CN1129600C - Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide - Google Patents
Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide Download PDFInfo
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- CN1129600C CN1129600C CN 99126224 CN99126224A CN1129600C CN 1129600 C CN1129600 C CN 1129600C CN 99126224 CN99126224 CN 99126224 CN 99126224 A CN99126224 A CN 99126224A CN 1129600 C CN1129600 C CN 1129600C
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- trisaccharide
- isopropylidene
- glucose
- lentinan
- sugar
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Abstract
The present invention relates to a method for synthesizing lentinan core fragments, namely trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide by using 1, 2:5, 6 di-O-isopropylidene glucose as an initiator. The trichloroacetyl imide ester or halogeno substances of acyl glucose is used as a glycosyl donor, and 1, 2:5, 6 di-O-isopropylidene glucose is used as a glycosyl receptor. The method comprises: firstly, 1 1 3-beta-connected disaccharide is obtained, and 5, 6-O-isopropylidene is selectively hydrolyzed; disaccharide with free hydroxyl in 5 position and 6 position is obtained; secondly, the obtained disaccharide is used as a receptor, and is coupled with the trichloroacetyl imide ester or halogeno substances of acyl glucose as a glycosyl donor; trisaccharide is obtained; thirdly, the trisaccharide is hydrolyzed under acid condition, and is then acetylated; acetyl in 1 position is the selectively removed; after the trisaccharide is activated, a trisaccharide donor at a non-reducing end is obtained. The similar method is used for synthesizing a reducing-end trisaccharide receptor of glucose with free hydroxyl in 3 position; the trisaccharide donor is coupled with the trisaccharide receptor; the lentinan core fragment, namely hexasaccharide is obtained by removing protection; heptasaccharide is synthesized by the similar method.
Description
Technical field
The invention relates to bioactive, particularly include may as medicine, with 1,2:5,6-two-O-isopropylidene glucose are the lentinan core fragment trisaccharide of initiator, tetrose, six sugar, seven sugar synthetic.
Background technology
Known at present, strengthen the animal immune ability, mostly be polysaccharide greatly, as lentinan, ganoderan etc. by the polysaccharide that extracts in the practical fungus, or the polysaccharide that extracts in the herbal medicine.Studied clearly, had clear and definite immunocompetent oligosaccharides and few, as 1, the mannooligo saccharide, 1 that 3-α connects, the grape oligosaccharides that 3-β connects etc.But no matter be from natural goods, extract, isolating, the synthetic oligosaccharides of still exering great efforts, its usefulness all do not reach resemble plant defensive avionics system activator height (require 10
-8-10
-10The concentration of mol).Lentinan is the polysaccharide that clear and definite anti-tumor activity is arranged, improve body immunity, it is not directly to remove to attack tumour cell, thereby but the immunity system kill tumor cell by human activin, it in action the time at first with which receptors bind, do not get clear yet so far.The Japanese scientist who finds the lentinan anti-tumor activity at first thinks, the triple helices structure of lentinan is to keep its active necessary structure, and for example undressed molecular weight is 1,000,000 lentinan, all has the triple helices structure with the little lentinan that through acid-hydrolyzed molecular weight is 1.4 ten thousand, therefore have similar activity [[Carbohydr.Res.1993,245,81-96.Nature 1969,222,687].But we think that its triple helices structure is by its primary structure, promptly form the structures shape of the repeating unit oligosaccharides of polysaccharide, by this oligosaccharides and receptor acting, start immunologic process.But the checking that this hypothesis remains to be tested, we are carrying out the research of this respect.Figure below is the structure of lentinan repeating unit 7 sugar.
Repeating unit of Ientinan heptasaccharide still is not easy when synthesizing some oligosaccharides with existing method because the structure of the antigenic oligosaccharides that interrelates with different diseases is different very much.Up to now, Shang Weijian is about the synthetic report of the oligosaccharides repeating unit of lentinan.
Summary of the invention
The objective of the invention is in our synthesis of oligose of invention [Chinese patent application numbers 97125788.4 in the past, 98103241.1,98103242.7] the basis on, adopt brand-new thinking, promptly with 1,2:5,6-two-O-isopropylidene glucose is initiator, provide a kind of step simple, save time, laborsaving and with low cost, might be as the lentinan core fragment trisaccharide of medicine, tetrose, six sugar, the synthetic method of seven sugar.
The object of the present invention is achieved like this: tribromo-acetyl imines ester or halides 1 with acyl glucose are glycosyl donor; with 1; 2:5; the glucose 2 of 6-two-O-isopropylidene is glycosyl acceptor; at first obtain 1; the disaccharide 3 of 3-β-connection; optionally hydrolysis falls 5, and the 6-O-isopropylidene obtains 5; 6 is the disaccharide 4 of free hydroxyl group; make glycosyl donor 1 and glycosyl acceptor 4 couplings again, obtain trisaccharide 5, with 5 under acidic conditions hydrolysis obtain 6; then acetylize obtains 7; the ethanoyl of optionally taking off 1 again obtains 8; activate 8, obtain three saccharide donors 9.With synthetic 3 of similar method is three saccharide acceptors of the glucose of free hydroxyl group, with three saccharide donors and three saccharide acceptor couplings, goes protection promptly to obtain required six sugar again.With synthetic 3 of similar method is the tetrose acceptor of free hydroxyl group, with three saccharide donors and the coupling of tetrose acceptor, goes to protect promptly to obtain seven required sugar again.
Synthetic method of the present invention is:
(1) be glycosyl donor with 1 mole acyl glucose 1; with 1.2 moles 1; 2:5, the glucose 2 of 6-two-O-isopropylidene protection is glycosyl acceptor, is dissolved in glycosyl donor and glycosyl acceptor in the methylene dichloride respectively; then with the two mixing; at Louis acid catalysis, under the stirring at room, reacted 2-4 hour; prepare 1, the disaccharide 3 of 3-β-connection.Optionally hydrolysis falls 5; the 6-O-isopropylidene; obtain 5; 6 is the disaccharide 4 of free hydroxyl group, and the glycosyl donor 1 that mol ratio such as makes again and glycosyl acceptor 4 be at Louis acid catalysis, coupling under the stirring at room; obtain trisaccharide 5; hydrolysis obtains 6 under acidic conditions with 5, then acetylize obtains 7, optionally takes off 1 ethanoyl again and obtain 8,8 and three chloroethene eyeballs and react, and obtains the SCHMIDT glycosyl donor 9 of trisaccharide.As shown below:
R=CH
3CO-(ethanoyl) or PhCO-(benzoyl)
X=Br or Cl or CCl
3C (NH)-(tribromo-acetyl imido grpup)
(2) be three saccharide acceptors of the glucose of free hydroxyl group with synthetic 3 of similar method; promptly use 3-O-non-benzoyl-2; 4, the glycosyl donor 10 of 6-three-O-benzoyl-alpha-D-glucose makes itself and disaccharide 2 under Louis acid catalysis; coupling obtains corresponding trisaccharide 11 under the stirring at room; hydrolysis is fallen isopropylidene and is obtained disaccharide 12, makes itself and 1 coupling obtain trisaccharide 13, and optionally 3 non-benzoyl is fallen in hydrolysis; promptly obtain three saccharide acceptors 14, as shown below:
R=CH
3CO-, ClCH
2CO-, All-, Bn-, X=Br or Cl or CCl such as MeOBn-
3C (NH)-
(3) will wait three saccharide donors 9 of mol ratio and three saccharide acceptors 14 under Louis acid catalysis, coupling under the stirring at room obtains 6 sugar 15 of part protection; hydrolysis is fallen isopropylidene while ring expansion and is obtained 16; with 16 acetylizes, take off acyl group with alkali then, promptly obtain free 6 sugar 18.As shown below:
R=CH
3CO-or PhCO-X=Br or Cl or CCl
3C (=NH) O-
(4) the tetrose acceptor prepares with the method that is similar to preparation three saccharide acceptors 14.Can adopt the whole bag of tricks, only exemplify a kind ofly here, be about to trisaccharide 13 hydrolysis, ring expansion, activation, obtain another three saccharide donor 19, make itself and three,, promptly obtain the tetrose acceptor 22 its three deprotections for monose 20 couplings of free hydroxyl group promptly obtain tetrose 21.
R=ClCH
2CO-, CH
3CO-, All-, Bn-or MeOC
6H
4CH
2-etc., R '=CH
3CO-or PhCO-, R "=alkyl or aryl
(5) with three saccharide donors 9 and the coupling of tetrose acceptor 22, seven sugar 23 that are protected go protection promptly to obtain needed seven sugar 24 again.
(6) use similar method, can synthesize bigger oligosaccharides as nine sugar, ten sugar, ten disaccharides, ten tetroses etc.
In the described glycosyl donor preparation, the R base is the acetyl or benzoyl base, and X is bromine, chlorine or tribromo-acetyl imines ester.
In the described glycosyl acceptor preparation, the R base is an ethanoyl, chloracetyl, and allyl group, the benzyl of Bian Ji or replacement etc., X is bromine, chlorine or three chloroethene eyeballs.
In six sugar of described protection, seven sugar, the R base is the acetyl or benzoyl base.
Described tetrose acceptor terminal group and seven sugared terminal group are that α or β connect, and non-sugared body is divided into alkyl or aryl.
Described Lewis acid is silver salt such as silver carbonate, silver trifluoromethanesulfonate, or is boron trifluoride, or is the trifluoromethanesulfonic acid trimethylsilyl group.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.
Embodiment
The preparation of 1 three saccharide donors 9:
(1) preparation of disaccharide 3
Benzoyl glucose tribromo-acetyl imines ester 1 (5.6 grams, 7.56 mmoles) is dissolved in 40 milliliters of methylene dichloride, gets solution A; 1; 2:5,6-two-O-isopropylidene glucose 2 (2.8 grams, 10.77. mmole) is dissolved in 20 milliliters of methylene dichloride; get solution B; with B mix with A solution C, in C, add trifluoromethanesulfonic acid trimethylsilyl group (TMSOTF, 0.08 mmole); after two hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.Reaction solution is diluted HCl/CH with 0.5% with 100 milliliters of methylene dichloride
3The OH solution dilution also stirred 1 hour, and optionally hydrolysis falls 5,6-O-isopropylidene, triethylamine neutralization, decompression steams solvent, and is refining with silica gel column chromatography, uses ethyl acetate/petroleum ether (1/2) as leacheate drip washing, collect respective components, obtain disaccharide 4 (5.43 gram), productive rate: 90%.
(2) preparation of trisaccharide 5:
Benzoyl glucose tribromo-acetyl imines ester 1 (3.7 grams; 5.01 mmole) be dissolved in 30 milliliters of methylene dichloride, get solution A, disaccharide 4 (4.0 grams; 5.01 mmole) be dissolved in 30 milliliters of methylene dichloride; solution B, with B mix with A solution C, under cryosel bathe to cool off; in C, add TMSOTF 0.05 mmole; naturally return to room temperature then, after 3 hours, thin-layer chromatographic analysis shows to react to be finished at room temperature reaction.Reaction solution is neutralized with triethylamine, wash with water, aqueous phase discarded, organic phase is drained under vacuum, and crude product is refining with silica gel column chromatography, uses ethyl acetate/petroleum ether (1/1) as leacheate drip washing, collect respective components, obtain pure trisaccharide 7 (5.86 gram), productive rate: 85%.
(3) preparation of trisaccharide 7:
Trisaccharide 5 (6.0 grams, 4.36 mmoles) is dissolved in 50 milliliter of 80% acetic acid aqueous solution, and the thin-layer chromatographic analysis detection reaction is used in hydrolysis under 60 ℃ of stirrings, after reaction is finished.With reaction solution evaporate to dryness under reduced pressure; crude product is refining with silica gel column chromatography; with ethyl acetate/petroleum ether (1/1) as leacheate drip washing; collect respective components; obtain pure trisaccharide 6 (5.24 gram) productive rate: 90%; use the quantitative acetylize of diacetyl oxide/pyridine according to a conventional method with 6, obtain the trisaccharide 7 of full acidylate.
The preparation of (4) three saccharide donors 9:
Trisaccharide 7 (5.5 grams, 3.76 millimoles) is dissolved in 30 milliliters of dimethyl formamides, adds NH
4HCO
33 grams, reaction is at room temperature carried out, and use the thin-layer chromatographic analysis detection reaction, after reaction is finished, the evaporated under reduced pressure solvent, crude product is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/1) as leacheate drip washing, collect respective components, obtain pure trisaccharide 8 (4.8 gram), productive rate: 90%, with 8 (6 grams, 4.2 millimole) be dissolved in 40 milliliters of methylene dichloride, add 3 milliliters in three chloroethene eyeballs, salt of wormwood 3 grams, stirred under the room temperature 23 hours, tlc analysis shows to react to be finished, and carries out aftertreatment with ordinary method, and crude product is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/1) as leacheate drip washing, collect respective components, obtain three pure saccharide donors 9 (6.01 gram), productive rate: 91%.
The preparation of 2 three saccharide acceptors 14:
By 1 and 2 link coupled conditions; make 3-O-allyl group-2; 4; 6-three-O-benzoyl-alpha-D-glucose tribromo-acetyl imines ester 10 (5 grams, 7.38 millimoles) and 1,2:5; 6 isopropylidene glucose 2 (2.13 grams, 8.20 millimoles) coupling; after reaction is finished, reaction solution is diluted HCl/CH with 100 milliliters of methylene dichloride with 0.5%
3The OH solution dilution also stirred 1 hour, and optionally hydrolysis falls 5,6-O-isopropylidene, triethylamine neutralization, decompression steams solvent, and is refining with silica gel column chromatography, uses ethyl acetate/petroleum ether (1/1) as leacheate drip washing, collect respective components, obtain disaccharide 12 (4.89 gram), productive rate 90%.By 1 and 2 link coupled conditions, make again 1 with disaccharide 12 couplings, obtain trisaccharide 13 (5.67 grams, 65%), be dissolved in 100 milliliters of exsiccant methanol solutions 13, add Palladous chloride 0.5 gram, under room temperature, stirring, react, and detect with tlc analysis, when detection shows that allyl group has been removed by selectivity, filter, decompression is solvent evaporated down, and crude product is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/1) as leacheate drip washing, collect respective components, obtain trisaccharide 14 (4.94 gram), productive rate: 90%.
3. the preparation of six sugar 18
With three saccharide donors 9 (3 grams; 1.92 millimole) with three saccharide acceptors 14 (2.44 grams; 1.92 millimole) be dissolved in 40 milliliters of methylene dichloride; under cryosel bath cooling, add TMSOTf (0.02 mmole); naturally return to room temperature then; in nitrogen protection; react under room temperature, the stirring, detect, after reaction is finished with tlc analysis; use the ordinary method aftertreatment; crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (2/1); obtain six sugar 15 (4.11 gram), productive rate 80%.15 (3.5 grams, 1.31 mmoles) are dissolved in 40 milliliter of 80% acetic acid aqueous solution, and the thin-layer chromatographic analysis detection reaction is used in hydrolysis under 60 ℃ of stirrings, after reaction is finished.With reaction solution evaporate to dryness under reduced pressure; crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (2/1); it is used the quantitative acetylize of diacetyl oxide/pyridine according to a conventional method, obtain six sugar 17 (3.25 gram) of full acidylate.Productive rate 90%.17 (2 grams, 0.72 millimoles) are dissolved in 40 ml methanol, saturated with ammonia, ambient temperature overnight, use the tlc analysis detection reaction, after reaction was finished, the evaporated under reduced pressure solvent was used washed with dichloromethane, discard washings, obtain powder dress product 18 (681 milligrams), productive rate 95%.4. the preparation of tetrose acceptor 22
R '=Ac-R "=Me (β) is converted into the condition of three saccharide donors 9 by trisaccharide 5; trisaccharide 13 is converted into three saccharide donors 19; then by 1 and 2 link coupled conditions; make 19 (3.25 grams; 2.16 millimoles) and monose acceptor 20 (0.80 gram; 2.50 millimoles) coupling, obtain 4 sugar 21 (2.50 restrain productive rate 70%).5. the preparation of seven sugar 24 prepares the tetrose acceptor 22 by 13 to 14 process.Prepare the method for six sugar 18 by 9 and 14 couplings,, obtain seven sugar 23 (3.10 restrain productive rate 70%) by 9 (2.35 grams, 1.50 millimoles) and 22 (2.40 grams, 1.45 millimoles) coupling.The deprotection base obtains lentinan repeating unit seven sugar 24.
Claims (6)
1. one kind with 1,2:5, and 6-two-O-isopropylidene glucose is the synthetic method of the lentinan core fragment trisaccharide of initiator, it is characterized in that:
With 1 mole acyl glucose 1 is glycosyl donor, with 1.2 moles 1,2:5, the glucose 2 of 6-two-O-isopropylidene protection is glycosyl acceptor, is dissolved in glycosyl donor and glycosyl acceptor in the methylene dichloride respectively, then with the two mixing, at Louis acid catalysis, under the stirring at room, reacted 2-4 hour, prepare 1, the disaccharide 3 of 3-β-connection; Optionally hydrolysis falls 5; the 6-O-isopropylidene; obtaining 5,6 is the disaccharide 4 of free hydroxyl group, and the glycosyl donor 1 that mol ratio such as makes again and glycosyl acceptor 4 are at Louis acid catalysis; coupling under the stirring at room; obtain trisaccharide 5, with 5 under acidic conditions hydrolysis obtain 6, then acetylize obtain 7, optionally take off again 1 ethanoyl obtain 8,8 with the Trichloroacetonitrile reaction; obtain the SCHMIDT glycosyl donor 9 of trisaccharide, as follows:
R=acetyl or benzoyl base
X=tribromo-acetyl imido grpup
2. one kind with 1,2:5, and 6-two-O-isopropylidene glucose is the synthetic method of the lentinan core fragment trisaccharide of initiator, it is characterized in that:
1; 2:5; the glucose 2 of 6-two-O-isopropylidene protection is glycosyl acceptor; with glycosyl donor 10 under Louis acid catalysis, coupling obtains corresponding disaccharides 11 under the stirring at room, hydrolysis is fallen isopropylidene and is obtained disaccharide 12; make itself and 1 coupling obtain trisaccharide 13; optionally 3 protecting group is fallen in hydrolysis, obtains three saccharide acceptors 14, and is as follows:
The R=ethanoyl, chloracetyl, allyl group-, benzyl or to methoxy-benzyl; X=tribromo-acetyl imido grpup
3. one kind with 1,2:5, and 6-two-O-isopropylidene glucose is the synthetic method of lentinan core fragment six sugar of initiator, it is characterized in that:
Resulting three saccharide donors 9 and resulting three saccharide acceptors 14 of claim 2 of claim 1; mol ratio such as press; under Louis acid catalysis; coupling under the stirring at room obtains six sugar 15 that part is protected, and hydrolysis is fallen isopropylidene while ring expansion and obtained 16; with 16 acetylizes; take off acyl group with alkali then, obtain free six sugar 18, as follows:
R=acetyl or benzoyl base X=tribromo-acetyl imido grpup
4. one kind with 1,2:5, and 6-two-O-isopropylidene glucose is the synthetic method of the lentinan core fragment tetrose of initiator, it is characterized in that:
With resulting trisaccharide 13 hydrolysis of claim 2, ring expansion, activation, obtain another three saccharide donor 19, make itself and three for monose 20 couplings of free hydroxyl group promptly obtain tetrose 21, with its three deprotections, promptly obtain the tetrose acceptor 22.
The R=allyl group, benzyl, chloracetyl or to methoxy-benzyl; R '=acetyl or benzoyl base; R "=alkyl or aryl
5. one kind with 1,2:5, and 6-two-O-isopropylidene glucose is the synthetic method of lentinan core fragment seven sugar of initiator, it is characterized in that:
With resulting three saccharide donors 9 and the coupling of the resulting tetrose acceptor 22 of claim 4 of claim 1, seven sugar 23 that are protected go protection promptly to obtain needed seven sugar 24 again.
6. as each described synthetic method in the claim 1 to 5, it is characterized in that described Lewis acid is silver carbonate, silver trifluoromethanesulfonate, boron trifluoride or trifluoromethanesulfonic acid trimethylsilyl group.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99126224 CN1129600C (en) | 1999-12-16 | 1999-12-16 | Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide |
| AU64240/00A AU6424000A (en) | 1999-12-16 | 2000-08-07 | Oligosaccharides, a process for preparation thereof and pharmaceutical combination containing the same compounds |
| PCT/CN2000/000224 WO2001044263A1 (en) | 1999-12-16 | 2000-08-07 | Oligosaccharides, a process for preparation thereof and pharmaceutical combination containing the same compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99126224 CN1129600C (en) | 1999-12-16 | 1999-12-16 | Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1303857A CN1303857A (en) | 2001-07-18 |
| CN1129600C true CN1129600C (en) | 2003-12-03 |
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| CN 99126224 Expired - Fee Related CN1129600C (en) | 1999-12-16 | 1999-12-16 | Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide |
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| CN (1) | CN1129600C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394867A (en) | 2001-07-06 | 2003-02-05 | 中国科学院生态环境研究中心 | Medicinal oligose and its preparation method and medicine composition containing said oligose |
| 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 |
| US8993740B2 (en) * | 2010-02-19 | 2015-03-31 | Glycom A/S | Method for preparation of the tetrasaccharide lacto-N-neotetraose (LNnt) containing N-acetyllactosamine |
| CN114409817A (en) * | 2022-01-24 | 2022-04-29 | 艾立斯特(合肥)生物科技有限公司 | Heptasaccharide synthesis method of lentinan core fragment beta- (1 → 6) branched chain beta- (1 → 3) main chain |
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