The coupling of isonitriles and carboxylic acids occurring by sequential concerted rearrangement mechanisms

Org Lett. 2008 Sep 18;10(18):4093-6. doi: 10.1021/ol8016287. Epub 2008 Aug 16.

Abstract

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Anhydrides / chemistry
  • Carboxylic Acids / chemistry*
  • Nitriles / chemistry*
  • Quantum Theory

Substances

  • Anhydrides
  • Carboxylic Acids
  • Nitriles