Six- vs seven-membered ring formation from the 1- bicyclo[4.1.0]heptanylmethyl radical: Synthetic and ab initio studies

Eric J. Kantorowski, Shawn W E Eisenberg, William H. Fink, Mark J. Kurth

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

The viability of utilizing 1-bicyclo[4.1.0]heptanylmethyl radical (3) to serve as a progenitor of seven-membered carbocycles was examined. Rate constants for the rearrangement of this radical to 3-methylenecycloheptyl radical (4) and 2-methylenecyclohexyl-1-methyl radical (6) were measured using the competition method of 3 with thiophenol over the temperature range of -75 to 59 °C. Arrhenius functions were calculated for the conversions of 3 to 4 and 3 to 6 and found to be log(k/s-1) = (12.38 ± 0.20) - (5.63 ± 0.23)/θ and log(k/s-1) = (11.54 ± 0.32) - (5.26 ± 0.37)/θ, respectively. The rate constants for these conversions at 25 °C are 1.86 x 108 s-1 and 5.11 x 107 s-1, respectively. Hence, the seven-membered ring-expanded carbocycle is formed 3.6 times faster at 25 °C than the nonexpanded species. This suggests that the 1-bicyclo[4.1.0]heptanylmethyl radical system may be synthetically useful in seven-membered ring-forming methodology. Preliminary theoretical examination of this radical system qualitatively predicted the experimentally determined energies of activation: PMP4/6-31G*//HF/6-31G*ΔE(a) (3 → 6 - 3 → 4) = 3.0 kcal/mol with zero point energy correction. The HF/6-31G* optimized reaction coordinate stationary points suggest cyclopropyl substituent eclipsing interactions play an important role in determining the kinetic outcome of these rearrangements.

Original languageEnglish (US)
Pages (from-to)570-580
Number of pages11
JournalJournal of Organic Chemistry
Volume64
Issue number2
DOIs
StatePublished - Jan 22 1999

ASJC Scopus subject areas

  • Organic Chemistry

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