A thermal decarbonylation of penam β-lactams

Journal of Organic Chemistry

Volumn 73, Issue 8, 2008, Pages 3024-3031

  Wiitala, Keith W ^a   Tian, Zhixin ^a   Cramer, Christopher J ^a   Hoye, Thomas R ^a  

^a UNIVERSITY OF MINNESOTA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON MONOXIDE; CARBOXYLIC ACIDS; CHEMICAL ACTIVATION; DECARBONIZATION; ESTERIFICATION; MASS SPECTROMETRY; STOICHIOMETRY;

DEESTERIFICATION; RING OPENING; THERMAL DECARBONYLATION;

ESTERS;

ACID ANHYDRIDE; AMPHOLYTE; BETA LACTAM; CARBON MONOXIDE; CARBOXYLIC ACID DERIVATIVE; CATION; HETEROCYCLIC COMPOUND; METHYL GROUP; PENAM DERIVATIVE; THIAZOLE DERIVATIVE;

ARTICLE; CARBONYLATION; DENSITY FUNCTIONAL THEORY; ENERGY; ESTERIFICATION; FRAGMENTATION REACTION; GAS CHROMATOGRAPHY; ISOMER; MASS SPECTROMETRY; PROTON TRANSPORT; QUANTUM YIELD; STOICHIOMETRY; THERMAL ANALYSIS;

EID: 84961982140     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7023834     Document Type: Article

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19. (a) For the anionic reaction pathways for 5′ and 7′, reactant structures and TS structures corresponding to loss of carbon monoxide could be located, but no intermediate structures could be found. Attempts to generate, for example, intermediates associated with ring opening of the lactam following attack of the carboxylate on the amide carbonyl led smoothly back to reactants. Thus, lactam ring opening is computed to occur with concerted loss of carbon monoxide [e.g., see TS in brackets for 5′(anion) to 9′(anion)] However, the computed activation free energies for the reactions of each of 5′ and 7′ are in excess of 45 kcal/mol, suggesting that the anionic reaction does not play a significant role in the observed decarbonylations. (b) In the cases of neutral 5′ and 7′, bicyclic anhydrides formed by ring opening of the lactam together with proton transfer from the carboxylic acid to the 1,3-thiazolidine were identified as stable intermediates having free energies of 4.2 and 18.4 kcal/mol relative to precursors 5′ and 7′, respectively. Decarbonylation TS structures that produce zwitterionic thiazolinium carboxylate products could be located. Again, however, the computed free energies of activation were too high to be experimentally relevant: 53.7 and 59.4 kcal/mol for 5′ and 7′, respectively.
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