Origins of Regioselectivity in the Reactions of α-Lactams with Nucleophiles. Two Distinct Acid-Catalyzed Pathways Involving O- and N-Protonation

Sterically stabilized α-lactams react by two distinct acid-catalyzed pathways. Protonation on oxygen results in nucleophilic attack at the acyl carbon and gives C-2 products. Protonation on nitrogen leads to nucleophilic attack at the C-3 carbon and yields C-3 products. The mechanism thus developed...

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Bibliographic Details
Published in:Journal of organic chemistry 2002-07, Vol.67 (15), p.5284-5294
Main Authors: Hoffman, Robert V, Zhao, Zhiqiang, Costales, Abran, Clarke, David
Format: Article
Language:English
Subjects:
Chemical reactivity
Chemistry
Exact sciences and technology
Organic chemistry
Reactivity and mechanisms
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Summary:Sterically stabilized α-lactams react by two distinct acid-catalyzed pathways. Protonation on oxygen results in nucleophilic attack at the acyl carbon and gives C-2 products. Protonation on nitrogen leads to nucleophilic attack at the C-3 carbon and yields C-3 products. The mechanism thus developed is very useful for understanding the changes in rates and product distributions in the reactions of sterically stabilized α-lactams with nucleophiles. It can also be extrapolated to other α-lactams so that a more coherent picture of α-lactam reactivity can be developed.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo020246h