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

被引：26

作者：

Birney, DM ^{[1
]}

机构：

[1] Texas Tech Univ, Dept Chem & Biochem, Lubbock, TX 79409 USA

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 05期

关键词：

D O I：

10.1021/ol049867i

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Two possible pathways for the nitrosation of formamide and N-methyl formamide by nitrosonium ion (NO+) have been investigated at the B3LYP/6-31 G(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.

引用

页码：851 / 854

页数：4

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