Palladium-catalyzed intermolecular addition of formamides to alkynes.
Palladium-catalyzed intermolecular addition of formamides to alkynes.
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DOI：
10.1021/ja910038p
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发表时间：
2010-01
影响因子：
15
通讯作者：
Tetsuaki Fujihara;Yuko Katafuchi;Tomohiro Iwai;J. Terao;Y. Tsuji
中科院分区：
文献类型：
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作者：
Tetsuaki Fujihara;Yuko Katafuchi;Tomohiro Iwai;J. Terao;Y. Tsuji
开发了一种用于甲酰胺与炔烃分子间加成的新型钯体系。甲酰胺与内炔在钯催化剂存在下与酰基氯作为添加剂的反应可区域选择性和立体选择性地提供(E)-α,β-不饱和酰胺。相同的催化剂系统实现了甲酰胺与末端炔烃加成的第一个例子，得到带有末端亚甲基部分的相应α,β-不饱和酰胺作为主要产物。本反应广泛适用于具有各种功能的底物。该方法也可应用于N,N-二取代甲酰胺与降冰片烯的反应。在反应条件下，与原位生成的 HCl 会形成作为关键中间体的氢化钯物质。
A novel palladium system for an intermolecular addition of formamides to alkynes has been developed. The reaction of formamides with internal alkynes in the presence of a palladium catalyst with acid chloride as an additive afforded (E)-alpha,beta-unsaturated amides regio- and stereoselectively. The same catalyst system realized the first example of the addition of formamides to terminal alkynes giving the corresponding alpha,beta-unsaturated amides bearing a terminal methylene moiety as major products. The present reaction was widely applicable to substrates with various functionalities. This method also could be applied to the reaction of N,N-disubstituted formamides with norbornene. A hydridopalladium species would be formed as a key intermediate with in situ generated HCl under the reaction conditions.