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

具有拟酶功能的铜(I)配合物催化合成烯丙基衍生物

• 批准号: 04650762
• 负责人: MATSUBARA Yoshio
• 金额: $ 0.83万
• 依托单位: Faculty of Science and Engineering, Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04650762/
• 关键词: Catalytic synthesis; Allyl derivatives; Copper(I) Complexies; Enzymimic Function; Heterogeneous catalytic reaction Polymer supported copper(I); Optical Active 1-Buten-3-ol; Asymmetric Hydroxylation Catalyst; 二酸化炭素固定; アスコルビン酸; アリルハライド; 水酸化反応; pi

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.

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。

项目成果

松原凱男他5名: "一価銅とアスコルビン酸を触媒とする炭酸イオンと塩化アリルとの反応" Chemistry Express. 8. 733-736 (1993)

Kaio Matsubara 等 5 人：“一价铜和抗坏血酸催化的碳酸根离子与烯丙基氯的反应”，Chemistry Express 8. 733-736 (1993)。

Y.Matsubara, S.Uezawa, H.Hayasi, T.Taimatus, M.Yoshihara, and T.Maeshima: "Catalytic reaction of Allyl Chlorides with Corbonate Ion by Use of Ascorbic Acid and Copper(I) Ion System" Chemistry Express. 8. 733-736 (1993)

Y.Matsubara、S.Uezawa、H.Hayasi、T.Taimatus、M.Yoshihara 和 T.Maeshima：“使用抗坏血酸和铜 (I) 离子系统催化烯丙基氯与碳酸根离子的反应”化学快报。

Y.Matsubara, S.Uezawa, M.Morisawa, M.Yoshihara, and T.Maeshima: "Catalytic Hydroxylation of Allyl Chlorides with Ascorbic Acid and Poly(methyl methacrylate)-Supported Copper(I) Ion System" Kobunnshi Ronbunshu. 49. 155-160 (1992)

Y.Matsubara、S.Uezawa、M.Morisawa、M.Yoshihara 和 T.Maeshima：“用抗坏血酸和聚甲基丙烯酸甲酯负载的铜 (I) 离子体系催化烯丙基氯的羟基化”Kobunnshi Ronbunshu。

Y.Matsubara, S.Uezawa, M.Morisawa, M.Yoshihara, and T.Maeshima: "Direct Hydroxylation of Aromatic Compounds Using Heterogeneous Catalytic System" Kobunnshi Ronbunshu. 50. 641-644 (1993)

Y.Matsubara、S.Uezawa、M.Morisawa、M.Yoshihara 和 T.Maeshima：“使用多相催化系统直接羟基化芳香族化合物”Kobunnshi Ronbunshu。

松原凱男他4名: "一価担持光学活性ポリマーを用いる1-クロロ-2-ブテンの不斉水酸化反応" 高分子論文集. 50. 587-590 (1993)

Kaio Matsubara 等 4 人：“使用单价支撑的光学活性聚合物进行 1-氯-2-丁烯的不对称羟基化”Kobunshi Ronshu 50. 587-590 (1993)。