One-Pot Synthesis of Glutathione Trisulfide from Oxidized Glutathione.

The excellent medicinal efficacy of glutathione trisulfide, an endogenous compound consisting of sulfane sulfur and two molecules of reduced glutathione, has been reported in recent years. However, no efficient procedure for the synthesis of trisulfide is yet available. Herein, we investigated the optimal conditions for the oxidation reaction of oxidized glutathione to thiosulfinate and its subsequent trisulfidation reaction using commercially available materials.

Highly regio- and stereoselective (3 + 2) annulation reaction of allenoates with 3-methyleneindolin-2-ones catalyzed by a planar chiral [2.2]paracyclophane-based bifunctional phosphine-phenol catalyst.

A planar chiral [2.2]paracyclophane-based phosphine-phenol catalyst catalyzed the (3 + 2) annulation reaction of ethyl 2,3-butadienoate with 3-methyleneindolin-2-ones to produce 2,5-disubstituted cyclopentene-fused C3-spirooxindoles in high yields with high regio-, diastereo-, and enantioselectivities. This catalyst was suitable for reactions of not only benzylideneindolinones but also alkylideneindolinones, the chiral phosphine-catalyzed reactions of which have not yet been reported.

Solubilization and stabilization of lipoic acid trisulfide by creation of various β-cyclodextrin clathrates.

Lipoic acid trisulfide, a sulfane sulfur-containing trisulfide of α-lipoic acid, holds promise in pharmaceuticals, yet knowledge gaps persist regarding its synthesis, properties, and stability. Here, we synthesized the lipoic acid trisulfide with a purity exceeding 99% from α-lipoic acid on a gram scale and obtained novel β-cyclodextrin clathrates (84%-95% yield). Differential scanning calorimetry confirmed the inclusion of lipoic acid trisulfide in β-cyclodextrins.

Organocatalyzed Amine-Free O-Phosphorylation of Alcohols with 4-Methylpyridine N-Oxide.

Amine-free phosphorylation of various alcohols was developed with 4-methylpyridine N-oxide in the presence of 4 Å molecular sieves at room temperature. This mild method gave various phosphorylated products in high yield and could be applied to acid- or base-sensitive substrates. Furthermore, this method was also effective for the chemoselective phosphorylation of diols or polyols.