Three-component coupling reactions of thioformamides with organolithium and Grignard reagents leading to formation of tertiary amines and a thiolating agent
Three-component coupling reactions of thioformamides with organolithium and Grignard reagents leading to formation of tertiary amines and a thiolating agent
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DOI：
10.1021/ja068523f
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发表时间：
2007-01-31
影响因子：
15
通讯作者：
Asai, Fumio
中科院分区：
文献类型：
--
作者：
Murai, Toshiaki;Asai, Fumio
发展了一种硫代甲酰胺与有机锂和格氏试剂的高效三组分偶联反应。该方法的通用性已通过使用反应物和试剂的各种组合来证明。通过对关键中间体的H-1和C-13 NMR光谱检测，得到了有关反应机理的信息。通过将有机锂试剂添加到硫代甲酰胺中产生的中间体中的LiS基团用作离去基团。在这些反应中形成的固体副产物，配制为[LiSMgBr]，可以用作硫醇化剂以将酰氯转化为硫代酸和硫代酸酐。
A highly efficient three-component coupling reaction between thioformamides and organolithium and Grignard reagents was developed. The generality of the process has been demonstrated by using various combinations of reactants and reagents. Information about the mechanism of the reaction has come from H-1 and C-13 NMR spectroscopic detection of the key intermediate. The LiS group in the intermediates generated by addition of the organolithium reagents to the thioformamides serves as a leaving group. The solid byproduct formed in these reactions, formulated as [LiSMgBr], can be used as a thiolating agent to transform acid chlorides into thioic acids and thioic acid anhydrides.