240418-68-2

Upstream product

• 50-99-7 D-glucose 
• 30384-54-4 sodium S-(4-chlorophenyl) thiosulfate 
• 2873-29-2 D-glucal triacetate 
• 106-54-7 p-Chlorothiophenol 
• 118356-98-2 4,6-di-O-acetyl-3-O-D-glucal 
• 1142-19-4 4,4'-dichlorodiphenyl disulfide 

Relevant academic research and scientific papers

Unsaturated thioglycoside compound as well as selective synthesis method and application thereof

The invention discloses a synthesis method for selectively synthesizing an alpha-thioglycoside compound as shown in a formula (II) and a beta-thioglycoside compound as shown in a formula (III), which comprises the following steps: in a reaction solvent, by taking triacetyl glucose alkene as a reaction raw material and organic thiosulfates with different substituent groups as a sulfur source, under the action of a metal palladium salt and a ligand, selectively synthesizing an alpha-thioglycoside compound (II) and a beta-thioglycoside compound (III). The synthesis method provided by the invention has the advantages of easily available and cheap raw materials, simple reaction operation, mild reaction conditions, high yield and excellent functional group tolerance. According to the invention, synthesis and modification of some complex molecules are realized, and an efficient method for selectively constructing the thioglycoside compound containing the unsaturated bond is provided for research of pharmaceutical chemistry.

Diastereoselective Synthesis of Thioglycosides via Pd-Catalyzed Allylic Rearrangement

Stereoselective glycosylation is challenging in carbohydrate chemistry. Herein, stereoselective thioglycosylation of glycals via palladium-catalyzed allylic rearrangement yields various substituents on α-isomer thioglycosides. Two comprehensive series of aryl and benzyl thioglycosides were obtained via a combination of thiosulfates with glycals derived from glucose, arabinose, galactose, and rhamnose. Furthermore, diosgenyl α-l-rhamnoside and isoquercitrin achieved selectivity via stereospecific [2,3]-sigma rearrangements of α-sulfoxide-rhamnoside and α-sulfoxide-glucoside, respectively.

Synthesis of 3-S- and 3-Se-glycals by using R-S-S-R and R-Se-Se-R as the nucleophile precursors promoted by Hf(OTf)4 and the temperature-dependent formation of the above-mentioned 3-S- and 3-Se products

By using Hf(OTf)4 as the catalyst, under certain conditions, reaction of tri-O-acetyl-D-glucal and ((2R, 3S)-3-acetoxy-2,3-dihydrofuran-2-yl)methyl acetate with alkyl(aryl) bisulfide/alkyl(aryl) biselenide as nucleophile precursor leads to temperature-dependent formation of C-1-S/Se and C-3-S/Se product. A temperature-dependent profile of the yield of these two products is given.

Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst

In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-d-glucal and 6-deoxy-3,4-di-O-acetyl-l-glucal (3,4-di-O-acetyl-l-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol-1) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio α/β=4.129 in the case of peracetylated d-glucal and 8.740 in the case of l-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'α-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides.

Ruthenium Catalyzed Stereo/Chemo/Regioselective One-Pot Synthesis of C(2)-C(3) Unsaturated and α-d-Mannopyranosyl Sulfones

An efficient and divergent approach to C(2)-C(3) unsaturated glycosyl and α-d-mannopyranosyl sulfones has been developed via ruthenium-promoted direct glycosylation, oxidation, and dihydroxylation from glycal in one-pot. The presence of stoichiometric amounts of NaIO4 and in situ generation of RuO4 from a RuCl3-NaIO4 reagent system were crucial for chemoselective oxidation of sulfide in the presence of an olefin moiety. The dual-role of ruthenium in sequential glycosylation-oxidation-dihydroxylation is amenable to a wide range of thio acceptors to access α-d-mannopyranosyl sulfones in good yields with high regioselectivity.

3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated O- and S-glycosides and tetrahydropyranylation of alcohols and phenols

A simple procedure for the synthesis of 2,3-unsaturated glycosides in acetonitrile and tetrahydropyranylation of alcohols and phenols in dichloromethane in the presence of 3,5-dinitrobenzoic acid is described. A variety of alcohols and thiols are reacted with glycals to give the desired products in high yields with high α-selectivity.

Highly stereoselective synthesis of 2,3-unsaturated thioglycopyranosides employing molecular iodine

Molecular iodine has been utilized for the first time for the thioglycosidation of d-glycals with various thiols to afford the corresponding 2,3-unsaturated thioglycosides in high yields. In the case of tri-O-acetyl-d-glucal, the -anomer was obtained exclusively. The use of readily available iodine makes this method quite simple, more convenient, and practical. Georg Thieme Verlag Stuttgart.