Nitrosation of amides involves a pseudopericyclic 1,3-sigmatropic rearrangement

David M. Birney

doi:10.1021/ol049867i

Nitrosation of amides involves a pseudopericyclic 1,3-sigmatropic rearrangement

David M. Birney

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	851-854
Number of pages	4
Journal	Organic Letters
Volume	6
Issue number	5
DOIs	https://doi.org/10.1021/ol049867i
State	Published - Mar 4 2004

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abstract = "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.",

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AB - 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.

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