The coupling of isonitriles and carboxylic acids occurring by sequential concerted rearrangement mechanisms
The coupling of isonitriles and carboxylic acids occurring by sequential concerted rearrangement mechanisms
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DOI：
10.1021/ol8016287
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发表时间：
2008-09-18
期刊：
影响因子：
5.2
通讯作者：
Danishefsky, Samuel J.
中科院分区：
文献类型：
--
作者：
Jones, Gavin O.;Li, Xuechen;Danishefsky, Samuel J.
最近描述的异腈与羧酸的反应机理（Li，X.;达尼舍夫斯基，S。J·J·Am. Soc.2008，130，5446）用B3 LYP密度泛函方法研究。该机理涉及通过协同机理形成羧酸酯混合甲亚胺酸酐中间体。然后通过协调的假周环[1，3]-酰基转移将该中间体转化为N-甲酰胺。涉及两性离子或双自由基的机制被忽略。
Mechanisms for the recently described reactions of isonitriles with carboxylic acids (Li, X.; Danishefsky, S. J. J. Am. Chem. Soc. 2008, 130, 5446) are explored with the B3LYP density functional method. The mechanism involves the formation of a carboxylate mixed formimidic anhydride intermediate via a concerted mechanism. This intermediate is then transformed to an N-formylamide by a concerted pseudopericyclic [1,3]-acyl shift. Mechanisms involving zwitterions or diradicals are discounted.