碘(Ⅲ)介导的碳自由基参与的氧化偶联反应  

Iodine(Ⅲ)-Promoted Oxidative Cross-Coupling Reactions of C-H Bonds via a Free Radical Process

作　　者：吴福芳 李雪健 贾浩 韩宣振 沈晓宝 Wu Fufang;Li Xuejian;Jia Hao;Han Xuanzhen;Shen Xiaobao(Engineering Research Center of Biomass Conversion and Pollution Prevention of Anhui Educational Institutions,Fuyang Normal University,Fuyang,Anhui 236037)

机构地区：[1]阜阳师范大学生物质转化与污染防控安徽省高校工程技术研究中心,安徽阜阳236037

出　　处：《有机化学》2022年第3期884-890,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21602029);安徽省高校优秀人才支持计划重点(No.gxyqZD2020030);安徽省教育厅自然科学重点(No.KJ2020A0526);阜阳市政府-阜阳师范学院横向合作科研(No.XDHX201722);安徽省科技重大专项(No.18030701213)资助项目.

摘　　要：氧取代N-羟基邻苯二甲酰亚胺衍生物广泛存在于天然产物和药物中,其合成具有重要的意义.大多数烯烃、酮、酯、醛和醇的C=C/C—H键的活化方法通常需要用到金属或过氧化物.以廉价安全的醋酸碘苯作为脱氢剂,N-羟基邻苯二甲酰亚胺为自由基前体,实现了烯烃的双氧化、羰基α位氢的氧化、醛氢氧化及伯醇的氧化酯化反应.该方法主要通过自由基机理,具有环境友好、产率高及底物适用范围广等优点.反应体系简单实用,可以很好地应用于氧取代N-羟基邻苯二甲酰亚胺衍生物的合成.The synthesis of oxygen-substituted N-hydroxy phthalimide derivatives is essential due to their ubiquity in natural products and pharmaceuticals.Metals or peroxides are often required for most C=C/C—H bond activation methods used for olefins,ketones,esters,aldehydes and alcohols.Using cheap and safe iodobenzene diacetate as a feasible dehydrogenation agent and N-hydroxy phthalimide as free radical precursor,the dioxidation of olefins,α-oxidation of carbonyl compounds,oxidation of aldehydes,and oxidative esterification of primary alcohols were successfully realized.This method occurs via a radical mechanism and has the characteristics of mild metal-free reaction conditions,good compatibility and wide substrate scope.

关 键 词：氧化交叉偶联 PINO(phthalimide nitrogen-oxygen)自由基 非金属 碘(Ⅲ) 

分 类 号：O621.25[理学—有机化学]