Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents
Copper-Catalyzed Oxy-Alkynylation of Diazo Compounds with Hypervalent Iodine Reagents
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DOI：
10.1021/jacs.6b00278
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发表时间：
2016-02-24
影响因子：
15
通讯作者：
Waser, Jerome
中科院分区：
文献类型：
--
作者：
Hari, Durga Prasad;Waser, Jerome
炔烃在合成化学、生物学和材料科学中有着广泛的应用。近年来，基于亲电炔基化与高价碘试剂的方法使乙炔合成更加灵活和有效，但它们导致形成一当量的碘代芳烃作为副产物。在此，描述了一种更有效的策略，其涉及铜催化的重氮化合物与乙炔基苯碘酰（酮）（EBX）试剂的氧炔基化，其进行时产生氮气作为唯一的废物。该反应在EBX试剂和重氮化合物中都具有广泛的应用范围。此外，乙烯基重氮化合物选择性地产生烯炔作为单一的几何异构体。在转化过程中引入的官能团作为容易的手柄，可以获得合成和药物化学的有用构建模块。
Alkynes have found widespread applications in synthetic chemistry, biology, and materials sciences. In recent years, methods based on electrophilic alkynylation with hypervalent iodine reagents have made acetylene synthesis more flexible and efficient, but they lead to the formation of one equivalent of an iodoarene as side-product. Herein, a more efficient strategy involving a copper-catalyzed oxy-alkynylation of diazo compounds with ethynylbenziodoxol(on)e (EBX) reagents is described, which proceeds with generation of nitrogen gas as the only waste. This reaction is remarkable for its broad scope in both EBX reagents and diazo compounds. In addition, vinyl diazo compounds gave enynes selectively as single geometric isomers. The functional groups introduced during the transformation served as easy handles to access useful building blocks for synthetic and medicinal chemistry.