CN1324798A - Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity - Google Patents
Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity Download PDFInfo
- Publication number
- CN1324798A CN1324798A CN 00107722 CN00107722A CN1324798A CN 1324798 A CN1324798 A CN 1324798A CN 00107722 CN00107722 CN 00107722 CN 00107722 A CN00107722 A CN 00107722A CN 1324798 A CN1324798 A CN 1324798A
- Authority
- CN
- China
- Prior art keywords
- trisaccharide
- obtains
- tribromo
- disaccharide
- benzoyl
- 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.)
- Pending
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
The synthesis of tetrasaccharide repeating unit of manno-glucosan which possesses biological activity and can be used as anti-cancer medicine includes the following steps: firstly, coupling the benzoylated mannose trichloroacetyliminoester with glucose whose 3-position is free hydroxyl group to obtain disaccharide, then making acid hydrolysis and selectively removing 4,6-benzal group or 5,6 isopropylidene group, and selectively coupling with another benzoylated mannose trichloroacetyliminoester at 6-position to obtain trisaccharide, making acid hydrolysis and removing 1,2-position ethylidene group or isopropylidene group; after activation, coupling with monosaccharide receptor whose 4-position is free hydroxyl group, and making deprotection so as to obtain the tetrasaccharide repeating unit.
Description
The invention relates to bioactive, particularly relate to and can be used as the synthetic of tetrose repeating unit antitumour drug, sweet dew-polyglucose.
By being separated to a sweet dew-polyglucose among the microorganism Microellobosporia grisea, this polysaccharide has strong anti-tumor activity, (sees CarbohydrateResearch 114 (1983) 245-256 such as K.Inoue by the polysaccharide that a tetrose repeating unit is formed; 115 (1983) 199-208; 123 (1983) 305-314).This tetrose is made of two seminoses and two glucose, and its structure is:
This tetrose does not have the people synthetic so far as yet.We think that synthetic this tetrose is not only very important to the active relation of research oligosaccharide structure, and this tetrose might be as new antitumor drug.
The objective of the invention is to adopt new thinking, provide a kind of step simple, save time, the labour-saving, can be used as the synthetic method of tetrose repeating unit of the sweet dew-polyglucose of antitumor drug.
The object of the present invention is achieved like this: with the tetrose separated into two parts, and three saccharide donors of left and right-hand monose acceptor among the promptly last figure.As shown below:
R=acyl group or alkyl protecting group X=leavings group R '=hydrogen atom or alkyl
Synthetic method of the present invention is: 1. be glycosyl donor with benzoylated seminose tribromo-acetyl imines ester 1, with 4,6-O-benzal base-1, the glucose 2 of 2-O-ethidine protection is glycosyl acceptor, glycosyl donor and glycosyl acceptor are dissolved in respectively in the methylene dichloride, then the two are mixed, add the Lewis acid of catalytic amount, reaction is 2-4 hour under stirring, room temperature, prepares disaccharide 3; The benzal base of disaccharide 3 is removed through acid hydrolysis, obtain disaccharide 4; Be glycosyl donor with benzoyl seminose tribromo-acetyl imines ester 1 then, with etc. the disaccharide 4 of mol ratio be glycosyl acceptor, be dissolved in glycosyl donor and glycosyl acceptor in the methylene dichloride respectively, then with the two mixing, the Lewis acid that adds catalytic amount, reaction is 2-4 hour under stirring, room temperature, prepares trisaccharide 5; With trisaccharide 5 acetylizes, acid hydrolysis remove ethidine, acetylize obtains trisaccharide 7 again; Trisaccharide 7 is optionally removed 1 ethanoyl, make the tribromo-acetyl imines ester 8 of trisaccharide then by standard method;
Or with the tribromo-acetyl imines ester 8 of the synthetic trisaccharide of another kind of method, promptly with 1,2:5,6-two-O-isopropylidene glucose is initiator, at first obtain disaccharide with 1 coupling of benzoyl seminose tribromo-acetyl imines ester, optionally hydrolysis removes 5 then, and the 6-isopropylidene obtains 10, obtains trisaccharide 11 with 1 coupling again, then acid hydrolysis removes 1, the 2-isopropylidene, acetylize obtains trisaccharide again, makes the tribromo-acetyl imines ester 8 of trisaccharide by standard method;
Bz=benzoyl Ac=ethanoyl 2.2 among the above figure, 3, the monose alkylglycoside acceptor of 6 acyl groups protection is by 4, the glucose alkylglycoside 12 of 6 benzalizations is through 2,3 benzoylations obtain the glucoside 13 of full guard, acid hydrolysis removes the benzal base and obtains 14, and 6 benzoylations of selectivity obtain monose acceptor 15 then;
R=alkyl or aryl R '=acyl group 3. is dissolved in three saccharide donors 8 in the methylene dichloride with monose acceptor 15 in the formula, carries out linked reaction under Louis acid catalysis, and the tetrose 16 that is protected is taken off protection according to a conventional method, obtains tetrose 17;
R=hydrogen atom or alkyl or aryl R ' in the formula=acyl group Bz=benzoyl Ac=ethanoyl
Described Lewis acid is trimethyl silicane triflate (TMSOTf) or boron trifluoride-ether network and thing (BF
3.Et
2O).
Describe below in conjunction with embodiment.
Embodiment: the preparation method one of three saccharide donors 8
Disaccharide 3 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-4,6-O-benzylidene-1,2-O-(R, preparation S)-ethylidene-α-D-glucopyranose):
Benzoylated seminose tribromo-acetyl imines ester 1 (741 milligrams, 1 mmole) is dissolved in 20 milliliters of methylene dichloride, gets solution A; 4; 6-O-benzal base-1,2-O-ethidine glucose 2 (293 milligrams, 1 mmole) is dissolved in 10 milliliters of methylene dichloride; get solution B; with B mix with A solution C, in C, add TMSOTf (20 microlitres, 0.23 mmole); after two hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.Reaction solution is diluted with 10 milliliters of methylene dichloride, neutralize with triethylamine, wash solution with water, aqueous phase discarded, organic phase is drained under vacuum, and the crude product that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain 3 785 milligrams in pure disaccharide, productive rate: 90%; Fusing point: 140-145 ℃, specific rotatory power [α]
D+ 13 °;
2 disaccharide 4 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-1,2-O-(R, preparation S)-ethylidene-α-D-glucopyranose):
3 (872 milligrams, 1 mmole) are dissolved in 10 milliliters of acetate, 1 milliliter of the dichloro acetic acid of adding 80%, under agitation room temperature reaction is after six hours, and thin-layer chromatographic analysis shows to react to be finished.Reaction solution is diluted with water, and with 30 milliliters of dichloromethane extractions, organic phase is drained under vacuum then successively with saturated sodium bicarbonate and water washing, obtains 731 milligrams of the thick products of crystalline, productive rate: 91%; Fusing point: 150-152 ℃, specific rotatory power [α]
D-24 °;
3 trisaccharides 5 (2,3,4,6-Tetra-O-henzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-1,2-O-(R, preparation S)-ethylidene-α-D-glucopyranose):
Benzoylated seminose tribromo-acetyl imines ester 1 (741 milligrams; 1 mmole) is dissolved in 10 milliliters of methylene dichloride; get solution A, disaccharide 4 (784 milligrams, 1 mmole) is dissolved in 10 milliliters of methylene dichloride; get solution B; with B mix with A solution C, in C, add TMSOTf (20 microlitres, 0.23 mmole); after three hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.Reaction solution is diluted with 10 milliliters of methylene dichloride, neutralize with triethylamine, wash solution with water, aqueous phase discarded, organic phase is drained under vacuum, and the crude product that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain 5 1158 milligrams of pure trisaccharides, productive rate: 85%; Fusing point: 131-134 ℃, specific rotatory power [α]
D-1.5 °;
4 trisaccharides 6 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-4-O-acetyl-1,2-O-(R, preparation S)-ethylidene-α-D-glucopyranose):
Trisaccharide 5 (1362 milligrams, 1 mmole) is used the quantitative acetylize of diacetyl oxide-pyridine according to a conventional method, obtain 6,1376 milligrams of the trisaccharides of full guard, productive rate 98%; Fusing point: 131-134 ℃, specific rotatory power [α]
D-2.5 °;
5 trisaccharides 7 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-1,2,4-tri-O-acetyl-α, the preparation of β-D-glucopyranose):
With (1404 milligrams of trisaccharides 6; 1 Bo mole) is dissolved in 10 milliliter of 90% trifluoroacetic acid; under agitation, room temperature reaction is one hour; solution is drained under vacuum; the gained soup compound is used the quantitative acetylize of diacetyl oxide-pyridine according to a conventional method, obtain 7,1023 milligrams of trisaccharides; mainly form productive rate: 70% by αYi Gouti.Fusing point: 137-140 ℃, specific rotatory power [α]
D-5.1 °;
6 three saccharide donors 8 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-2, the preparation of 4-di-O-acetyl-α-D-glucopyranosyltrichloroacetimidate):
With (731 milligrams of trisaccharides 7,0.5 mmole) with (69 milligrams in salt of wormwood, 0.5 mmole) be dissolved among 10 milliliters of DMF, under agitation, room temperature reaction 12 hours, the reactant dilute with water, use dichloromethane extraction then, successively use 1N hydrochloric acid, water, sodium hydrogen carbonate solution washing organic phase, dry and concentrated organic phase, the soup compound that obtains is dissolved in 20 milliliters of methylene dichloride, add three chloroethene eyeballs (0.1 milliliter, 1 millimole) then, add DBU 14 microlitres again, reaction mixture under agitation, behind the room temperature reaction two hours, reaction mixture is drained under vacuum, refining with silica gel column chromatography, use ethyl acetate/petroleum ether (1/2) as leacheate drip washing, collect respective components, obtain 8,669 milligrams of trisaccharides, productive rate: 90%.Fusing point: 123-126, specific rotatory power [α]
D+ 1.5 °;
Embodiment: the preparation method two of three saccharide donors 8
Disaccharide 10 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-1,2:5, the preparation of 6-di-O-isopropylidene-α-D-glucofuranose):
Benzoylated seminose tribromo-acetyl imines ester 1 (741 milligrams; 1 mmole) is dissolved in 10 milliliters of methylene dichloride; get solution A; 1,2:5,6-two-O-isopropylidene glucose 9 (260 milligrams; 1 mmole) is dissolved in 10 milliliters of methylene dichloride; solution B, with B mix with A solution C, in C, add BF
3.OEt
2(20 microlitres, 0.16 mmole), after four hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.Reaction solution is diluted with 10 milliliters of methylene dichloride, with 1N salt acid elution, aqueous phase discarded, organic phase is drained under vacuum, the crude product that obtains is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/3), obtain 10 720 milligrams in pure disaccharide, productive rate: 90%; Fusing point: 110-113 ℃, specific rotatory power [α]
D+ 18 °;
2. trisaccharide 11 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-1, the preparation of 2-O-isopropylidene-α-D-glucofuranose):
Benzoylated seminose tribromo-acetyl imines ester 1 (741 milligrams, 1 mmole) is dissolved in 10 milliliters of methylene dichloride, gets solution A; disaccharide 10 (798 milligrams, 1 mmole) is dissolved in 10 milliliters of methylene dichloride, gets solution B; with B mix with A solution C, in C, add BF
3.OEt
2(20 microlitres, 0.16 mmole), after four hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.With triethylamine reactant is neutralized to neutrality, drains under vacuum then, the crude product that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain 11 970 milligrams of pure trisaccharides, productive rate: 80%; Fusing point: 120-123 ℃, specific rotatory power [α]
D+ 28 °;
Trisaccharide 7 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-1,2,4-tri-O-acetyl-α, the preparation of β-D-glucopyranose):
With (1216 milligrams of trisaccharides 11; 1 mmole) is dissolved in 10 milliliter of 90% trifluoroacetic acid; under agitation, room temperature reaction is one hour; solution is drained under vacuum; the gained soup compound is used the quantitative acetylize of diacetyl oxide-pyridine according to a conventional method, obtain 7,1042 milligrams of trisaccharides; mainly form productive rate: 71% by αYi Gouti.Product characteristics is with identical by the character described in the preparation method one, 5;
Embodiment: monose acceptor 15 (Allyl 2,3, the preparation of 6-tri-O-benzoyl-α-D-glucopyranoside):
With 4,6-O-benzal base-α-D-glucopyanosyl allyl group glycosides 12 (313 milligrams, 1 mmole), be dissolved in 10 milliliters of pyridines, in this solution, drip Benzoyl chloride (0.34 milliliter, 3 mmoles), be reflected at room temperature, carried out three hours under stirring, quantitatively obtain disaccharide 13, with ordinary method processing reaction liquid, the crude product that obtains is dissolved in the tetra oxygen furyl (20 milliliters), drips 3 milliliters in 1M sulfuric acid in this solution, then reactant under agitation is heated to 70 ℃, afterreaction was finished in two hours, was chilled to after the room temperature with the sodium hydrogen carbonate solution neutralization, used dichloromethane extraction, organic phase is drained under vacuum, the crude product that obtains is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/1), obtain 14 381 milligrams in disaccharide, productive rate 89%.With 14 being dissolved in 15 milliliters of pyridines of obtaining, under room temperature, stirring, drip (0.125 milliliter of Benzoyl chloride, 1 mmole), afterreaction was finished in three hours, and with ordinary method processing reaction liquid, the crude product that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/2) as leacheate drip washing, collect respective components, obtain 464 milligrams of pure monose receptor 9s, productive rate: 98%; Fusing point: 148-151 ℃, specific rotatory power [α]
D+ 28 °;
Embodiment: (Allyl 2 for tetrose 16,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-[2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 6)]-2,4-di-O-acetyl-β-D-glucopyranosyl-(1 → 4)-2,3, the preparation of 6-tri-O-benzoyl-α-D-glucopyranoside):
With 8 is (782 milligrams of glycosyl donors, 0.5 mmole), 15 is (266 milligrams of glycosyl acceptors, 0.5 mmole), they are dissolved in 10 milliliters of methylene dichloride, under agitation, in this solution, add TMSOTf (10 microlitres, 0.11 mmole), after four hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.With triethylamine reactant is neutralized to neutrality, drains under vacuum then, the crude product that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain 16 870 milligrams of pure tetroses, productive rate: 90%; Fusing point: 133-136 ℃, specific rotatory power [α]
D+ 38 °;
Embodiment: tetrose allyl group glycosides 17a (preparation of Allyl α-D-mannopyranosyl-(1 → 3)-α-D-mannopyranosyl-(1 → 6)--β-D-glucopyranosyl-(1 → 4)-α-D-glucopyranoside):
With (154 milligrams of tetroses 16,0.08 mmole) be suspended in 10 ml methanol, the solution that in this solution, adds the 2M0.1 milliliter, this solution spends the night under room temperature, stirring, the solution that obtains neutralizes with Zeo-karb, filter concentrated 48 milligrams of tetrose allyl group glycosides 17a, the productive rate: 85% of obtaining in back; Fusing point: 154-156 ℃, specific rotatory power [α]
D-7 °;
Embodiment: free tetrose 17b (α-D-mannopyranosyl-(1 → 3)-α-D-mannopyranosyl-(1 → 6)--β-D-glucopyranosyl-(1 → 4)-α, the preparation of β-D-glucopyranose):
With (307 milligrams of tetroses 16,0.16 mmole) be dissolved in 10 milliliters of methylene dichloride, add 10 ml methanol, under agitation add (30 milligrams of palladium chlorides, 0.17 mmole), react and finish after at room temperature 6 hours, filter and use the washed with dichloromethane filter cake, washings and reaction solution are merged, drain under the vacuum, it is suspended in 10 ml methanol then, add the solution of 0.18 milliliter of 2M in this solution, this solution is in room temperature, spend the night under stirring, the solution that obtains neutralizes with Zeo-karb, filter concentrated 90 milligrams of free tetrose 17b, the productive rate: 82% of obtaining in back; Specific rotatory power [α]
D-2 °.
Claims (4)
1. synthetic method that can be used as tetrose repeating unit antitumour drug, sweet dew-polyglucose, it is characterized in that: with benzoylated seminose tribromo-acetyl imines ester 1 is glycosyl donor, with 4,6-O-benzal base-1, the glucose 2 of 2-O-ethidine protection is glycosyl acceptor, is dissolved in glycosyl donor and glycosyl acceptor in the methylene dichloride respectively, then with the two mixing, the Lewis acid that adds catalytic amount, reaction is 2-4 hour under stirring, room temperature, prepares disaccharide 3; The benzal base of disaccharide 3 is removed through acid hydrolysis, obtain disaccharide 4; Be glycosyl donor with benzoyl seminose tribromo-acetyl imines ester 1 then, with etc. the disaccharide 4 of mol ratio be glycosyl acceptor, be dissolved in glycosyl donor and glycosyl acceptor in the methylene dichloride respectively, then with the two mixing, the Lewis acid that adds catalytic amount, reaction is 2-4 hour under stirring, room temperature, prepares trisaccharide 5; With trisaccharide 5 acetylizes, acid hydrolysis remove ethidine, acetylize obtains trisaccharide 7 again; Trisaccharide 7 is optionally removed 1 ethanoyl, make the tribromo-acetyl imines ester 8 of trisaccharide then by standard method;
Or with the tribromo-acetyl imines ester 8 of the synthetic trisaccharide of another kind of method, promptly with 1,2:5,6-two-O-isopropylidene glucose is initiator, at first obtains disaccharide with 1 coupling of benzoyl seminose tribromo-acetyl imines ester, optionally hydrolysis removes 5 then, the 6-isopropylidene obtains 10, obtains trisaccharide 11 with 1 coupling again, and then acid hydrolysis removes 1, the 2-isopropylidene, acetylize obtains trisaccharide 7 again; 1 ethanoyl of selective removal is made the tribromo-acetyl imines ester 8 of trisaccharide then by standard method;
Bz=benzoyl Ac=ethanoyl among the above figure
2. synthetic method that can be used as tetrose repeating unit antitumour drug, sweet dew-polyglucose; it is characterized in that: 2; 3; the monose alkylglycoside acceptor of 6 acyl groups protection is by 4; the glucose alkylglycoside 12 of 6 benzalizations is through 2; 3 benzoylations obtain the glucoside 13 of full guard, and acid hydrolysis removes the benzal base and obtains 14, and 6 benzoylations of selectivity obtain monose acceptor 15 then:
R=alkyl or aryl R '=acyl group in the formula
3. synthetic method that can be used as tetrose repeating unit antitumour drug, sweet dew-polyglucose, it is characterized in that: three saccharide donors 8 are dissolved in the methylene dichloride with monose acceptor 15, under Louis acid catalysis, carry out linked reaction, the tetrose 16 that is protected, take off protection according to a conventional method, obtain tetrose 17;
R=hydrogen atom or alkyl or aryl R ' in the formula=acyl group Bz=benzoyl Ac=ethanoyl
4. the Lewis acid described in the right 1,3 is trimethyl silicane triflate (TMSOTf) or boron trifluoride-ether network and thing (BF
3.Et
2O).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00107722 CN1324798A (en) | 2000-05-24 | 2000-05-24 | Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00107722 CN1324798A (en) | 2000-05-24 | 2000-05-24 | Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1324798A true CN1324798A (en) | 2001-12-05 |
Family
ID=4578898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00107722 Pending CN1324798A (en) | 2000-05-24 | 2000-05-24 | Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1324798A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357305C (en) * | 2005-12-30 | 2007-12-26 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
| CN100432089C (en) * | 2005-05-13 | 2008-11-12 | 湖南中烟工业有限责任公司 | Process of synthesizing 2,3,4,6-tetraacyl pyrane glucose |
| CN100457766C (en) * | 2006-09-26 | 2009-02-04 | 重庆邮电大学 | Active dextran tetra saccharide alkyl glycoside and its prepn process and application |
| CN101935313A (en) * | 2010-09-15 | 2011-01-05 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN102212088A (en) * | 2011-01-24 | 2011-10-12 | 南京工业大学 | Method for synthesizing beta-D glucose(1->3)alpha-L rhamnose(1-3)alpha-L rhamnose(1-3)alpha-L rhamnose |
| CN108912239A (en) * | 2018-06-19 | 2018-11-30 | 朱玉亮 | A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals |
| CN112266398A (en) * | 2020-09-30 | 2021-01-26 | 中国科学院海洋研究所 | Key disaccharide repeating unit of glucuronic acid mannan oligosaccharide and preparation method thereof |
-
2000
- 2000-05-24 CN CN 00107722 patent/CN1324798A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432089C (en) * | 2005-05-13 | 2008-11-12 | 湖南中烟工业有限责任公司 | Process of synthesizing 2,3,4,6-tetraacyl pyrane glucose |
| CN100357305C (en) * | 2005-12-30 | 2007-12-26 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
| CN100457766C (en) * | 2006-09-26 | 2009-02-04 | 重庆邮电大学 | Active dextran tetra saccharide alkyl glycoside and its prepn process and application |
| CN101935313A (en) * | 2010-09-15 | 2011-01-05 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN101935313B (en) * | 2010-09-15 | 2011-12-28 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN102212088A (en) * | 2011-01-24 | 2011-10-12 | 南京工业大学 | Method for synthesizing beta-D glucose(1->3)alpha-L rhamnose(1-3)alpha-L rhamnose(1-3)alpha-L rhamnose |
| CN108912239A (en) * | 2018-06-19 | 2018-11-30 | 朱玉亮 | A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals |
| CN112266398A (en) * | 2020-09-30 | 2021-01-26 | 中国科学院海洋研究所 | Key disaccharide repeating unit of glucuronic acid mannan oligosaccharide and preparation method thereof |
| CN112266398B (en) * | 2020-09-30 | 2022-10-04 | 中国科学院海洋研究所 | Key disaccharide repeating unit of glucuronic acid mannan oligosaccharide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kong | Recent studies on reaction pathways and applications of sugar orthoesters in synthesis of oligosaccharides | |
| Bai et al. | 2, 3-Anhydrosugars in glycoside bond synthesis. Application to α-d-galactofuranosides | |
| Ning et al. | Synthesis of β-(1→ 6)-branched β-(1→ 3) glucohexaose and its analogues containing an α-(1→ 3) linked bond with antitumor activity | |
| Li et al. | Recent advances in transition metal–catalyzed O-glycosylations | |
| Walvoort et al. | Stereoselective Synthesis of 2, 3-Diamino-2, 3-dideoxy-β-D-mannopyranosyl Uronates | |
| Yashunsky et al. | Synthesis of 3-aminopropyl glycosides of linear β-(1→ 3)-D-glucooligosaccharides | |
| Horník et al. | Synthesis and in vitro cytotoxicity of acetylated 3-fluoro, 4-fluoro and 3, 4-difluoro analogs of D-glucosamine and D-galactosamine | |
| Xue et al. | A total synthesis of OSW-1 | |
| CN1324798A (en) | Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity | |
| Zong et al. | Convenient synthesis of sulfated oligofucosides | |
| Ohtake et al. | A highly stereoselective construction of β-glycosyl linkages by reductive cleavage of cyclic sugar ortho esters | |
| Wessel et al. | Strategies for the synthesis of branched oligosaccharides of the Shigella flexneri 5a, 5b, and variant X serogroups employing a multifunctional rhamnose precursor | |
| Hada et al. | Synthetic studies on glycosphingolipids from the parasite Echinococcus multilocularis | |
| Dax et al. | Fluorinated Carbohydrates: Some New Aspects in Synthesis and Application | |
| Krog-Jensen et al. | Efficient synthesis of differently protected methyl (ethyl 1-thio-β-d-glucopyranosid) uronates and their evaluation as glucuronic acid donors and acceptors | |
| Borbás et al. | Scope and limitation of the application of the (methoxydimethyl) methyl group in the synthesis of 2′-O-, 6′-O-and 2′, 6′-di-O-(α-l-arabinofuranosyl)-β-d-galactopyranosyl-(1→ 6)-d-galactoses | |
| Di Brisco et al. | Development of a fluorescent probe for the study of the sponge-derived simplexide immunological properties | |
| CN1054607C (en) | Zone selection using saccharous ortho-ester as key intemediate and method for stereospecific synthesis of oligose | |
| CN102212088A (en) | Method for synthesizing beta-D glucose(1->3)alpha-L rhamnose(1-3)alpha-L rhamnose(1-3)alpha-L rhamnose | |
| Murguía et al. | An efficient synthetic route to O-(2-O-benzyl-3, 4-di-O-acetyl-α/β-l-fucopyranosyl)-trichloroacetimidate | |
| Chatterjee et al. | Stereoselective α-glycosidation using FeCl 3 as a Lewis acid catalyst | |
| CN1450075A (en) | Group No.1 oligose and sulfated products, their preparation process and medicine composition containing said oligose | |
| CN1072677C (en) | Method for synthesizing disaccharide and trisaccharide ortho-esters | |
| Krylov et al. | Stereoselective Synthesis of the 3-Aminopropyl Glycosides of α-d-Xyl-(1→ 3)-β-d-Glc and α-d-Xyl-(1→ 3)-α-d-Xyl-(1→ 3)-β-d-Glc and of Their Corresponding N-Octanoyl Derivatives | |
| CN1338462A (en) | Chemical synthesis of echinocystic saponin 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 | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |