去芳构化反应的发展与展望  

The Development and Perspective of Dearomatization Reaction

作　　者：程远征 李木子 王瑞祥 祝龙浩 沈文杰 邹馨璇 顾庆[1] 游书力[1] Yuan-Zheng Cheng;Muzi Li;Rui-Xiang Wang;Long-Hao Zhu;Wen-Jie Shen;Xin-Xuan Zou;Qing Gu;Shu-Li You(New Cornerstone Science Laboratory,State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,345 Lingling Lu,Shanghai 200032,China)

机构地区：[1]中国科学院上海有机化学研究所金属有机化学国家重点实验室新基石科学实验室,上海200032

出　　处：《化学进展》2024年第12期1785-1829,共45页Progress in Chemistry

基　　金：国家自然科学基金项目(No.22031012)资助。

摘　　要：芳香化合物是一种大宗化学品,价廉易得。其芳香性去除或减弱的转化过程被称为去芳构化反应。该反应可以快速获取螺环、并环、桥环等环状化合物,有效拓展化学空间,实现三维立体分子构建,在天然产物合成和医药研发中发挥重要作用。近二十年来,去芳构化反应吸引了众多研究者的兴趣,过渡金属催化、小分子催化、酶催化、可见光催化、电催化等去芳构化体系被建立起来。通过去芳构化反应,吲哚、吡咯、(苯并)呋喃、(苯并)噻吩、(异)喹啉、吡啶、苯、萘等多种芳香化合物转化成了结构丰富的多环分子,大大缩短了一些天然产物的合成步骤。形式多样的亲核试剂、亲电试剂、偶极子、自由基、卡宾等偶联试剂不断被开发出来,为去芳构化反应提供了多样的官能团来源。本文概述了去芳构化反应的发展历程,按照芳香化合物的种类,总结了已发展的去芳构化反应体系,分析了当前去芳构化反应中存在的问题和挑战,并对发展趋势进行了展望。Representing an important class of ubiquitous chemical feedstock,aromatics have been extensively utilized in the nucleophilic aromatic substitution(SNAr)reactions,nitration reactions,Friedel-Crafts alkylation and acylation reactions,cross-coupling reactions,C-H bond functionalization reactions etc.Dearomatization reaction is another type of transformations of aromatics,in which their aromaticity is destroyed or reduced.Since its first report,dearomatization reaction has served as an efficient platform to create C(sp3)-H-rich spiro,fused and bridged polycyclic structures,widely applied in material and medicinal chemistry.In the past two decades,various dearomatization reactions have been established by using transition-metal catalysis,organocatalysis,enzymatic catalysis,photocatalysis,and electrocatalysis.Diverse polycyclic structures have been obtained by the dearomatization of indoles,pyrroles,(benzo)furans,(benzo)thiophenes,quinolines,pyridines,benzenes,naphthalenes,etc.The coupling reagents,including nucleophiles,electrophiles,dipoles,radicals,and carbenes have been developed to assemble different functional groups on dearomative framework.In this review,we briefly summarized the developed dearomatization reactions,which were categorized by the kinds of aromatic compounds.The remaining challenges and perspectives on the future development of dearomatization reactions are also included here.

关 键 词：芳香化合物 不对称催化 去芳构化反应 环状化合物 

分 类 号：O625[理学—有机化学]