Nitrosation of amides involves a pseudopericyclic 1,3-sigmatropic rearrangement.
Two possible pathways for the nitrosation of formamide and N-methyl formamide by nitrosonium ion (NO(+)) have been investigated at the B3LYP/6-31G(d,p) level. The key steps are pseudopericyclic 1,3-sigmatropic rearrangements to give the observed N-nitrosamides. The transition structures (8a and 8b) are close to planar on the amide moiety and have remarkably low barriers of only 6.6 and 4.8 kcal/mol from the lowest energy conformations of 6a and 6b, respectively. [reaction: see text]
Birney
David M
DM
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061, USA. david.birney@ttu.edu