铜催化杂芳—炔分子内烯基化去芳构及合成应用

The synthesis of three-dimensional hetero-cyclic compounds via transition-metal-catalyzed dearomatization of hetero-aromatic rings is of high step-economy and stereochemical characteristics. However, the methods involved are mostly based on arylation and allylation dearoamtizations with palladium and iridium as the main catalysts. Thus, there is a pressing need to develop novel metallic catalyst to achieve new pathway for dearomatization, such as vinylation dearomatization, by which the products possess multiple reactive sites and are of much synthetic value. . This project aims at vinylation dearomatization of heteroaryl-alkynes catalyzed by cheap copper metals. The following topics will be investigated as part of this project: copper-catalyzed vinylation dearomatization of heteroaryl-alkynes via a free-radical pathway; vinylation dearomatization of heteroaryl-alkynes mediated by [Cu-H] species; vinylation dearomatization of heteroaryl-alkynes mediated by [Cu-B] species; vinylation dearomatization of heteroaryl-alkynes in [Cu]-O2 system; We expect this project to pave the way for the disclosing of new bond cleavage and reconnection of aryl rings and acetylenes, on the basis of SET between the cuprate and aryl rings, electrophilic cupration of aryl rings and vinylcupration of acetylenes. By using these new reactions, new pathways for the transformation of hetero-aromatic rings and efficient synthesis of some heteropolycycles will be established.

基于过渡金属催化杂芳环去芳构化合成多取代三维杂环具有高步骤经济性和立体化学特色。但目前反应类型主要为芳基化和烯丙基化去芳构，催化剂主要是钯和铱等贵金属，迫切需要发展新的金属催化体系以拓展去芳构新反应类型，如烯基化去芳构（其产物具有多反应位点和重要的合成用途）。.鉴于铜催化剂具有廉价易得、多变化合价和优良电子受体等特性,本项目开展铜催化杂芳–炔分子内烯基化去芳构及合成应用研究。内容包括铜催化自由基途径的杂芳–炔烯基化去芳构；铜氢体系下杂芳–炔烯基化去芳构；铜硼体系下杂芳–炔烯基化去芳构；铜氧体系下杂芳–炔烯基化去芳构串连偶联。本项目将揭示基于铜和芳环间单电子转移、芳环亲电铜化、炔基的烯铜化等过程导致的芳环和炔键活化断裂及重组新模式，进而为一些杂芳环转化和重要三维杂环分子高效合成提供新途径。

过渡金属催化杂芳环去芳构反应化合成多官能团化的复杂三维杂环具有高步骤经济性和立体化学特色。已报道的反应类型主要为芳基化和烯丙基化去芳构，催化剂主要是钯和铱等贵金属，迫切需要发展新的金属催化体系以拓展去芳构新反应类型，如烯基化去芳构获得具有多反应位点和重要的合成用途产物。.鉴于铜催化剂具有廉价易得、多变化合价和优良电子受体等特性, 本项目主要开展了铜催化杂芳–炔分子内烯基化去芳构及合成应用研究。内容包括铜氧体系下杂芳–炔烯基化去芳构串连偶联；铜催化自由基途径的杂芳–炔烯基化去芳构；铜氢体系下杂芳–炔烯基化去芳构； 此外进行了部分研究内容调整，研究了无金属调价下和钯光共催化条件下非活化苯环及杂芳环的去芳构化新反应。本项目揭示了基于铜和芳环间单电子转移、芳环亲电铜化、炔基的烯铜化等过程导致的芳环和炔键活化断裂及重组新模式，进而为一些杂芳环和苯环的转化和重要三维杂环分子高效合成提供新途径。