New guaianolides from Berlandiera Pumila and B. Texana,and the X-ray crystal structure of pumilin

The isolation and structure determination of two new guaianolides, pumilin and its 2,3-epoxide, from Berlandiera pumila and B. texana are reported. The structure of pumilin was determined from nmr and mass spectral data, and from an X-ray single crystal study; the structure of the epoxide was found by comparison of nmr spectra. Pumilin is shown to be a Δ¹⁽¹⁰⁾-cis-guaianolide with a cyclopentenone ring attached to C1 and C5, and an α-methylene-γ-lactone ring trans-fused to C6 and C7. The absolute configuration was inferred from spectral considerations and knowledge of previous structural determinations. The cd spectrum of pumilin exhibits a negative Cotton effect, and the lactone chromophore has left-handed chirality. The cyclo-heptene ring is in the chair configuration, with the lactone a half-chair and the cyclopentenone essentially planar. Crystals are orthorhombic, a = 7.065, b = 13.652, c = 19.586 Å, space group P2₁2₁2₁, Z = 4, and the final R value is 3.9%. The crystal structure is strengthened by an O···O hydrogen bond linking the molecules into infinite chains.