ALPHA-LACTAM INTERMEDIATES IN BASE-PROMOTED REACTIONS OF O-SULFONYLATED HYDROXAMIC ACIDS WITH NUCLEOPHILES

Authors
HOFFMAN RV NAYYAR NK CHEN WT
Citation
Rv. Hoffman et al., ALPHA-LACTAM INTERMEDIATES IN BASE-PROMOTED REACTIONS OF O-SULFONYLATED HYDROXAMIC ACIDS WITH NUCLEOPHILES, Journal of the American Chemical Society, 115(12), 1993, pp. 5031-5034
Citations number
24
Categorie Soggetti
Chemistry
Journal title
Journal of the American Chemical Society → ACNP
ISSN journal
00027863
Volume
115
Issue
12
Year of publication
1993
Pages
5031 - 5034
Database
ISI
SICI code
0002-7863(1993)115:12<5031:AIIBRO>2.0.ZU;2-G
Abstract
The reaction of N-(sulfonyloxy) amides with bases proceeds by initial formation of an alpha-lactam intermediate. A primary kinetic deuterium isotope effect, k(H)/k(D) = 2.17, a leaving group effect, beta(lg)CH3 = 0.50, and nucleophilic trapping all confirm that the alpha-lactam i s produced in the rate-determining step. Ring opening to an ion pair a nd nucleophilic addition to C-2 produce 2-substituted amide products.