Studies on the Biomimetic Synthesis of Marine Ladder Polyethers via Endo-Selective Epoxide-to-Epoxonium Ring-Opening Cascades.

Marine ladder polyethers have attracted the attention of chemists and biologists because of their potent biological activities. Synthetic chemists have attempted to construct their polyether frameworks by epoxide ring-opening cascades, as Nakanishi hypothesis describes. However, Baldwin's rules of ring closure state that exo-selective intramolecular cyclization of epoxy alcohols is preferred over endo-selective cyclization. Herein, we investigated epoxide ring-opening cascades of polyepoxy alcohols in [EMIM]BF4/PFTB (1-ethyl-3-methylimidazolium tetrafluoroborate /perfluoro-tert-butyl alcohol) and found that all-endo products were formed via epoxide-to-epoxonium ring-opening cyclizations (not restricted by Baldwin's rules, which only apply to intramolecular hydroxyl-to-epoxide cyclizations). We determined that the key factor enabling polyepoxy alcohols to undergo a high proportion of all-endo-selective cyclization was inhibition of exo-selective hydroxyl-to-epoxide cyclization starting from the terminal hydroxyl group of a polyepoxy alcohol. By introducing a slow-release protecting group to the terminal hydroxyl group, we could markedly increase the cyclization yields of polyether fragments with hydrogen atoms at the ring junctions. For the first time, we constructed consecutively fused six-membered-ring and fused seven-, eight-, and nine-membered-ring polyether fragments by epoxide-to-epoxonium ring-opening cyclizations through the addition of a suitable Lewis acid. We also suggest that the biosynthesis of marine ladder polyethers may proceed via epoxide-to-epoxonium ring-opening cyclization of polyepoxide.

Redox-neutral α-functionalization of pyrrolidines: facile access to α-aryl-substituted pyrrolidines.

α-Aryl-substituted pyrrolidine moiety is found in many natural alkaloids. Starting from pyrrolidine, we were able to synthesize α-aryl-substituted pyrrolidines in one step using quinone monoacetal as the oxidizing agent and DABCO as the base. We also discovered the reaction condition needed to efficiently remove the N-aryl moiety from the α-arylated product. When the above reaction was carried out without the addition of an aryl nucleophile, the reaction of pyrrolidine and quinone monoacetal in 2,2,2-trifluoroethanol afforded octahydro-dipyrroloquinoline in high yield, which has the same skeleton as that of natural product incargranine B.

Purification, Characterization and Bioactivity of Different Molecular-Weight Fractions of Polysaccharide Extracted from Litchi Pulp.

Litchi polysaccharides are a kind of macromolecular polymers with various biological activities and a wide range of molecular weights. In this study, two separate fractions, with average molecular weights of 378.67 kDa (67.33%) and 16.96 kDa (6.95%), which were referred to as LP1 and LP2, respectively, were separated using an ultrafiltration membrane. Their physicochemical properties, and immunomodulatory and prebiotic activity were compared. The results revealed that LP2 contained more neutral sugar, arabinose, galactose and rhamnose, but less uronic acid, protein, mannose and glucose than LP1. Compared with LP1, LP2 possessed higher solubility and lower apparent viscosity. LP2 exhibited stronger stimulation on macrophage secretion of NO, TNF-α and IL-6, as well as better proliferation of Lactobacillus plantarum, Leuconostoc mesenteroides, Lactobacillus casei and Bifidobacterium adolescentis. These results suggest that an ultrafiltration membrane might be used to prepare a highly-active polysaccharide fraction from litchi pulp that may be used for food or drug development.

Physicochemical properties and prebiotic activities of polysaccharides from Zizyphus jujube based on different extraction techniques.

Zizyphus jujube polysaccharide was extracted with hot water, ultrahigh pressure, deep eutectic solvent (DES) and ultrahigh pressure-assisted DES. Comparative analyses were conducted on the yield, physicochemical properties and prebiotic activity of four polysaccharides (JP-H, JP-U, JP-D and JP-UD). The yield of JP-UD (10.42 %) was 3.3 times that of JP-H (3.12 %), and its sugar content was the highest. JP-UD possessed the lowest Mw, while JP-H possessed the highest. Four JPs were acidic pyranose and mainly composed of galacturonic acid, arabinose and galactose. NMR results demonstrated that they contained not only similar glycosidic linkage but also the specific glycosidic linkage of →4)-α-D-Glcp-(l→ appeared in JP-U and JP-UD, the esterified units of GalA and CONH2 group appeared in JP-D and JP-UD, and the Terminal ß-D-Galp and →4)-α-GalpA-(1→ appeared in JP-UD. JPs showed different proliferation effects on four lactobacillus strains, among which JP-UD exhibited the strongest prebiotic activity. Zizyphus jujube polysaccharides have great potential for application in the functional food and medical industry.

Application of DMSO as a methylthiolating reagent in organic synthesis.

In the past decades, DMSO has been widely used not only as a common solvent but also as an environmentally benign oxidant in various organic transformations. Most strikingly, DMSO can be used as a sulfur source to construct methylthiolated building blocks of potential biologically active molecules, which is a remarkable achievement in the field of organic sulfur chemistry. The purpose of this review article is to summarize and discuss the main developments in the application of DMSO as a methylthiolating reagent to introduce the -SMe functionality in organic synthesis.