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Chemical Reactivity of Oxo‐ and Aza‐ γ ‐lactam Rings
Author(s) -
Borosky Gabriela L.,
Muñoz Francisco
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20010228)84:2<526::aid-hlca526>3.0.co;2-c
Subject(s) - chemistry , lactam , cleavage (geology) , reactivity (psychology) , bond cleavage , ab initio , fragmentation (computing) , tetrahedral carbonyl addition compound , hydrolysis , tetrahedron , computational chemistry , stereochemistry , crystallography , medicinal chemistry , organic chemistry , catalysis , nucleophile , medicine , alternative medicine , geotechnical engineering , pathology , fracture (geology) , computer science , engineering , operating system
Different mechanisms for the alkaline hydrolysis of oxo and aza‐ γ ‐lactam rings have been studied by ab initio calculations at the MP2/6‐31+G*//MP2/6‐31+G* and B3LYP/6‐31+G*//B3LYP/6‐31+G* levels. The tetrahedral intermediate can undergo two different reactions, the cleavage of the C 2 −N 2 bond (the classical mechanism) and the cleavage of the C 2 −X 6 bond (X=O, N). Both compounds present similar energy barriers for the classical fragmentation, and show considerably lower barriers for the alternative mechanism. Because of this reactivity, the compounds studied are expected to be β ‐lactamase inhibitors.