过渡金属催化的羰基化的杂环化合成和官能团化

doi:10.6023/cjoc201809004

摘要/Abstract

杂环化合物广泛的存在于天然产物、药物、有机材料以及其他官能团化的分子中.所以发展杂环合成的新的方法学有着极其重要的意义.在所有的有机合成策略中，过渡金属催化的反应，由于其相对温和的反应条件和高效的原子利用率，无疑是一种理想的选择.这其中，过渡金属催化的羰基化反应又是一个比较理想的反应.自从20世纪30年代首度报道以来，羰基化反应经历了长足的发展.时至今日，各种羰基化反应类型都得到发展.反应底物也囊括了卤代芳烃、烯烃、炔烃及其它未经活化的化合物.羰基来源也从一氧化碳气体拓展到了其他原位释放一氧化碳的化合物，例如甲酸、醇、醛、生物质等.对我们课题组在过去5年中在过渡金属催化的羰基化合成杂环及杂环的官能团化领域的工作进行了总结.使用铜、钯、铑、钌和铱作为催化剂，基于碳卤键和碳氢键的活化，各种杂环化合物都能被高效的合成.

关键词: 过渡金属催化, 羰基化, 杂环合成, 羰基来源, 环化反应, 多米诺反应

Heterocycles are ubiquitous in natural products, pharmaceuticals, organic materials, and numerous functional molecules. These structural units probably constitute the largest and most varied family of organic compounds. Hence the development of new procedures for heterocycles synthesis has been a hot research topic for over centuries. Among all the new synthetic methods, transition-metal-catalyzed reactions are attractive. Those reactions can formulate complicated heterocycles efficiently from available starting materials under mild conditions and atom economical routes. Among them, transition-metal-catalyzed carbonylation reaction has become an efficient and useful tool in organic synthesis since the first hydroformylation reaction developed by W. Reppe at BASF in the 1930s. Since then impressive progress has been achieved in this area. In nowadays, various types of carbonylation reactions were established. Substrates including aryl halides, olefins, alkynes or simply C-H bond can be activated and produce the corresponding carbonyl-containing compounds smoothly. On the other hand, carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry around 80 years ago, academic and industrial laboratories have explored uses of CO in chemical reactions broadly. However, because of the special physical properties of CO, organic chemists were often reluctant to apply carbonylations frequently in laboratories. Hence, different kinds of CO surrogates were developed and applied in carbonylation reactions, such as metal carbonyl compounds M(CO) _x, formates, alcohols, formic acid, aldehyde, biomass and carbon dioxide. Those CO surrogates offer interesting opportunities for carbonylation reactions. This account mainly outlines our progress in the development of transition-metal-catalyzed carbonylative synthesis and functionalization of heterocycles from 2012 to 2018. With copper, palladium, rhodium, ruthenium and iridium as the catalysts and relying on the activation of carbon-halogen and carbon-hydrogen bonds, we are able to synthesis various of heterocycles by using CO gas or CO surrogates as the C1 building blocks.

Key words: transition metal catalyst, carbonylation, heterocycle synthesis, CO surrogates, cyclization, Cascade reaction

引用此文

尹志平, 王泽超, 吴小锋. 过渡金属催化的羰基化的杂环化合成和官能团化[J]. 有机化学, 2019, 39(3): 573-590.

Yin Zhiping, Wang Zechao, Wu Xiao-Feng. Transition-Metal-Catalyzed Carbonylative Synthesis and Functionalization of Heterocycles[J]. Chin. J. Org. Chem., 2019, 39(3): 573-590.

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