Structures and cytotoxic activity relationship of casearins, new clerodane diterpenes from Casearia sylvestris Sw

Casearins G-R, new cytotoxic clerodane diterpenes have been isolated from the leaves of Casearia sylvestris Sw. (Flacourtiaceae). Their structures have been elucidated by spectroscopic methods and chemical conversions, and their structure-activity relationships have been discussed.     

Semiempirical calculation of electronic spectra of organic compounds by using the improved method of new-γ electron repulsion integral. Part 2. Polycyclic aromatic hydrocarbons (PAHs)

Excitation energies of 123 polycyclic aromatic hydrocarbons were calculated by incorporating the improved method of new-γ for the two-center electron repulsion integral into two semiempirical molecular orbital methods (CNDO/S and INDO/S). This variable method well reproduced experimental excitation energies of them. The average error of the improvement is about 0.162 (CNDO/S) or 0.237 eV (INDO/S) though the average error without the improvement is about 0.541 (CNDO/S) or 0.536 eV (INDO/S). The improvement was useful for the calculations of other organic compounds including hetero atoms, such as organic dye.     

First isolation of 1,3,2-dithiaphosphetane 2-sulfide

The treatment of tert-alkyl phenyl thioketones with Lawesson’s reagent (LR) gave two diastereomeric 1,3,2-dithiaphosphetane 2-sulfides in high yields. The structure of one of the major diastereomers was determined by X-ray crystallography. The reaction of 2-adamantanethione with LR yielded the corresponding spiro-1,3,2-dithiaphosphetane 2-sulfide derivative in 87% yield.     

Stereoselective synthesis of (25R)-25,26-dihydroxy-23-oxovitamin D3 and its enzymatic conversion to (25R)-1α,25,26-trihydroxy-23-oxovitamin D3, a putative metabolite of vitamin D3

(25$\text{R}$)-25,26-Dihydroxy-23-oxovitamin D₃ was synthesized efficiently and stereoselectively, and it was converted enzymatically to (25$\text{R}$)-1α,25,26-trihydroxy-23-oxovitamin D₃, a putative metabolite of 1α,25-dihydroxyvitamin D₃. The spectral and chemical properties of (25$\text{R}$)-25,26-dihydroxy-23-oxovitamin D₃ and its 1α,hydroxylated derivative disagree with those reported for the isolated metabolite.     

Heteroatom-guided torquoselective olefination of alpha-oxy and alpha-amino ketones via ynolates

Ynolates were found to react with alpha-alkoxy-, alpha-siloxy-, and alpha-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the beta-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, alpha-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and gamma-butyrolactams in good yield.