摘要/Abstract

形成C（sp³）—C（sp³）键的偶联反应在有机合成中具有重要意义.其中，过渡金属参与及催化的还原自偶联反应在对称结构分子合成方面具有独特优势.这类反应操作简便，直接利用易得的有机卤化物作为底物，避免了高活性的有机金属试剂的使用.同时，偶联反应的催化剂一般基于廉价金属，因此具有良好的规模化应用前景.近年来发展的基于光氧化还原催化、离子液体及无机纳米材料的反应体系进一步提升了还原偶联反应的效率及选择性.系统介绍了钴、镍、铜、铑、钛等不同金属参与或催化的还原偶联反应，探讨了近年来发展的光介导还原偶联反应体系，并对还原偶联反应在天然分子及高分子合成方面的应用进行详细介绍.
关键词: C(sp³)—C(sp³)键, 还原自偶联, 过渡金属催化, 光氧化还原催化, 全合成
C(sp³)-C(sp³) bond coupling is of great significance in organic synthesis, among which reductive homocoupling has showed its special superiority in construction of symmetrical molecular structures. These reactions are usually operationally simple, which utilize organohalides as substrates, avoiding the handling of highly reactive organometallic reagents. The use of non-precise metals as the catalyst makes reductive homocouplings amenable for large-scale synthesis. Improved efficiency and selectivity have been observed in systems involving photoredox catalytic processes, ionic-liquids, and inorganic nanomaterials. This review aims to summarize the development of reductive couplings. In this review, various reductive homocouplings are summarized, where transition metals, such as cobalt, nickel, copper, titanium, and rhodium are involved. Photo-mediated reductive couplings are then highlighted followed by a discussion on applications of reductive couplings in natural products synthesis and polymer sciences.
Key words: C(sp³)-C(sp³) bond formation, reductive homocoupling, transition-metal catalysis, photoredox catalysis, total synthesis


PDF全文下载地址:

点我下载PDF