CN1160363C - Prepn. method for mannosan antigen factor 4 and mannosan antigen factor 6 - Google Patents
Prepn. method for mannosan antigen factor 4 and mannosan antigen factor 6 Download PDFInfo
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- CN1160363C CN1160363C CNB001209507A CN00120950A CN1160363C CN 1160363 C CN1160363 C CN 1160363C CN B001209507 A CNB001209507 A CN B001209507A CN 00120950 A CN00120950 A CN 00120950A CN 1160363 C CN1160363 C CN 1160363C
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Abstract
The present invention relates to the simple preparation of mannosan antigenic factors 4 and mannosan antigenic factors 6. The ortho ester of mannose is used as raw materials and condensed to directly obtain alpha 1-2 connected mannobiose which can be used for preparing alpha1-2 connected mannotetraose and mannotriose, wherein the alpha1-2 connected mannotetraose is coupled with alpha1-3 connected mannobiose so as to obtain the mannosan antigenic factors 4, and the alpha1-2 connected mannotriose is coupled with 3, 6 branched mannobiose so as to obtain the mannosan antigenic factors 6.
Description
The invention belongs to the preparing technical field of bioactive oligosaccharides, particularly relate to the mannocarolose antigenic factor 4 of the screening that can be used for medicine and the simple method for preparing of mannocarolose antigenic factor 6.
Oligosaccharides, polysaccharide and glycoconjugate (glycoprotein, glycolipid) is important information substance in the organism, participates in the contact process of all cells, the communication of the oligosaccharides of cell surface between cell, identification and interaction, the embryo is taken place, and shifts, in the signal transmission, cell movement with stick, and the interaction aspect of cause of disease and host cell plays an important role.Up-to-date studies show that, oligosaccharides not only with they conjugate in action, a lot of oligosaccharides itself just have the important physical function, the oligosaccharides that has can excite the immunity system of plant, the oligosaccharides that has can be induced the nitrogen fixation of root nodule bacterium; The oligosaccharides that has can combine with the glycoprotein on the microorganism of invading and stop the invasion and attack of these microorganisms to the human normal cell, some oligosaccharides then have the function of heparin (haparin), the medicine of the anti-curing cancers that blood group decision family oligosaccharides gets a good chance of especially.Oligosaccharides is in agricultural, and the pharmaceutical sector aspect has wide practical use.And oligosaccharides and polysaccharide are removed disease directly as drug use, improve health, and will cause the renewal of disease preventing and treating idea, also are that of life science makes progress greatly.Emerging " sugared engineering " (based on drug development of carbohydrate) is in flourish ground zero, according to " biotechnology news " (Biotech News) 1995,14 (4), 7 the report, the market share of carbohydrate medicine will from 1993 13% increase to 2000 24%.
Mannocarolose antigenic factor 4 and mannocarolose antigenic factor 6 all are the compositions that is present in cell wall polysaccharides, they are reactive sites of polysaccharide, to some tetter is crucial virulence factor, synthetic their also further preparation vaccines just can be made and cure tetter or other new drug by the microbial disease of beads.
The structure of mannocarolose antigenic factor 4 is α-D-Man-1 → 3-(α-D-Man-1 → 6)-α-D-Man-1 → 2-α-D-Man-1 → 2-α-D-Man-1 → 2-D-Man and the structure of mannocarolose antigenic factor 6 is α-D-Man-1 → 3-α-D-Man-1 → 2-α-D-Man-1 → 2-α-D-Man-1 → 2-α-D-Man-1 → 2-D-Man, does not see the synthetic report of these two antigenic factors so far as yet.
The objective of the invention is to adopt brand-new thinking, provide a kind of step simple, time saving and energy saving, be method initiator, that prepare these two antigenic factors with the ortho ester of sugar.
The object of the present invention is achieved like this: with the simplest bromo acyl group seminose is raw material; at first be translated into benzoylated ortho ester; condensation under triflate catalysis then; obtain the disaccharide that 1-2 connects, make it be converted into tetrose acceptor and three saccharide acceptors through simple chemical conversion, the sweet dew disaccharide donor coupling that the former is connected with 1-3; deprotection promptly obtains antigenic factor 6 again; and the mannotriose donor coupling of the latter and 3,6 branching, deprotection promptly obtains antigenic factor 4 again.
Synthetic method of the present invention is: with bromo ethanoyl seminose (1) is raw material; prepare the ortho ester (2) of seminose, in sodium methylate-methyl alcohol, take off ethanoyl and obtain (3), with pyridine-Benzoyl chloride benzoylation; obtain benzoylated ortho ester (4), as shown below:
Ortho ester (4) condensation under trimethyl silicane triflate (TMSOTf) or triethyl silicon triflate (TESOTf) effect obtains the disaccharide (5) that α 1-2 connects, and is as shown below:
Disaccharide (5) selectivity is taken off 1 R base, and activation obtains disaccharide donor (6) then, and disaccharide (5) selectivity is taken off ethanoyl and obtained disaccharide (7), and is as shown below:
Disaccharide (7) and disaccharide donor (6) coupling obtain tetrose (8), and disaccharide (7) and monose donor (9) coupling obtain trisaccharide (10), and be as shown below:
Tetrose (8) selectivity deacetylation obtains tetrose acceptor (11); And trisaccharide (10) selectivity deacetylation obtains three saccharide acceptors (12), and is as shown below:
R=alkyl or aryl in the said structure formula, the Bz=benzoyl;
Tetrose acceptor (11) and disaccharide donor (13) coupling obtain six sugar (14); And three saccharide acceptors (12) and three saccharide donors (15) coupling obtain six sugar (16), and are as shown below:
R=alkyl or aryl in the said structure formula, R '=acyl group or alkyl, Bz=benzoyl, X=halogen, acyl group or tribromo-acetyl imines ester;
Take off the protecting group of six sugar (14) with ordinary method, promptly obtain mannocarolose antigenic factor 6 (17); Take off the protecting group of six sugar (16) with ordinary method, promptly obtain mannocarolose antigenic factor 4 (18).As shown below:
R=H, alkyl or aryl in the said structure formula
Described linked reaction is carried out under the Lewis acid catalysis, and used Lewis acid is silver salt, boron trifluoride, trimethyl silicane triflate (TMSOTf), triethyl silicon triflate (TESOTf).
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1: and benzoylated ortho ester 4 (3,4,6-tri-O-benzoyl-β-D-mannopyranose 1,2-allylorthoester) preparation
Bromo acetylated mannan sugar (tetra-O-acetyl-α-D-mannopyranosyl bromide) (1,8220 milligrams, 20 mmoles) be dissolved in 40 milliliters of vinyl carbinols (allyl alcohol), in this solution, add 2, (2.3 milliliters of 4-lutidine, 20 mmoles), be reflected at room temperature, carry out under stirring, with the thin-layer chromatographic analysis monitoring, after reaction is finished, reactant concentrated cause the dried crude product 2 that obtains, be suspended in 20 milliliters of anhydrous methanols adding sodium methylate (0.4 milliliter, 2 mol) with 2, solution is ambient temperature overnight under agitation, and thin-layer chromatographic analysis shows to react to be finished.Reaction solution concentrated cause dried 3 4.7 grams that obtain, productive rate 90% is dissolved in 30 milliliters of pyridines 3, slowly drip Benzoyl chloride (8.2 milliliters, 70 mmoles), be reflected under stirring, the room temperature and carry out, monitor with thin-layer chromatographic analysis, finish after 3 hours, with ordinary method reactant is handled, the resistates that obtains is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain pure hepatin acid ester 4 10 grams, productive rate 97%.Fusing point: 142 ℃ of specific optical rotations [α]
D-12 °
Embodiment 2: the disaccharide 5 that α 1-2 connects (All 2-O-acetyl-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside)
With 4 under vacuum dry 2 hours, be dissolved in then in 80 milliliters of exsiccant methylene dichloride, under-40 ℃, add TMSOTf 100 microlitres, reactant under agitation returns to room temperature naturally, after 1 hour, reaction is finished, with triethylamine neutralization reaction liquid, decompression concentrates down, and is refining with silica gel column chromatography, with ethyl acetate/petroleum ether (1/3) as leacheate drip washing, collect respective components, obtain pure disaccharide 5 6.72 grams, productive rate 66%.
Embodiment 3: the preparation of disaccharide donor 6 (2-O-Acetyl-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate)
With 5 (2100 milligrams, 2mmol) join 90% acetic acid (20mL), add acetic acid again and receive 590 milligrams (6 mmoles) and PdCl
20.18 milligram (1 mmole), reaction is at room temperature stirred after 12 hours and is finished, mixture is diluted with 60 milliliters of methylene dichloride, water and unsaturated carbonate hydrogen are received solution washing, organic phase is evaporate to dryness under reduced pressure, obtaining 1 with the silica gel column chromatography separation is the disaccharide 2-O-acetyl-3 of free hydroxyl group, 4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-D-mannopyranose (1820 milligrams) is dissolved in this disaccharide in 20 milliliters of methylene dichloride, adds CCl then
3CN 0.4ml (8 mmole) and DBU (56 μ L, 0.72 mmole), reaction is at room temperature stirred after 2 hours and is finished, and the concentration response thing obtains 6 1890 milligrams of crystalline disaccharide donors after the column chromatography for separation, 139-142 ℃ of two step productive rate 82%:m.p; [α]
D-1.5 ° of (c1.1, CHCl
3)
Embodiment 4: (Allyl 3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside) for disaccharide 7
Disaccharide 5 (2100 milligrams, 2 mmoles) is joined in the 60mL anhydrous methanol, in this solution, add 1.8 milliliters of Acetyl Chloride 98Min.s down, stirred 10 hours under the room temperature, add 1.2 milliliters of Acetyl Chloride 98Min.s again, use the TLC detection reaction, finish until reaction at 0 ℃.Solution Et
3N is neutralized to neutrality, is concentrated into driedly, and column chromatography for separation obtains 7 (1870 milligrams, 93%): fusing point 147-150 ℃; [α]
D-3.6 ° of (c1.4, CHCl
3);
Embodiment 5: tetrose 8 (Allyl 2-O-acetyl-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside)
With (1150 milligrams of disaccharide donors 6; 1 mmole) and (1010 milligrams of disaccharides 7; 1 mmole) under vacuum dry together 2 hour; be dissolved in then in 60 milliliters of anhydrous methylene chlorides, under-42 ℃, nitrogen protection, stirring, add TMSOTf (20 microlitres, 0.10 mmole) to this solution; reaction was carried out 3 hours; and heat up naturally, solution Et is finished in TLC demonstration reaction
3N is neutralized to neutrality, is concentrated into driedly, and column chromatography for separation obtains 8 (1700 milligrams, 85%): fusing point 140-145 ℃; [α]
D-2.2 ° of (c1.3, CHCl
3);
13C NMR δ 168.96,, 166.25,166.18,166.00,165.69,165.61,165.44,165.36,165.29,165.23,165.18,165.10,164.93,117.89,100.74,100.46,99.22,98.02,77.18,76.27,70.91,70.83,70.71,69.65,69.58,69.38,69.35,69.15,68.88,68.68,67.76,67.29,67.13,67.13,63.75,63.75,63.54,62.95;
Embodiment 6: trisaccharide 10 (Allyl 2-O-acetyl-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1-2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside)
Condition by 6 and 7 condensations, carry out monose donor 2-O-acetyl-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (9,747 milligrams, 1.1 mmoles) with the condensation of disaccharide 7 (980 milligrams, 1 mmole), obtain 10 1217 milligrams, productive rate 88%.
Embodiment 7: (Allyl 3 for the tetrose receptor 11,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside)
Condition by by 5 preparations 7 makes 890 milligrams of tetrose receptor 11s, 137-141 ℃ of productive rate 91%:m.p by tetrose 8 (1000 milligrams, 0.5 mmole); [α]
D-0.4 ° of (c1.2, CHCl
3);
Embodiment 8: (Allyl 3,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3 for the trisaccharide receptor 12,4,6-tri-O-benzoyl-α-D-mannopyranosyl-(1 → 2)-3,4, the preparation of 6-tri-O-benzoyl-α-D-mannopyranoside)
Condition by by 5 preparations 7 makes trisaccharide receptor 12 1112mg, 86% by trisaccharide 10 (1220 milligrams, 0.5 mmole): fusing point 132-134 ℃; [α]
D-1.7 ° of (c1.0, CHCl
3);
Embodiment 9: disaccharide donor 13 (2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-, 2,4,6-tri-O-acetyl-α-D-mannopyranosyl trichloroacetimidate) preparation
By 2,3,4, and 6-Tetra-O-benzoyl-α-D-mannopyranosyl trichloroacetimidate (1290 milligrams, 2 mmoles, R.R.Schmidt is seen in its preparation, Adv.Carbohydr.Chem.Biochem., Vol 50,1994,21-124) with 4,6-O-benzylidene-1, and 2-O-ethylidene-β-D-mannopyranose (560 milligrams, 2 mmoles, its preparation sees that the king is Kong Fanzuo Carbohydr.Res., 151,1999,117-226) obtain disaccharide 2 by the standard conditions condensation, 3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl-(1 → 3)-4,6-O-benzylidene-1,1570 milligrams of 2-O-ethylidene-β-D-mannopyranose, 128-132 ℃ of productive rate 90%:m.p; [α]
D-1.5 ° of (c1.0, CHCl
3); , the disaccharide 1310 milligrams (1.5 mmoles) that obtains is used 90%F
3CCOOH (5 milliliters) at room temperature handled 1 hour; reaction solution is concentrated; resistates with pyridine (5mL), diacetyl oxide (3mL) at room temperature; finished acetylize in 2 hours; processing reaction liquid according to a conventional method; with (207 milligrams in the resistates that obtains and salt of wormwood; 1.5 mmole) be dissolved among 10 milliliters of DMF; at room temperature stirred 12 hours; with ordinary method processing reaction liquid, organic phase concentrates, column chromatography for separation; resulting 1 for the disaccharide crude product of free hydroxyl group is dissolved in the methylene dichloride (20 milliliters), add CCl then
3CN (0.3 milliliter, 3 mmoles) and DBU (42 microlitres, 0.3 mmole). after at room temperature handing over to the next shift hour, finishes reaction mixture, the concentration response thing, column chromatography for separation obtains 13 960 milligrams of disaccharide donors, 125-127 ℃ of four step overall yield 62%:m.p; [α]
D-0.9 ° of (c1.2, CHCl
3);
Embodiment 10: the preparation of antigenic factor 6 six sugar 14 of full guard
By the condition of 6 and 7 condensations, make disaccharide donor 13 (103 milligrams, 0.1 mmole) and tetrose receptor 11 (195 milligrams, 0.1 mmole) condensation, obtain antigenic factor six sugar 14,212mg, productive rate 75%:mp142-146 ℃; [α]
D-2.9 ° of (c1.1, CHCl
3);
1H NMR δ 8.05-7.26,6.34,6.29,6.14,6.00-5.70,5.62,5.56,5.48,5.30,5.28,5.23,5.15,5.13,5.05,4.92,4.75-4.70,4.68-4.50,4.48,4.45,4.42-4.26,3.88-3.84,3.69-3.64,3.59-3.55,2.35,2.24,2.04.
Embodiment 11: the preparation of antigenic factor 4 six sugar 16 of full guard
(king is Kong Fanzuo Angew.Chem.Int.Ed.Engl. at first to use known method, 38,1999,1247-1249.) by 1,2-ethidine seminose and benzoylated seminose Schmidt reagent preparation go out 3, the mannotriose (2 of 6 branching, 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-O-ethylidene-β-D-mannopyranose) its fusing point is 141-144 ℃; [α]
D-1.4 ° of (c1.1, CHCl
3); Trisaccharide 1 millimole that obtains was so at room temperature handled 2 hours with 90% trifluoroacetic acid, remove ethidine, use the quantitative acetylize of pyridine-diacetyl oxide then, 1 ethanoyl of selectively removing again, then with three chloroethenes eyeball-DBU activation, three saccharide donors 15 (2 have been obtained, 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-α-D-mannopyranosyl trichloroacetimidate) 1048 milligrams, to 68%:mp125-127 ℃ of four-step reaction overall yield; [α]
D-2.2 ° of (c1.1, CHCl
3);
1H NMR δ 8.97,8.07-7.26,6.37,6.22,6.13,5.89,5.80,5.69,5.64,5.54,5.52,5.42,5.11,4.69-4.65,4.64-4.60,4.52-4.47,4.26-4.22,4.02-3.98,3.77-3.74,2.38,2.30.
By the method for 6 and 7 condensations, make three saccharide donors 15 (313 milligrams, 0.2 mmole) and trisaccharide receptor 12 (291 milligrams, 0.2 mmole) condensation, obtain 16 437 milligrams of antigenic factor six sugar, productive rate 77%:mp126-129 ℃; [α]
D-3.8 ° of (c1.1, CHCl
3);
1H NMR δ 8.08-7.24,6.36,6.12,6.00-5.68,5.61,5.48,5.41,5.09,5.08,5.06,4.98,4.85-4.79,4.61-4.40,4.32-4.27,4.25,4.13,4.02-3.98,3.92,3.85-3.81,3.72-3.68,3.62-3.58,2.27,2.04.
Embodiment 12: the preparation of antigenic factor 6 six glucosides 17, antigenic factor 6 six sugared 17a and antigenic factor 4 six glucosides 18:
14 (1410 milligrams, 0.5 mmole) or 16 (1432 milligrams, 0.5 mmole) be dissolved in in 15 milliliters of the saturated methyl alcohol of ammonia, reaction is 6 days under the room temperature, solvent is under reduced pressure drained, use the ethyl acetate debris, by 14 17 410 milligrams in antigenic factor 6 six glucosides that obtain the off-white powder shape, productive rate 79%:[α]
D+ 75 ° of (c1.1, D
2O);
1HNMR δ 5.90,5.42,5.34,5.10; Mass spectroscopy: m/z is to C
39H
66O
31: theoretical value 1030; Measured value: m/z1053 (M+ sodium); By 16 18 414 milligrams in antigenic factor 4 six glucosides that obtain the off-white powder shape, productive rate 80%:[α]
D+ 62 ° of (c2.3, D
2O);
1H NMR δ 5.20,4.98,3.41; Mass spectroscopy: m/z is to C
39H
66O
31: theoretical value 1030; Measured value: m/z 1053 (M+ sodium).
14 (1410 milligrams, 0.5 mmole) are joined 90% acetic acid (10 milliliters), add acetic acid again and receive 150 milligrams (1.4 mmoles) and PdCl
2(0.06g 0.3 mmole), reaction is at room temperature stirred after 12 hours and is finished, removed 1 allyl group, reaction mixture is diluted with 20 milliliters of methylene dichloride, water and unsaturated carbonate hydrogen are received solution washing, organic phase is evaporate to dryness under reduced pressure, obtaining 1 with the silica gel column chromatography separation is six sugar of free hydroxyl group, it is dissolved in in 15 milliliters of the saturated methyl alcohol of ammonia, reaction is 6 days under the room temperature, and solvent is under reduced pressure drained, and uses the ethyl acetate debris, obtain 362 milligrams of the free six sugared 17a of off-white powder shape, productive rate 73%: mass spectroscopy: m/z is to C
36H
62O
31: theoretical value 990; Measured value: m/z 1013 (M+ sodium).
Claims (2)
1. the simple method for preparing of mannocarolose antigenic factor 4 and mannocarolose antigenic factor 6 is characterized in that:
(1) be raw material with bromo ethanoyl seminose (1), prepare the ortho ester (2) of seminose, in sodium methylate-methyl alcohol, take off ethanoyl and obtain (3),, obtain benzoylated ortho ester (4) with pyridine-Benzoyl chloride benzoylation, as shown below:
(2) ortho ester (4) condensation under trimethyl silicane triflate or the effect of triethyl silicon triflate obtains the disaccharide (5) that α 1-2 connects, and is as shown below:
(3) disaccharide (5) selectivity is taken off 1 R base, and activation obtains disaccharide donor (6) then, and disaccharide (5) selectivity is taken off ethanoyl and obtained disaccharide (7), and is as shown below:
(4) disaccharide (7) and disaccharide donor (6) coupling obtain tetrose (8), and disaccharide (7) and monose donor (9) coupling obtain trisaccharide (10), and be as shown below:
(5) tetrose (8) selectivity deacetylation obtains tetrose acceptor (11); And trisaccharide (10) selectivity deacetylation obtains three saccharide acceptors (12), and is as shown below:
R=alkyl or aryl in the said structure formula, the Bz=benzoyl;
(6) tetrose acceptor (11) and disaccharide donor (13) coupling obtain six sugar (14); And three saccharide acceptors (12) and three saccharide donors (15) coupling obtain six sugar (16), and are as shown below:
R=alkyl or aryl in the said structure formula, R '=acyl group or alkyl, Bz=benzoyl, X=halogen, acyl group or tribromo-acetyl imines ester;
(7) take off the protecting group of six sugar (14) with ordinary method, promptly obtain mannocarolose antigenic factor 6 (17); Take off the protecting group of six sugar (16) with ordinary method, promptly obtain mannocarolose antigenic factor 4 (18), as shown below:
R=H, alkyl or aryl in the said structure formula.
2. the simple method for preparing of mannocarolose antigenic factor 4 as claimed in claim 1 and mannocarolose antigenic factor 6, it is characterized in that described linked reaction carries out under the Lewis acid catalysis, used Lewis acid is silver salt, boron trifluoride, trimethyl silicane triflate, triethyl silicon triflate.
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