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CN-119553292-B - Method for constructing S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compound to synthesize glycosyl sulfenamide

CN119553292BCN 119553292 BCN119553292 BCN 119553292BCN-119553292-B

Abstract

The invention discloses a method for constructing S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compounds to synthesize glycosyl sulfenamide, and belongs to the technical field of synthesis of pharmaceutical intermediates. The method takes an organic solution containing glycosyl mercaptan, amine compounds and electrolyte salt as electrolyte, places an anode and a cathode in the electrolyte, and introduces direct current to perform electrochemical reaction to obtain glycosyl sulfenamide compounds. The method has strong reaction universality and high target product yield, is realized through one-step chemical reaction, has mild reaction conditions, and does not need any transition metal catalyst.

Inventors

  • YAN NAN
  • JIANG QINGHUI
  • YANG SHU
  • WEN SHAN
  • WU YUEFEI
  • ZHANG XIAOWEI

Assignees

  • 江西师范大学

Dates

Publication Date
20260505
Application Date
20241129

Claims (6)

  1. 1. A method for constructing S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compound to form glycosyl sulfenamide is characterized in that an organic solution containing glycosyl mercaptan, amine compound and electrolyte salt is used as electrolyte, a carbon rod anode and a platinum sheet cathode are placed in the electrolyte, direct current is introduced, and electrochemical reaction is carried out to obtain glycosyl sulfenamide compound; The electrolyte salt comprises sodium iodide and/or potassium iodide; acetonitrile and water are adopted as mixed solvents for the electrolyte; The electrochemical reaction is carried out under the condition of air or protective atmosphere, the current of direct current is 5-15 mA, the temperature is 20-30 ℃ and the time is 40-50 min.
  2. 2. The method for constructing S-N bond to glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compounds according to claim 1, wherein the glycosyl mercaptan has the structure of formula 1: Formula 1: ; wherein R is a five-membered sugar ring, a six-membered sugar ring or a multi-membered sugar ring.
  3. 3. The method for constructing S-N bond to glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compound according to claim 1, wherein the amine compound has a structure of formula 2: formula 2: ; Wherein R 1 and R 2 are independently selected from hydrogen, primary, secondary or quaternary carbon, and R 1 and R 2 are not both hydrogen.
  4. 4. The method for constructing S-N bond to glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compound according to claim 1, wherein the glycosyl sulfenamide compound has the structure of formula 3: Formula 3: ; Wherein, the R is a five-membered sugar ring, a six-membered sugar ring or a multi-membered sugar ring; R 1 and R 2 are independently selected from hydrogen, primary, secondary or quaternary carbon, and R 1 and R 2 are not both hydrogen.
  5. 5. The method for constructing S-N bond into glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compounds according to any one of claims 1-4, wherein the molar ratio of the glycosyl mercaptan to the amine compounds is 1:1.5-2.5.
  6. 6. The method for constructing S-N bond into glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compounds according to any one of claims 1-4, wherein the molar ratio of the glycosyl mercaptan to the electrolyte salt is 1.0:0.5-1.5.

Description

Method for constructing S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compound to synthesize glycosyl sulfenamide Technical Field The invention relates to a method for constructing an S-N bond, in particular to a method for constructing an S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compounds to form glycosyl sulfenamide, belonging to the technical field of synthesis of pharmaceutical intermediates. Background Thioglycosides are a class of glycoside compounds that link a sugar group to an aglycone through a sulfur atom, and have a variety of important biological activities and physiological functions in an organism. The compounds have important biological activity in organisms, including antioxidant, anti-inflammatory, antibacterial, antiviral and other effects. Therefore, thioglycoside has wide application prospect in the fields of health care and medicine, and the synthesis and biological activity research of the compound has become one of research hotspots in the fields of biochemistry and medicinal chemistry. Thioglycosides possess a greater acid-base and enzymatic hydrolysis resistance than readily hydrolyzable oxyglycosides. Has good glycosidase inhibitory activity. And because of the weak bond energy of the C-S bond, the characteristic can be used as a donor and an acceptor, and can be widely applied to the synthesis of N-glycoside, C-glycoside, oligosaccharide and polysaccharide. In addition, thiosugars are widely found in pharmaceuticals, natural products and bioactive substances. For example, auranofin (Auranofin) for a wide range of applications in the treatment of arthritis while also exhibiting anti-cancer activity. hSGLT 1A inhibitor can effectively inhibit the absorption of glucose and galactose by human body, and is a clinically common diabetes drug. Calicheamicin (CALICHEAMICIN GAMMA) and Hsp 90 have good anti-tumor activity. Afrostyraxthioside A are used clinically in the treatment of nematode parasites. MUS-CB is a fluorescent non-hydrolytic analog of cellulase, and the like. Among the various thioglycosides developed to date, glycosylsulfenamides are particularly attractive. This class of stable thioglycoside compounds is widely used in industry and pharmaceutical chemistry. However, only a few reports have been made so far concerning the preparation of S-glycosyl sulfonamides. Itzstein and colleagues report a ALKYL HALIDES catalyzed process (Owen,D.J.;von Itzstein,M.,A one-pot synthesis of novel N,N-dialkyl-S-glycosylsulfenamides.Carbohydrate Research 2000,328,287-292.).Szilagyi for preparing thioglycosylsulfenamides from glycosyl thiols and secondary amines and colleagues report a silver catalyzed reaction (Illyés,T.-Z.;Molnár-Gábor,D.;Szilágyi,L.,Novel approaches to thesyntheses of N-substituted S-glycosyl-sulfenamides.Carbohydrate Research 2004,339,1561-1564.).Misra for synthesizing glycosylsulfenamides from disulfide compounds and amine compounds and colleagues report NBS catalyzed reaction for synthesizing sulfenamides from glycosyl thiols and amine compounds, however, this process requires (Gucchait,A.;Jana,K.;Misra,A.K.,Convenient preparation of thioglycomimetics:S-glycosylsulfenamides,sulfinamides and sulphonamides.RSC Advances 2017,7,32478-32487.).Gang He at a low temperature of-40 ℃ and colleagues report a copper catalyzed process (Bai,Z.;Zhu,S.;Hu,Y.;Yang,P.;Chu,X.;He,G.;Wang,H.;Chen,G.,Synthesis of N-acyl sulfenamides via copper catalysis and their use as S-sulfenylating reagents of thiols.Nature Communications 2022,13.). for synthesizing sulfenamides from glycosyl thiols and 3-methyldioxazolone but these processes still require the use of metal catalysts and oxidants. Therefore, the development of an environment-friendly method for synthesizing the compound has important significance. Disclosure of Invention In order to solve the technical problems in the prior art, the invention aims to provide a method for efficiently constructing S-N bond into glycosyl sulfenamide by electrochemically oxidizing glycosyl mercaptan and amine compounds, which is completed by one-step electrochemical reaction, the method has the advantages of high yield of the target substance, simple experimental operation, mild conditions and strong substrate universality, does not need to add any chemical reagents which are unfavorable for environment, such as metal catalysts, oxidants, reducing agents and the like, and is favorable for efficiently synthesizing the glycosyl sulfenamide. In order to achieve the technical aim, the invention provides a method for constructing S-N bond by electrochemically oxidizing glycosyl mercaptan and amine compound into glycosyl sulfenamide, which comprises glycosyl mercaptan and amine compound And taking the organic solution of the substance and the electrolyte salt as electrolyte, placing an anode and a cathode in the electrolyte, and introducing direct current to perform electrochemical reaction to obtain the glycosyl su