Indium-catalyzed 2-alkenylation of 1,3-dicarbonyl compounds with unactivated alkynes
Indium-catalyzed 2-alkenylation of 1,3-dicarbonyl compounds with unactivated alkynes
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DOI：
10.1021/ja0702014
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发表时间：
2007-04-25
影响因子：
15
通讯作者：
Nakamura, Eiichi
中科院分区：
文献类型：
--
作者：
Endo, Kohei;Hatakeyama, Takuji;Nakamura, Eiichi
1，3-二羰基化合物在催化量的三氟甲磺酸铟存在下与未活化的炔烃反应，以高到极高的产率得到2-烯基化的1，3-二羰基化合物，对乙炔部分上C-C键的形成位置具有唯一的区域选择性。在大多数情况下，反应需要少于1-摩尔%的催化剂，并且不需要溶剂。该反应可以容忍多种官能团，包括酯、醚、烯丙基卤化物、呋喃、噻吩和保护胺。实验和理论研究表明，该反应是通过铟(III)烯醇酸与乙炔的协同碳金属化反应进行的，其中铟-乙炔相互作用是重要的。
1,3-Dicarbonyl compounds add to unactivated alkynes in the presence of a catalytic amount of indium(III) trifluoromethanesulfonate in high to excellent yield to give 2-alkenylated 1,3-dicarbonyl compounds with exclusive regioselectivity as to the position of C-C bond formation on the acetylene moiety. In most of the cases, the reaction requires less than 1-mol % loading of the catalyst and does not require solvent. The reaction tolerates a wide variety of functional groups including ester, ether, allylic halide, furan, thiophene, and protected amine. Experimental and theoretical studies suggested that the reaction proceeds via a concerted carbometalation reaction of an indium(III) enolate with the acetylene, where indium-acetylene interaction is important.