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A Highly Efficient Palladium-Catalyzed Decarboxylative ortho-Acylation of Azobenzenes with a-Oxocarboxylic Acids: Direct Access to Acylated Azo Compounds

机译:高效钯催化偶氮苯与α-羰基羧酸的脱羧邻酰化:直接获得酰化偶氮化合物

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摘要

Recently, transition-metal-catalyzed decarboxylative cross-coupling reactions involving the use of readily available a, b-unsaturated and aryl carboxylic acids as potential coupling partners, in place of aryl halides or organometallic reagents, has attracted much attention and has provided a powerful tool for the construction of chemical bonds in organic synthesis.[1] Early in 2002, Myers reported a palladium- catalyzed decarboxylative Heck-type olefination of benzoic acids.[2] Since then, significant progress has been made on decarboxylative cross-coupling reactions.[3] For example, Goossen,[3a-d] Forgione,[3e] Li,[3f] Liu,[3g,h] Miura,[3i] Lee,[3j] and Tunge[3k,l] have studied decarboxylative biaryl coupling, olefination, alkynylation, aryl ketone formation and so forth. Very recently, Ge,[4] Duan,[5] Kim,[6] Tan,[7] Zhu,[8] and Saxena[9] have further demonstrated the feasiblity of decarboxylative acylation of arenes and other substrates by Pdcatalyzed group-directed C-H activation. Despite the achievements that have been made with respect to decarboxylation reactions, high reaction temperatures, and additives required for the decarboxylative process partially limit their potential applications. Therefore, it is desirable to develop a mild decarboxylative cross-coupling reaction that proceeds in the absence of any additives.
机译:最近,过渡金属催化的脱羧交叉偶联反应涉及使用容易获得的α,b-不饱和和芳基羧酸作为潜在的偶联伙伴,以取代芳基卤化物或有机金属试剂,引起了广泛关注并提供了强大的功能。有机合成中化学键的构建工具。[1] 2002年初,迈尔斯(Myers)报告了钯催化的苯甲酸的Heck型脱羧烯化反应。[2]从那时起,脱羧交叉偶联反应取得了重大进展。[3]例如,Goossen,[3a-d] Forgione,[3e] Li,[3f] Liu,[3g,h] Miura,[3i] Lee,[3j]和Tunge [3k,l]研究了脱羧联芳基偶联,烯烃化,炔基化,芳基酮形成等。最近,Ge,[4]段,[5] Kim,[6] Tan,[7] Zhu,[8]和Saxena [9]进一步证明了钯催化的芳烃和其他底物的脱羧酰化的可行性-定向CH激活。尽管在脱羧反应方面已经取得了成就,但是高反应温度和脱羧过程所需的添加剂部分地限制了它们的潜在应用。因此,需要开发在没有任何添加剂的情况下进行的温和的脱羧交叉偶联反应。

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