.0 under an argon atmosphere at 30ﾟC, and to give optical active 1-buten-3-ol. The polymeric cactalyst systems showed fairly high asymmetric induce as compared with that in the absence of the polymeric supports. This phenomenon was explained in terms of an increase stabilized interaction between reaction substrate and optical active ligand by the hydrophobic micro atmosphere on the surface of the polymeric support and also of the via pi-allyl copper chloride intermediate formation.These background informations indicate a high utility method for synthesis of allyl derivatives on chemical industrially process.