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