三氟甲磺酸硅基乙炔基碘鎓盐与苯并三唑的炔基化反应。2-乙炔基-2H-苯并三唑衍生物的区域选择性合成。

Alkynylation of benzotriazole with silylethynyliodonium triflates. Regioselective synthesis of 2-ethynyl-2H-benzotriazole derivatives.

机构信息

Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University, Honjo-machi, Saga 840-8502, Japan.

出版信息

J Org Chem. 2011 Oct 7;76(19):8117-20. doi: 10.1021/jo2015467. Epub 2011 Aug 29.

DOI:10.1021/jo2015467

PMID:21854042

Abstract

Phenyl(trimethylsilylethynyl)iodonium and tert-butyldimethylsilylethynyl(phenyl)iodonium triflates were applied to alkynylation of benzotriazole. Treatment of the silylethynyliodonium triflates with the potassium salt of benzotriazole ion in (t)BuOH and CH(2)Cl(2) gave 2-(trimethylsilylethynyl)-2H-1,2,3-benzotriazole and 2-(tert-butyldimethylsilylethynyl)-2H-1,2,3-benzotriazole in 74% and 76% yields, respectively. The regioisomers, 1-silylethynyl-1H-1,2,3-benzotriazole derivatives, were minor. In both cases of the silyl-substitued ethynyliodonium salts, novel regioselective alkynylation of benzotriazole at the 2 position was observed.

摘要

苯基（三甲基甲硅烷基乙炔基）碘𬭩和叔丁基二甲基甲硅烷基乙炔基（苯基）碘𬭩三氟甲磺酸酯被应用于苯并三唑的炔基化反应。在（t）BuOH 和 CH（2）Cl（2）中，将硅基乙炔基碘𬭩三氟甲磺酸酯与苯并三唑的钾盐处理，分别以 74%和 76%的产率得到 2-（三甲基甲硅烷基乙炔基）-2H-1,2,3-苯并三唑和 2-（叔丁基二甲基甲硅烷基乙炔基）-2H-1,2,3-苯并三唑。区域异构体，1-硅基乙炔基-1H-1,2,3-苯并三唑衍生物，是次要产物。在这两种硅取代的乙炔基碘𬭩盐的情况下，观察到苯并三唑在 2 位的新型区域选择性炔基化反应。