【作者】 杨帅；

【导师】 张扬会；

【作者基本信息】 同济大学 ， 化学， 2023， 博士

【摘要】 近几十年,过渡金属催化的C–H键官能团化反应得到了快速发展。为了解决区域选择性的问题,该类反应一般需要使用导向基,限制了反应的在有机合成中的应用。本论文主要研究烯烃传导的钯催化C–H键活化反应,该类反应为C–H键官能团化提供了新策略。论文将从以下四部分的研究工作展开探讨:一、烯烃传导的钯催化芳基碘化物分子间C–H键烷基化反应基于烯烃传导C–H键活化新策略,我们发展了一种马来酰胺传导的钯催化2-碘联苯的C–H键烷基化反应。该反应为琥珀酰亚胺稠合的9,10-二氢菲提供了一种简便快捷的高效合成方法。苊烯也可作为烯烃传导基团,实现高效的C–H键官能团化反应并形成相应的环化产物。二、烯烃传导的钯催化C–H键硼化和硅基化反应利用马来酰亚胺传导钯催化C–H键活化策略,实现了碘代芳基的原位烷基化和邻位硼化或硅烷基化反应。该反应具有优异的区域选择性和良好的底物兼容性,能以高达89%或92%的收率分别得到硼化和硅基化产物。芳基硼化物和芳基硅烷是重要的有机合成中间体,苯琥胺是一种可用于癫痫研究和相关研究的药物分子结构单元。三、钯催化溴代芳基烯酰胺和溴代烯烃的螺环化合成螺茚-氧化吲哚骨架的反应通过钯催化的2-溴芳酰胺与溴乙烯的螺环化反应,发展了一种简单有效构建螺环烯烃-2-氧化吲哚的方法。该反应经过2-溴芳酰胺的碳钯化和C–H官能团化形成螺环环钯中间体,该环钯中间体被1-溴乙烯捕获后生成螺环烯烃-2-吲哚酮化合物。四、钯催化溴代烯烃和2-碘联苯的C–H键烯基化合成9-芴基烯的反应通过钯催化2-碘联苯和乙烯基溴的交叉偶联反,可以简便高效的合成了一系列9-芴基衍生物和二苯基二苯并富烯化合物。该反应经历2-碘联苯的C–H活化和两个C–C键的构建。总之,我们通过烯烃传导钯催化C–H键官能团化方案,开发了烯烃与2-碘联苯以及碘苯衍生物的反应,实现了C–H键烷基化反应、硼化(硅基化)反应、多米诺环化Heck过程的烯基化反应,以及在此基础上发展的2-碘联苯和苯乙烯基溴的分子间烯基化环化反应。更多还原

【Abstract】 Transition-metal-catalyzed C–H functionalization has gained rapid development over the past decades.To achieve high regioselectivity,a directing group often has to be used,which restricts the applications of the reactions in organic synthesis.This thesis focuses on alkene-relayed palladium-catalyzed C–H bond activation,which represent a novel strategy for C–H functionalization.The thesis includes four projects as below:1.Alkene-relayed Pd-catalyzed intermolecular C–H alkylation of aryl iodides.Alkene-relayed C–H activation represents a novel strategy for C–H functionaliza-tion.We developed maleimide-relayed Pd-catalyzed annulation reaction of 2-iodobi-phenyls.The reaction providing a straightforward and high efficiency method for the synthesis of succinimide-fused 9,10-dihydrophenanthrenes.When acenaphthylene was used as the relay,the C–H functionalization reaction also proceeded efficiently to form the corresponding cyclization products.2.Alkene-relayed Pd-catalyzed the C–H borylation and silylation reactionsIpso-alkylation and ortho-borylation or silylation reactions of aryl iodides have been developed via alkene-relayed palladium-catalyzed C–H activation.The reactions had excellent regioselectivity and broad substrate scope,and formed borylation and si-lylation products in up to 89%and 92%yields respectively.Aryl borates and aryl silanes are important intermediates in organic synthesis,and phensuximide is structural motif of drug molecules that can be used in epilepsy and related research.3.Pd-catalyzed spirocyclization reactions of 2-Bromoarylamides and vinyl bro-mides to synthesize spiroindyl-oxidoindole skeletonAn approach for the simple and effective construction of spirocyclic alkene-2-ox-indole via palladium-catalyzed spirocyclization of 2-bromoarylamide with vinyl bro-mides.The reaction formed spiropalladacycles as the intermediates via carbopallada-tion and the C–H activation.The spiropalladacycles reacted with vinyl bromides to form spiroindenyl-2-oxindoles.4.Pd-catalyzes C–H alkenylation of vinyl bromides and 2-iodobiphenyl to synthe-size 9-fluorenylidenes derivativesA simple and efficient method for the synthesis of 9-fluorenylidenes and diphe-nyldibenzofulvenes has been developed through palladium-catalyzed cross-coupling of2-iodobiphenyls and vinyl bromides.This reaction involves C–H activation of 2-io-dobiphenyl and formation of two C–C bonds.In summary,we have developed a range of reactions of 2-iodobiphenyls and iodo-benzene derivatives with olefins through alkene-relayed palladium-catalyzed C–H bond activation.The reactions include:C–H alkylation,C–H borylation and silylation,and cyclization reactions,reactions,and alkenylation reaction via a domino cyclization and Heck process,as well as the intermolecular alkylating cyclization reaction of 2-iodobiphenyls and vinyl bromides.更多还原