Molecular Disorder in (‒)-Encecanescin

(‒)-Encecanescin (1) has been isolated from the leaves of Eupatorium aschembornianum. Two conformers are present in the crystal structure as a result of molecular disorder. The structure of 1 was established by (1)H- and (13)C-NMR spectroscopy in CDCl(3) solution using 2D NMR techniques (gHSQC, gHMBC and NOESY). A Monte Carlo random search using molecular mechanics followed by the geometry optimization of each minimum energy structure using density functional theory (DFT) calculations at the B3LYP/6–31G* level and a Boltzmann analysis of the total energies generated accurate molecular models describing the conformational behavior of 1. The three most stable conformers 2–4 of compound 1 were reoptimized at the B3LYP/6-311++G(d,p) level of theory using CHCl(3) as a solvent. Correlations between the experimental (1)H- and (13)C-NMR chemical shifts (δ(exp)) have been found, and the GIAO/B3LYP/6-311++G(d,p) calculated magnetic isotropic shielding tensors (σ(calc)) for conformers 2 and 3, δ(exp) = a + b σ(calc), are reported. A good linear relationship between the experimental and calculated NMR data has been obtained for protons and carbon atoms.