Synthesis method of 3-sulfur-1-glycal compound

A synthesis method and technology of ensaccharides, applied in the field of synthesis of 3-thio-1-enose compounds, can solve the problems that the stereoselectivity of products needs to be improved, the regioselectivity needs to be improved, etc.

Active Publication Date: 2020-11-27
CHINA THREE GORGES UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 1991, Professor Waldemar Priebe reported that 3-thiol-1-ene rhamnose was produced by reacting thiol with enose by a method similar to Macheal addition, but the stereoselectivity of the product needs to be improved
In 2014, Professor Chen Peiran used Sm(OTf)3 to synthesize a series of 1-thio-2-enose and 3-thio-1-enose with good yield, but the regioselectivity needs to be improved

Method used

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  • Synthesis method of 3-sulfur-1-glycal compound
  • Synthesis method of 3-sulfur-1-glycal compound
  • Synthesis method of 3-sulfur-1-glycal compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025]

[0026] Taking 3,4-O-carbonate galactenose and p-cresol as an example to optimize the experimental conditions, the details are as follows:

[0027]

[0028] Note: Unless otherwise stated, all experiments use 0.1mmol galactenose and 0.2mmol p-cresol, 10mol% cobalt catalyst, 20mol% monodentate phosphine ligand (or 10mol% bidentate phosphine ligand) in 2mL solvent 100 Schlenk tube reaction at ℃; isolated yield; regioselectivity and stereoselectivity >20:1 as measured by H NMR. XantPhos: 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene, DPPB: 1,4-bis(diphenylphosphine)butane, DPPF: 1,1'-bis( Diphenylphosphino) ferrocene.

[0029] The screening test of reaction conditions showed that the reaction conditions of cobalt tetrafluorobororide hydrate catalyst and Xantphos ligand in different solvents were different (entries 1-4), and Co(BF 4 ) 2 Catalyst, Xantphos ligand can get 3-thio-1-enose sugar in low yield (entries 1-2) in solvents such as dichloromethane and tetrah...

Embodiment 2

[0034]

[0035] Cobalt tetrafluoroborate hydrate Co(BF 4 ) 2 ·6H 2O (3.4mg, 0.01mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (Xantphos, 5.8mg, 0.010mmol), zinc powder (0.01mmol) and 3, 4-O-carbonate galactenose 1 (0.1 mmol) was added to 2 mL of acetonitrile and m-cresol (0.2 mmol). Stir at 100 degrees Celsius, TLC detects the reaction progress, when the sugar raw material completely disappears, stop the reaction, extract and collect the organic phase, distill the solvent under reduced pressure to obtain the crude product, and then use petroleum ether / ethyl acetate solution as the mobile phase for column chromatography 4-Hydroxy-3-m-methylphenylthio-1-enose was obtained (93% yield).

Embodiment 3

[0037]

[0038] Cobalt tetrafluoroborate hydrate Co(BF 4 ) 2 ·6H 2 O, 3.4 mg, 0.01 mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (Xantphos, 5.8 mg, 0.010 mmol), zinc powder (0.01 mmol) and 3, 4-O-carbonate galactenose 1 (0.1 mmol) was added to 2 mL of acetonitrile and o-cresol (0.2 mmol). Stir at 100-120 degrees Celsius, TLC to detect the reaction process, when the sugar raw material completely disappears, stop the reaction, extract and collect the organic phase, distill the solvent under reduced pressure to obtain the crude product, and then use petroleum ether / ethyl acetate solution as the mobile phase for column Chromatography afforded 4-hydroxy-3-o-methylphenylthio-1-enose (89% yield).

[0039] Substrate range

[0040] Mercaptans: preparation steps refer to Example 1

[0041]

[0042] Thiophenols: preparation steps reference example 1

[0043]

[0044] Aromatic heterocycles: preparation steps refer to Example 1

[0045]

[0046] Spectral data

...

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Abstract

The invention provides a synthesis method of a 3-sulfur-1-glycal compound. The preparation method comprises the following steps of: adding a catalyst, a ligand and galactan into an organic solvent andmercaptan/phenol; adding zinc powder, stirring and reacting at the temperature of 100 to 120 DEG C; detecting the reaction process through TLC, terminating the reaction when the galactan raw materialcompletely disappears, thereby obtaining 3-sulfur-1-glycal. The structural formula of mercaptan/phenol is R2-SH, and the structural formula of R2 comprises any one of methylene carboxylate, benzyl, alkyl, phenyl, substituted phenyl and five-membered or six-membered heterocyclic groups; and R1 comprises any one of a silicon group, an alkyl group, a C1-C18 alkyl group, a benzyl group, a phenyl group, a triphenylmethyl group, a pyridyl group, benzoate, pyridine acid ester and quinolinecarboxylic acid ester. According to the method, the cheap cobalt catalyst is adopted, the proper ligand and solvent are added to facilitate formation of a high-activity catalytic intermediate, and the zinc powder is added to promote smooth catalytic circulation of the cobalt catalyst.

Description

technical field [0001] The present invention mainly relates to a synthesis method of 3-thio-1-ene sugar compound. Background technique [0002] Thiosaccharides play an important role in the research fields of glycochemistry and medicinal chemistry. 1-Thiosugar is one of the most commonly used glycosyl donors, which plays a vital role in various glycosylation reactions, such as fatty sulfhydryl (-SH) and arylthiol (-SAr) groups Monosaccharide glucosinolates have been widely used in the synthesis of monosaccharides, oligosaccharides and polysaccharides, as well as glycoconjugates such as glycopeptides and glycoproteins. In addition, it is reported that a variety of thiosaccharides have been found to have good pharmacological activity, and have even been used as clinical drugs for many years. For example, the oral antirheumatic drug auranofin is a kind of glucosinolate containing gold; One of the star molecules in anti-tumor research. Not only is 1-thiosugar widely used as a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/18C07D309/30
CPCC07F7/1804C07F7/1892C07D309/30C07B2200/09Y02P20/584
Inventor 姚辉黄年玉焦阳罗华军邹坤
Owner CHINA THREE GORGES UNIV
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