Development of molecular mechanics torsion parameters for α,β-cyclopropyl ketones and conformational analysis of bicyclo[m.1.0]alkan-2-ones

Eugene A Mash, Timothy M. Gregg, Matthew T. Stahl, W. Patrick Walters

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Conformations of cyclopropyl methyl ketone have been studied using ab initio methods in an effort to quantify the effects of conjugative overlap between the cyclopropane ring and an adjacent ketone carbonyl. Results were comparable with previous experimental and theoretical studies. Cyclopropyl methyl ketone exhibits a global energy minimum in the s-cis conformer and a local energy minimum near the s-trans conformer. The potential energy curve obtained was used to derive torsion parameters which were employed in molecular mechanics studies of the conformations of the set of bicyclo[m.1.0]alkan-2-ones having larger ring sizes from five- to 16-membered. Similar conformations for the cyclopropyl ketone substructure are observed for all the medium and large ring systems examined. Possible synthetic ramifications of local conformational anchoring by this functional group array are discussed.

Original languageEnglish (US)
Pages (from-to)2738-2742
Number of pages5
JournalJournal of Organic Chemistry
Volume61
Issue number8
StatePublished - Apr 19 1996

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Molecular mechanics
Ketones
Torsional stress
Conformations
Potential energy
Functional groups

ASJC Scopus subject areas

  • Organic Chemistry

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Development of molecular mechanics torsion parameters for α,β-cyclopropyl ketones and conformational analysis of bicyclo[m.1.0]alkan-2-ones. / Mash, Eugene A; Gregg, Timothy M.; Stahl, Matthew T.; Walters, W. Patrick.

In: Journal of Organic Chemistry, Vol. 61, No. 8, 19.04.1996, p. 2738-2742.

Research output: Contribution to journalArticle

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abstract = "Conformations of cyclopropyl methyl ketone have been studied using ab initio methods in an effort to quantify the effects of conjugative overlap between the cyclopropane ring and an adjacent ketone carbonyl. Results were comparable with previous experimental and theoretical studies. Cyclopropyl methyl ketone exhibits a global energy minimum in the s-cis conformer and a local energy minimum near the s-trans conformer. The potential energy curve obtained was used to derive torsion parameters which were employed in molecular mechanics studies of the conformations of the set of bicyclo[m.1.0]alkan-2-ones having larger ring sizes from five- to 16-membered. Similar conformations for the cyclopropyl ketone substructure are observed for all the medium and large ring systems examined. Possible synthetic ramifications of local conformational anchoring by this functional group array are discussed.",
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