Salvileucalin C, a novel rearranged neoclerodane diterpene from Salvia leucantha

Salvileucalin C (1), a novel neoclerodane diterpene having an unprecedented carbon framework and a structurally closely related salvileucalin D (2) were isolated and their absolute structures were elucidated by the vibrational circular dichroism (VCD) spectra.     

Total synthesis and biological assessment of (-)-exiguolide and analogues

We describe herein an enantioselective total synthesis of (-)-exiguolide, the natural enantiomer. The methylene bis(tetrahydropyran) substructure was efficiently synthesized by exploiting olefin cross-metathesis for the assembly of readily available acyclic segments and intramolecular oxa-conjugate cyclization and reductive etherification for the formation of the tetrahydropyran rings. The 20-membered macrocyclic framework was constructed in an efficient manner by means of Julia-Kocienski coupling and Yamaguchi macrolactonization. Finally, the (E,Z,E)-triene side chain was introduced stereoselectively via Suzuki-Miyaura coupling to complete the total synthesis. Assessment of the growth inhibitory activity of synthetic (-)-exiguolide against a panel of human cancer cell lines elucidated for the first time that this natural product is an effective antiproliferative agent against the NCI-H460 human lung large cell carcinoma and the A549 human lung adenocarcinoma cell lines. Moreover, we have investigated structure-activity relationships of (-)-exiguolide, which elucidated that the C5-methoxycarbonylmethylidene group and the length of the side chain are important for the potent activity.     

Right handed or left handed? Forbidden x-ray diffraction reveals chirality

Enantiomers, or stereoisomers, have crystal structures that are mirror images of each other and are thus handed, like our right and left hands. The physical properties of enantiomers are identical except for optical activity, which rotates linearly polarized light by equal amounts but in opposite directions. While conventional x-ray Bragg diffraction can determine crystal structures, it does not distinguish between right- and left-handed crystals. We show resonant Bragg diffraction using circularly polarized x rays reveals the handedness of crystals by coupling x-ray helicity to a crystal screw axis. The intensity of resonantly allowed reflection of alpha-quartz is well described by an admixture of a parity-even and a parity-odd process. Our results are of general importance and demonstrate a new method to directly study chiral motifs in structures that include biomaterials, liquid crystals, magnets, multiferroics, etc.     

Coherent and Incoherent Excitations of Electron-Doped SrTiO3

Resonant photoemission at the Ti 2p and O 1s edges on a Nb-doped SrTiO(3) thin film revealed that the coherent state (CS) at the Fermi level (E(F)) had a mainly Ti 3d character whereas the incoherent in-gap state (IGS) positioned approximately 1.5 eV below E(F) had a mixed character of Ti 3d and O 2p states. This indicates that the IGS is formed by a spectral-weight transfer from the CS and subsequent spectral-weight redistribution through d-p hybridization. We discuss the evolution of the excitation spectrum with 3d band filling and rationalize the IGS through a mechanism similar to that proposed by Haldane and Anderson.