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

研究了具有酶功能的铜(I)配合物催化合成烯丙基衍生物。以抗坏血酸聚合物（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)为催化剂（具有酶功能），在30℃的氩气气氛下，在相应的亲核试剂存在下，进行了烯丙基酰氯（1-氯-2-丙烯、1-氯-2-丁烯、3-氯-1-丁烯和肉桂酰氯）的非均相催化反应。这些催化体系表现出非常高的活性，与没有聚合物支撑的反应相比，在聚合物支撑的Cu(I)和抗坏血酸（1/100 mol /底液）的催化量下，反应很容易产生相应的烯丙基衍生物。同时，在30℃氩气条件下，在pH为4.0的丙酮水溶液中，用抗坏血酸和负载coppre(I)的光学活性聚合物聚甲基丙烯酸甲酯（PMnMA）和聚甲基丙烯酸甲酯（PBoMA）对1-氯-2-丁烯进行了非均相不对称羟基化反应，得到了光学活性的1-丁烯-3-醇。与没有聚合物载体的体系相比，聚合物催化剂体系表现出相当高的不对称诱导。这种现象可以解释为反应底物与光学活性配体之间的稳定相互作用增加了，这是由于聚合物载体表面的疏水微气氛以及通过-烯丙基氯化铜中间形成。这些背景资料表明，在化学工业过程中合成烯丙基衍生物是一种非常实用的方法。

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.