Constituents of holothuroidea.9. Isolation and structure of a new ganglioside molecular species from the sea cucumber Holothuria pervicax

A new ganglioside molecular species, HPG-7 (1) was obtained from the polar fraction of the chloroform/methanol extract of the sea cucumber, Holothuria pervicax. On the basis of chemical and spectroscopic evidence, the structure of 1 was determined, and the major component was 1-O-[alpha-L-fucopyranosyl-(1-->4)-(N-acetyl-alpha-D-neuraminosyl) - (2-->11)-(N-glycolyl-alpha-D-neuraminosyl)-(2-->4)-(N-acetyl -alpha-D- neuraminosyl)-(2-->6)-beta-D-glucopyranosyl]-(2S,3S,4R)-2-[(2R)-2- hydroxytetracosanoylamino]-14-methyl-hexadecane-1,3,4-triol. This is the first report on the isolation and structure elucidation of trisialo-ganglioside from sea cucumber. 1 showed neuritogenic activity toward the rat pheochromocytoma cell line, PC-12 cell.     

Synthetic studies toward maytansinoids (2) a new strategy based on asymmetric induction by heteroconjugate addition of methyllithium onto pyranosyl hetero-olefins

The functionalized pyranosyl hetero-olefins $\text{4a}$, $\text{13}$ and $\text{15}$ received a remarkable diastereoselective addition of methyllithium to form $\text{threo}$ adducts, one of which was introduced into a possible synthetic intermediate as $\text{3}$ for maytansine ($\text{1}$) along Scheme I.     

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.     

Fock representations of the affine Lie algebraA 1 (1)

The aim of this note is to show that the affine Lie algebraA ₁ ⁽¹⁾ has a natural family _, ,v of Fock representations on the spaceC[x _i,y _j;i andj ], parametrized by (,v) C ². By corresponding the highest weight _, of _, to each (,), the parameter spaceC ₂ forms a double cover of the weight spaceC₀C –₁ with singularities at linear forms of level –2; this number is (–1)-times the dual Coxeter number. Our results contain explicit realizations of irreducible non-integrable highest wieghtA ₁ ⁽¹⁾ -modules for generic (,v).     

Aurilide, a cytotoxic depsipeptide from the sea hare Dolabella auricularia: isolation, structure determination, synthesis, and biological activity

The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S₃ cells with an IC₅₀ of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1.     

First radical cation salts of 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions: β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4

New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)₄Cu₂Cl₆ and (BDA-TTP)₂CuCl₄, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting BDA-TTP layers alternate with the [Cu₂Cl₆]²⁻ or [CuCl₄]²⁻ anions. Both salts show the semiconductor-type temperature dependence of the conductivity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007.