Conformation and Dynamics of (−)-β-Caryophyllene

(?)-β-Caryophyllene (1) adopts three conformations in solution: αα(48%), βα(28%), and ββ(24%). The conformations were identified by an analysis of the ¹³C- and ¹H-NMR spectra at ?87.2 and ?153.8° in connection with APT, HETCOR, and COSY spectra, and subsequent NOESY experiments. The activation parameters of the conversion αα → βα were determined from a bandshape analysis of exchange-broadened ¹³C-NMR spectra of 8-[methylene-¹³C]- 1 to give ΔH^≠ = 5.9 ± 0.3 kcal/mol, ΔS^? = ?8.1 ± 1.8 cal/mol. · K. and ΔG = ?8.3 ± 0.8 kcal/mol. The observed population ratio of the different conformers is best described by MM3.