Metal-Mediated Oxidative Cross-Coupling of Terminal Alkynes: A Promising Strategy for Alkyne Synthesis**

炔烃末端用金属媒介来氧化交叉耦合

—一种有前景炔合成方法

 Alkynes are a recurring functional group in numerous natural products, bioactive compounds, and organic materials as well as versatile intermediates in synthesis. Among the methods for the incorporation of alkynyl functionality into organic molecules, metal-mediated cross-coupling reactions have a prominent role.Arguably, one of the most valuable transformations in this context is the Sonogashira reaction involving terminal alkynes reacting with aryl or vinyl halides,
and even alkyl halides as coupling partners.
A recent addition to the arsenal of cross-coupling-based synthesis of substituted alkynes is the “inverse Sonogashira coupling”involving metal-catalyzed direct alkynylation of arenes and heterocycles with alkynyl halides.In view of the diverse
requirements of CC bond-forming reactions, the development of a complementary and, especially conceptually innovative strategy would be highly desirable. Recently,
metal-mediated oxidative cross-coupling reactions of alkynyl metal reagents or terminal alkynes have emerged as a promising new strategy for access to various alkynes.

在众多天然产物、生物活性化合物、有机材料以及合成中的多功能中间体中，炔烃是一个反复出现的官能团。把炔基官能团加入有机分子的众多方法中，金属媒介交叉耦合反应占有相当重要的地位。可以说，在这篇文章中最有价值的转变时涉及到末端炔烃与芳基或乙烯基卤化物甚至是烷基卤化物作为耦合部分的Sonogashira反应。最近除了以交叉耦合为基础的合成取代炔烃的阿森那，就是“逆Sonogashira耦合”。考虑到需要不同的C-C键形成反应，后续的发展，尤其是概念策略的创新是必须的。末端炔烃或金属炔基试剂的用金属媒介来氧化交叉耦合已作为生成炔烃的一个有前景的策略。

The first copper-mediated oxidative acetylenic homocoupling was pioneered by Glaser in 1869, however, metal-
mediated oxidative cross-coupling reactions of alkynyl metal reagents or terminal alkynes with other nucleophiles remain a significant challenge, largely because of the lack of solutions to overcome the undesired homocoupling under oxidative conditions. In 2006, Lei and co-workers reported a remark-
able example of metal-mediated oxidative cross-coupling of alkynyl metal reagents in high yields and selectivity。

1869年，Glaser第一次用铜媒介氧化乙炔的自身耦合，然而，末端炔烃或金属炔基试剂的用金属媒介来氧化交叉耦合与其他亲核试剂的反应仍存在具有重大意义的挑战，绝大部分是因为在氧化条件下缺少解决自身耦合中副反应的方案。2006年，Lei 和他的团队报道在高效益与选择性下金属炔基试剂的用金属媒介来氧化交叉耦合