Medium effects on the rates of stereomutation of a pair of diastereomeric cyclopropanones. Ground state stabilization in nucleophilic solvents induces deviation from solvent polarity controlled behavior

Matthew Hj Cordes, Jerome A. Berson

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The synthesis of the two stereoisomers of spiro(bicyclo[2.2.1]heptane-2,1'-cyclopropan)-2'-one, 3a and 4a, from diazomethane and the ketene 2-carbonylylbicyclo[2.2.1]heptane in ether at 195 K yields a ~1.6 to 1 ratio. At 245 K, the ratio changes in a first-order manner, with an observed rate constant of 1.7 x 10-4 s-1, to an equilibrium ratio of 0.8 to 1. The temperature dependence of the interconversion of 3a and 4a (GC method) and that of their dideuterio derivatives 3b and 4b (NMR method) have been determined and yield activation parameters E(a) = 16.3 ± 1.4 kcal/mol and log A = 10.4 ± 1.4 (A in s-1) (GC method) and E(a) = 15.3 ± 1.4 and log A = 9.6 ± 1.4 (NMR method). The free energies of activation at 239 K have been determined in four solvents: dichloromethane (16.1 kcal/mol), acetone (17.7), hexane (17.9), and ether (19.1). The solvent dependence does not correlate well with commonly used measures of solvent polarity, and the reaction is unexpectedly slow in acetone and ether. This deceleration is explained in terms of nucleophilic association of these solvents with the carbonyl groups in the cyclopropanones, leading to a ground state stabilization.

Original languageEnglish (US)
Pages (from-to)6241-6251
Number of pages11
JournalJournal of the American Chemical Society
Issue number26
Publication statusPublished - Jul 3 1996
Externally publishedYes


ASJC Scopus subject areas

  • Chemistry(all)

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