CN104262422A - A chemical synthesis method of 4-(3,4-dihydroxybenzoyloxymethyl)-phenyl-O-beta-D-glucopyranoside - Google Patents

A chemical synthesis method of 4-(3,4-dihydroxybenzoyloxymethyl)-phenyl-O-beta-D-glucopyranoside Download PDF

Info

Publication number
CN104262422A
CN104262422A CN201410415034.7A CN201410415034A CN104262422A CN 104262422 A CN104262422 A CN 104262422A CN 201410415034 A CN201410415034 A CN 201410415034A CN 104262422 A CN104262422 A CN 104262422A
Authority
CN
China
Prior art keywords
glucopyranoside
phenyl
tetra
dihydroxybenzoyl
ethanoyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410415034.7A
Other languages
Chinese (zh)
Other versions
CN104262422B (en
Inventor
李玉文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Agricultural University
Original Assignee
Qingdao Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Agricultural University filed Critical Qingdao Agricultural University
Priority to CN201410415034.7A priority Critical patent/CN104262422B/en
Publication of CN104262422A publication Critical patent/CN104262422A/en
Application granted granted Critical
Publication of CN104262422B publication Critical patent/CN104262422B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20Carbocyclic rings
    • C07H15/203Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/55Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)

Abstract

A chemical synthesis method of 4-(3,4-dihydroxybenzoyloxymethyl)-phenyl-O-beta-D-glucopyranoside is disclosed. The method includes following steps of: reacting 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl bromide and p-hydroxybenzyl alcohol in a dry solvent under the action of an accelerant to obtain 4-hydroxymethylphenyl-O-beta-D-2,3,4,6-tetra-O-acetyl glucopyranoside; reacting the 4-hydroxymethylphenyl-O-beta-D-2,3,4,6-tetra-O-acetyl glucopyranoside and 3,4-diacetoxybenzoyl chloride to obtain 4-(3,4-diacetoxybenzoyloxymethyl)-phenyl-O-beta-D-2,3,4,6-tetra-O-acetyl glucopyranoside; and removing protective groups of the 4-(3,4-diacetoxybenzoyloxymethyl)-phenyl-O-beta-D-2,3,4,6-tetra-O-acetyl glucopyranoside to obtain the target product that is the 4-(3,4-dihydroxybenzoyloxymethyl)-phenyl-O-beta-D-glucopyranoside. The method has characteristics of cheap and easily available raw materials, short reaction steps, convenient separation, low preparation cost, little three-waste discharge, and suitability for industrial production.

Description

A kind of method of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl-O-β-D-glucopyranoside
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside.
Background technology
4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- o-β-D-glucopyranoside is a kind of Polyphenols glucoside of separation and Extraction from herbal medicine wild marjoram; there is anti-oxidant and scavenging free radicals function; liver cell and skin cells can be protected from oxidative damage; thus makeup and foodstuff additive [Chia-Hua Liang, Leong-Peng Chan, Hisou-Yu Ding can be used as; et al.; J. Agri. Food and Chem., 2012,7690-7696].But, 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe content of-β-D-glucopyranoside in wild marjoram very low (only 0.083%) [Nobuji Nakatani, Hiroe Kikuzaki, Agri. Biol. Chem., 1987,51 (10), 2727-2732], from wild marjoram, extract 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- o-β-D-glucopyranoside is very uneconomical, and destroys ecological resources, therefore studies 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe synthesis of-β-D-glucopyranoside is significant.
Summary of the invention
In view of from wild marjoram separation and Extraction 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- oit is high to there is cost in-β-D-glucopyranoside, destroys the drawback such as ecological resources, and the present inventor develops one on the basis of large quantity research in early stage can chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl in a large number)-phenyl- othe method of-β-D-glucopyranoside.
The object of this invention is to provide a kind of easy to operate, cost is low, can mass-producing synthesis 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside.
Chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl of the present invention)-phenyl- othe method of-β-D-glucopyranoside, its step is as follows:
1) by 2,3,4,6-tetra-- o-ethanoyl-α-D-bromo Glucopyranose with to hydroxy-benzyl alcohol in the dipolar aprotic solvent of drying, under the catalysis of Anhydrous potassium carbonate and cesium chloride promotor obtained 4-hyd roxymethyl phenyl- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside;
2) 4-hyd roxymethyl phenyl step 1) obtained- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside and 3,4-diacetoxy Benzoyl chloride are obtained by reacting 4-(3 in dry chlorinated hydrocarbon organic solvent and acid binding agent, 4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside;
3) by step 2) 4-(3 that obtains, 4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside in absolute alcohol kind solvent under the catalysis of tin type oxide the Acetyl Protecting Groups sloughed on sugared ring and phenyl ring obtain target product 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- o-β-D-glucopyranoside.
Chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl of the present invention)-phenyl- othe reaction formula of-β-D-glucopyranoside is as follows, wherein structural formula 1for 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- o-β-D-glucopyranoside, structural formula 2be 2,3,4,6-tetra-- o-ethanoyl-α-D-bromo Glucopyranose, structural formula 3for p-Hydroxybenzylalcohol, structural formula 4for 4-hyd roxymethyl phenyl- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside, structural formula 5be 3,4-diacetoxy Benzoyl chloride, structural formula 6for 4-(3,4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside.
Benefit of the present invention is: reactions steps is few, and reaction raw materials is cheap and easy to get, and each step reaction product is without the need to column chromatography for separation, and cost is low, and three waste discharge is few, is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
By 2,3,4,6-tetra-- o-ethanoyl-α-D-bromo Glucopyranose (50mmol; 20.5g) be dissolved in 50 milliliters of dry DMF; add p-Hydroxybenzylalcohol (55mmol; 6.85g) and Anhydrous potassium carbonate (60mmol; 8.3g); add catalytic amount (2.5mmol; 0,42g) cesium chloride, room temperature reaction 2 hours; by in reaction mixture impouring frozen water; separate out white solid, collecting by filtration white solid, gained white solid dehydrated alcohol recrystallization obtains white crystal 16.2g; yield 71%, fusing point 108.9-109.7 DEG C.
1HNMR(400MHz, CDCl 3) d 2.04, 2.05, 2.06, 2.08 (4 s, each 3H, 4OCOC H 3), 3.84-3.88(m, 1H, H-5), 4.18(dd, J = 12.4Hz, 4.2Hz, 1H, H-6a), 4.29(dd, J = 12.4Hz, 5.2Hz, 1H, H-6b), 4.64 ( s, 2H, ArC H 2OH), 5.07(d, J = 7.2 Hz, 1H, H-1), 5.16(t, J = 9.6Hz, 1H, H-4), 5.24-5.32(m, 2H, H-2, H-5), 6.98(d, J =8.4 Hz, 2H, Ar- H ), 7.27-7.31(m, 2H, Ar- H)。
By above-mentioned obtained 4-hyd roxymethyl phenyl- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside (20mmol; 9.08g) dissolve in 50ml dry methylene chloride; add acid binding agent triethylamine (22mmol; 2.22g); (21mmol is dripped under ice bath; 5.38g) 3,4-diacetoxy Benzoyl chlorides are at the solution of 10ml methylene dichloride, finish; remove ice bath; room temperature reaction 2 hours, reaction mixture uses water, saturated common salt water washing successively, separates dichloromethane layer; concentrating under reduced pressure obtains light yellow solid; white crystal 12.4g is obtained, yield 92.1%, fusing point 57-58 DEG C with dehydrated alcohol recrystallization. 1HNMR(400MHz, CDCl 3) d 2.03, 2.04, 2.7, 2.08 (4 s, each 3H, 4OCOC H 3), 2.32(s, 6H, ArOAc), 3.85(ddd, J = 10.0, 5.4, 2.0 Hz, 1H ), 4.18(dd, J = 12.4, 2.4 Hz , 1H ), 4.27(dd, J = 12.4, 5.4 Hz, 1H ), 5.08(d, J = 7.3Hz, 1H ), 5.17(t, J = 9.5Hz, 1H ), 5.24-5.33(m, 2H), 5.31(s, 2H), 7.02(d, J = 8.6Hz, 2H ), 7.29(d, J = 8.5Hz, 1H ), 7.36(d, J = 8.6Hz, 2H ), 7.85(d, J = 1.9Hz,1H ),7.98
(dd, J = 8.5, 1.9 Hz, 1H )。
By above-mentioned obtained 4-(3,4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside 6(15mmol, 10.1g) dissolve in 50ml anhydrous methanol, add catalytic amount Dibutyltin oxide (0.5mmol, 0.125g) heating reflux reaction 3 hours, concentrating under reduced pressure, resistates dehydrated alcohol-chloroform mixed solvent recrystallization (chloroform: dehydrated alcohol 8:1) obtains white crystal 5.76g, yield 92%, fusing point 203-204 DEG C. 1HNMR(400MHz, CD 3OD) d3.32-3.48 (m, 4H ), 3.68(dd, J = 12.1, 5.4 Hz , 1H ), 3.89(dd, J = 12.1, 2.1 Hz, 1H ), 4.91 (m, 1H), 6.79(d, J = 8.1Hz, 1H ), 7.12(d, J = 8.8Hz, 2H ), 7.38(d, J = 8.8Hz, 2H ), 7.42 (m, 2H )。
Embodiment 2
By 2,3,4,6-tetra-- o-ethanoyl-α-D-bromo Glucopyranose (0.1mol; 41g) be dissolved in 100 milliliters of dry DMF; add p-Hydroxybenzylalcohol (0.12mol; 7.47g) and Anhydrous potassium carbonate (0.24mol; 16.6g); add catalytic amount (5mmol; cesium chloride 0.84g); 40 DEG C are reacted 2 hours, by reaction mixture impouring frozen water, separate out white solid; collecting by filtration white solid; gained white solid dehydrated alcohol recrystallization obtains white crystal 33.3g, yield 73%, fusing point 108.1-109.4 DEG C.
By above-mentioned obtained 4-hyd roxymethyl phenyl- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside (0.04mol; 18.16g) dissolve in 100ml dry methylene chloride; add acid binding agent triethylamine (0.45mol; 4.45g); (0.42mol is dripped under ice bath; 10.76g) 3,4-diacetoxy Benzoyl chlorides are at the solution of 15ml methylene dichloride, finish; remove ice bath; room temperature reaction 2 hours, reaction mixture uses water, saturated common salt water washing successively, separates dichloromethane layer; concentrating under reduced pressure obtains light yellow solid; white crystal 24.8g is obtained, yield 92.4%, fusing point 57-58 DEG C with dehydrated alcohol recrystallization.
By above-mentioned obtained 4-(3,4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside 6(0.3mol, 20.2g) dissolve in 100ml anhydrous methanol, add catalytic amount Dibutyltin oxide (1mmol, 0. 25g) heating reflux reaction 3 hours, concentrating under reduced pressure, resistates dehydrated alcohol-chloroform mixed solvent recrystallization (chloroform: dehydrated alcohol 8:1) obtains white crystal 11.56g, yield 92.3%, fusing point 203-204 DEG C.

Claims (5)

1. a chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside, its step is as follows:
By 2,3,4,6-tetra-- o-ethanoyl-α-D-bromo Glucopyranose with to hydroxy-benzyl alcohol in the dipolar aprotic solvent of drying, under the catalysis of Anhydrous potassium carbonate and cesium chloride promotor obtained 4-hyd roxymethyl phenyl- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside;
The 4-hyd roxymethyl phenyl that step 1) is obtained- o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside and 3,4-diacetoxy Benzoyl chloride are obtained by reacting 4-(3 in dry chlorinated hydrocarbon organic solvent and acid binding agent, 4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside;
By step 2) 4-(3 that obtains, 4-diacetoxy benzoyloxymethy)-phenyl o-β-D-2,3,4,6-tetra-- o-ethanoyl glucopyranoside in absolute alcohol kind solvent under the catalysis of tin type oxide the Acetyl Protecting Groups sloughed on sugared ring and phenyl ring obtain target product 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- o-β-D-glucopyranoside.
2. according to claim 1described chemical 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside, is characterized in that used promotor is cesium chloride.
3. according to claim 1described chemical 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside, the dipolar aprotic solvent that it is characterized in that using in glycosylation reaction is acetone, DMF and dimethyl sulfoxide (DMSO).
4. according to claim 1described chemical 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside, it is characterized in that the chlorinated hydrocarbon solvent used in esterification is methylene dichloride, Benzene Chloride etc., the acid binding agent used is triethylamine, salt of wormwood etc.
5. according to claim 1described chemical 4-(3,4-dihydroxybenzoyl oxygen methyl)-phenyl- othe method of-β-D-glucopyranoside, is characterized in that the alcoholic solvent used in deprotection reaction is anhydrous methanol or ethanol, and the tin type oxide catalyzer used is Dibutyltin oxide.
CN201410415034.7A 2014-08-22 2014-08-22 A kind of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl) method of-phenyl-O-β-D-pyranglucoside Expired - Fee Related CN104262422B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410415034.7A CN104262422B (en) 2014-08-22 2014-08-22 A kind of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl) method of-phenyl-O-β-D-pyranglucoside

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410415034.7A CN104262422B (en) 2014-08-22 2014-08-22 A kind of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl) method of-phenyl-O-β-D-pyranglucoside

Publications (2)

Publication Number Publication Date
CN104262422A true CN104262422A (en) 2015-01-07
CN104262422B CN104262422B (en) 2016-06-29

Family

ID=52154030

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410415034.7A Expired - Fee Related CN104262422B (en) 2014-08-22 2014-08-22 A kind of chemosynthesis 4-(3,4-dihydroxybenzoyl oxygen methyl) method of-phenyl-O-β-D-pyranglucoside

Country Status (1)

Country Link
CN (1) CN104262422B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325136A (en) * 2017-08-10 2017-11-07 昆药集团股份有限公司 A kind of Acegastrodine compound and preparation method thereof, pharmaceutical composition, preparation and application
CN107383125A (en) * 2017-08-15 2017-11-24 昆药集团股份有限公司 A kind of Acegastrodine compound and preparation method thereof, preparation and application
CN108047285A (en) * 2017-12-18 2018-05-18 厦门医学院 A kind of cheap synthetic method of the glucose phenol glycosides compound of ortho position ester group substitution
CN111018928A (en) * 2019-12-06 2020-04-17 北京悦康科创医药科技股份有限公司 Synthetic method and application of gastrodin hemihydrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256472A (en) * 2003-02-27 2004-09-16 Japan Science & Technology Agency Dihydroxybenzoate derivative, method for producing the same and utilization thereof
CN103275146A (en) * 2013-06-13 2013-09-04 青岛农业大学 Gastrodin chemical synthesis method suitable for industrialization
WO2014052889A1 (en) * 2012-09-27 2014-04-03 The Board Of Trustees Of The University Of Illinois Anti-inflammatory agents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256472A (en) * 2003-02-27 2004-09-16 Japan Science & Technology Agency Dihydroxybenzoate derivative, method for producing the same and utilization thereof
WO2014052889A1 (en) * 2012-09-27 2014-04-03 The Board Of Trustees Of The University Of Illinois Anti-inflammatory agents
CN103275146A (en) * 2013-06-13 2013-09-04 青岛农业大学 Gastrodin chemical synthesis method suitable for industrialization

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHIA-HUA LIANG,等: "Free Radical Scavenging Activity of 4‑(3,4-Dihydroxybenzoyloxymethyl)phenyl‑O‑β‑D‑glucopyranoside from Origanum vulgare and Its Protection against Oxidative Damage", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 *
CHIA-HUA LIANG,等: "Free Radical Scavenging Activity of 4‑(3,4-Dihydroxybenzoyloxymethyl)phenyl‑O‑β‑D‑glucopyranoside from Origanum vulgare and Its Protection against Oxidative Damage", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》, vol. 60, 16 July 2012 (2012-07-16), pages 7691 *
ELENA V. STEPANOVA,等: "Synthesis of acyl derivatives of salicin, salirepin, and arbutin", 《CARBOHYDRATE RESEARCH》 *
李雯,等: "对位取代苯酚氧甙类化合物的相转移催化合成与结构表征", 《有机化学》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325136A (en) * 2017-08-10 2017-11-07 昆药集团股份有限公司 A kind of Acegastrodine compound and preparation method thereof, pharmaceutical composition, preparation and application
CN107383125A (en) * 2017-08-15 2017-11-24 昆药集团股份有限公司 A kind of Acegastrodine compound and preparation method thereof, preparation and application
CN108047285A (en) * 2017-12-18 2018-05-18 厦门医学院 A kind of cheap synthetic method of the glucose phenol glycosides compound of ortho position ester group substitution
CN108047285B (en) * 2017-12-18 2020-07-03 厦门医学院 Cheap synthesis method of ortho-ester-substituted glucose phenolic glycoside compound
CN111018928A (en) * 2019-12-06 2020-04-17 北京悦康科创医药科技股份有限公司 Synthetic method and application of gastrodin hemihydrate

Also Published As

Publication number Publication date
CN104262422B (en) 2016-06-29

Similar Documents

Publication Publication Date Title
Huang et al. A novel and efficient ionic liquid supported synthesis of oligosaccharides
CN104262422A (en) A chemical synthesis method of 4-(3,4-dihydroxybenzoyloxymethyl)-phenyl-O-beta-D-glucopyranoside
CN102304157B (en) Salidroside chemical synthesis method for industrialization
Unoh et al. Synthesis of highly substituted isocoumarins by rhodium-catalyzed annulation of readily available benzoic acids
CN102627675A (en) Method for preparing cane sugar-6-ester
Bergeron-Brlek et al. Synthesis of a small library of bivalent α-d-mannopyranosides for lectin cross-linking
Xu et al. Organotin-catalyzed regioselective benzylation of carbohydrate trans-diols
CN104045669A (en) Separation method suitable for chemical synthesis of salidroside for industrial production
Pischl et al. A convergent and stereoselective synthesis of the glycolipid components phthioceranic acid and hydroxyphthioceranic acid.
CN102617302B (en) Process for synthesizing trimethoxyphenyl stilbene
Xie et al. Regioselective debenzylation of C-glycosyl compounds by boron trichloride
Dey et al. Glycosidic bond hydrolysis in septanosides: a comparison of mono-, di-, and 2-chloro-2-deoxy-septanosides
Ayed et al. Indium-mediated alkynylation of sugars: synthesis of C-glycosyl compounds bearing a protected amino alcohol moiety
Shao et al. 1, 2-Migration of 2 ‘-Oxoalkyl Group and Concomitant Synthesis of 2-C-Branched O-, S-Glycosides and Glycosyl Azides via 1, 2-Cyclopropanated Sugars
Chen et al. Sm (OTf) 3 as a highly efficient catalyst for the synthesis of 2, 3-unsaturated O-and S-pyranosides from glycals and the temperature-dependent formation of 4-O-acetyl-6-deoxy-2, 3-unsaturated S-pyranosides and 4-O-acetyl-6-deoxy-3-alkylthio glycals
CN101481300B (en) Preparation of trans-polyhydroxy diphenyl ethylene
Schmölzer et al. Gram scale de novo synthesis of 2, 4-diacetamido-2, 4, 6-trideoxy-D-galactose
Yen et al. Concise synthesis of α-galactosyl ceramide from d-galactosyl iodide and d-lyxose
CN105237602B (en) A kind of preparation method of 2- amino arabinosy ladenosine
Hanashima et al. Thioester-assisted α-sialylation reaction
Huang et al. Large‐scale synthesis of per‐O‐acetylated saccharides and their sequential transformation to glycosyl bromides and thioglycosides
Yamada et al. Aryl C-glycosylation using an ionic liquid containing a protic acid
JP4950521B2 (en) Trehalose derivatives and process for producing the same
Liang et al. Efficient one-pot syntheses of α-D-arabinofuranosyl tri-and tetrasaccharides present in cell wall polysaccharide of Mycobacterium tuberculosis
CN103804283B (en) One prepares the method for 1,2-dihydrogen pyridine derivative

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160629

Termination date: 20170822