title: The coupling of isonitriles and carboxylic acids occurring by sequential concerted rearrangement mechanisms.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
authors.forename: Gavin O
authors.initials: GO
authors.lastname: Jones
authors.forename: Xuechen
authors.initials: X
authors.lastname: Li
authors.forename: Amy E
authors.initials: AE
authors.lastname: Hayden
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Samuel J
authors.initials: SJ
authors.lastname: Danishefsky
mesh_terms: D000812:Anhydrides / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000812:Anhydrides; D002264:Carboxylic Acids; D009570:Nitriles