Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/10901
Title: Reliable Determination of Amidicity in Acyclic Amides and Lactams
Contributor(s): Glover, Stephen  (author)orcid ; Rosser, Adam A  (author)orcid 
Publication Date: 2012
DOI: 10.1021/jo300347k
Handle Link: https://hdl.handle.net/1959.11/10901
Abstract: Two independent computational methods have been used for determination of amide resonance stabilization and amidicities relative to N,N-dimethylacetamide for a wide range of acyclic and cyclic amides. The first method utilizes carbonyl substitution nitrogen atom replacement (COSNAR). The second, new approach involves determination of the difference in amide resonance between N,N-dimethylacetamide and the target amide using an isodesmic trans-amidation process and is calibrated relative to 1-aza-2-adamantanone with zero amidicity and N,N-dimethylacetamide with 100% amidicity. Results indicate excellent coherence between the methods, which must be regarded as more reliable than a recently reported approach to amidicities based upon enthalpies of hydrogenation. Data for acyclic planar and twisted amides are predictable on the basis of the degrees of pyramidalization at nitrogen and twisting about the C-N bonds. Monocyclic lactams are predicted to have amidicities at least as high as N,N-dimethylacetamide, and the β-lactam system is planar with greater amide resonance than that of N,N-dimethylacetamide. Bicyclic penam/em and cepham/em scaffolds lose some amidicity in line with the degree of strain-induced pyramidalization at the bridgehead nitrogen and twist about the amide bond, but the most puckered penem system still retains substantial amidicity equivalent to 73% that of N,N-dimethylacetamide.
Publication Type: Journal Article
Source of Publication: Journal of Organic Chemistry, 77(13), p. 5492-5502
Publisher: American Chemical Society
Place of Publication: United States of America
ISSN: 0022-3263
Field of Research (FOR): 030401 Biologically Active Molecules
030799 Theoretical and Computational Chemistry not elsewhere classified
030505 Physical Organic Chemistry
Socio-Economic Outcome Codes: 970106 Expanding Knowledge in the Biological Sciences
970103 Expanding Knowledge in the Chemical Sciences
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
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