CN108912239A - A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals - Google Patents
A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals Download PDFInfo
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- CN108912239A CN108912239A CN201810631305.0A CN201810631305A CN108912239A CN 108912239 A CN108912239 A CN 108912239A CN 201810631305 A CN201810631305 A CN 201810631305A CN 108912239 A CN108912239 A CN 108912239A
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- glucose
- sugar
- saccharide
- donor
- glycosyl
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 41
- 239000008103 glucose Substances 0.000 claims abstract description 40
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 28
- -1 glucose tetrose Chemical class 0.000 claims abstract description 21
- 239000000386 donor Substances 0.000 claims abstract description 15
- 239000000370 acceptor Substances 0.000 claims abstract description 14
- 239000000348 glycosyl donor Substances 0.000 claims abstract description 13
- 239000000937 glycosyl acceptor Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- NZLVBVLCSAJQEY-VFUOTHLCSA-N C([C@@H]1[C@H]([C@@H]([C@H]([C@](O1)(O)[SiH3])O)O)O)O Chemical compound C([C@@H]1[C@H]([C@@H]([C@H]([C@](O1)(O)[SiH3])O)O)O)O NZLVBVLCSAJQEY-VFUOTHLCSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 3
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 claims abstract 4
- 230000007062 hydrolysis Effects 0.000 claims abstract 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000004043 trisaccharides Chemical class 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 16
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 125000006239 protecting group Chemical group 0.000 claims description 6
- 150000003538 tetroses Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- LNFJGCJNPDUWDR-BTVCFUMJSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O LNFJGCJNPDUWDR-BTVCFUMJSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 241000219095 Vitis Species 0.000 claims 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 229930014626 natural product Natural products 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- 238000004440 column chromatography Methods 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 0 C*(C(*C1COC(c2ccccc2)=O)C(*)C(*)C1OC(c1ccccc1)=O)=N Chemical compound C*(C(*C1COC(c2ccccc2)=O)C(*)C(*)C1OC(c1ccccc1)=O)=N 0.000 description 5
- 201000010099 disease Diseases 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 229920001542 oligosaccharide Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 210000000987 immune system Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229930192334 Auxin Natural products 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920005654 Sephadex Polymers 0.000 description 1
- 239000012507 Sephadex™ Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007233 immunological mechanism Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000021918 systemic acquired resistance Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
The present invention discloses one kind 3,The synthetic method of poly- seven sugar in the Portugal of 6 branchings,Belong to the technical field of natural products synthesis,Using the tri- chloroacetimidate of glucose as glycosyl donor,Tert-butyldimethyl silyl-α-D- glucopyranose is glycosyl acceptor,Through being coupled,Sour water solution and activation,Obtain three saccharide donor of glucose,With the tri- chloroacetimidate of glucose and 4,6- benzal base -2,Bis--O- benzoyl glucose tri- chloroacetimidate of 3- is glycosyl donor,Tert-butyldimethyl silyl-α-D- glucopyranose is glycosyl acceptor,Through being coupled,Glycosyl acceptor is used as after hydrolysis,Again with 4,6- benzal base -2,Bis--O- benzoyl glucose tri- chloroacetimidate of 3- is glycosyl donor,Through being coupled,Hydrolysis,Obtain four saccharide acceptor of glucose,By three saccharide donor of glucose and glucose tetrose coupled receptors,Obtain seven sugar,Deprotect to obtain target product 3,Poly- seven sugar in the Portugal of 6 branchings,Synthetic operation of the present invention is convenient,Raw material availability is high,It is a kind of efficient synthetic method.
Description
Technical field
The invention belongs to the technical fields of natural products synthesis, and in particular to a kind of synthesis of poly- seven sugar in 3,6 branching Portugals
Method.
Background technique
The main chain of glucose oligosaccharide is 1 → 6 β connection, and side chain is 1 → 3 β connection.Glucose oligosaccharide is a kind of novel life
Object pesticide can excite plant immune system, achieve the purpose that diseases prevention insect prevention, itself is simultaneously non-toxic, but it can excite plant to produce
Raw systemic acquired resistance, excites the immunologic mechanism of inside plants, plays disease-resistant, diseases prevention purpose.Since glucose oligosaccharide exists
There is highly significant in terms of the self-defence immune system and coordinate plant growth of activated plant, and free from environmental pollution, it is right
Human health will replace pesticide and auxin without harmless, change the industrial structure of pesticide in future and pesticidal preparations, at
For the new direction of Agrochemicals.The structural formula of the substance is：
That reports at present is all complex about glucose oligosaccharide synthetic method, and raw material availability is lower, increases production
Cost is unfavorable for large-scale industrial production.
Summary of the invention
According to the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to propose a kind of synthetic method letter
Single, raw material availability is high, easy to operate, the synthetic method of poly- seven sugar in 3,6 high branching Portugals of combined coefficient, above-mentioned in order to solve
Technical problem, the technical solution adopted by the present invention are：
A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals, first three saccharide donor of synthesis of glucose and glucose tetrose by
Body then by three saccharide donor of glucose and glucose tetrose coupled receptors, then sloughs protecting group, obtains target product.
Preferably, the synthetic method of three saccharide donor of glucose is as follows：It is sub- with the tribromo-acetyl of benzoyl glucose
Amine ester is glycosyl donor, using tert-butyldimethyl silyl-α-D- glucopyranose as glycosyl acceptor, by glycosyl donor and glycosyl acceptor
It is dissolved in methylene chloride, then mixes the two respectively, catalyst TMSOTf is added, after reaction 2-6h is stirred at room temperature, prepare
Trisaccharide protects the hydroxyl of trisaccharide with benzoyl, and end position protecting group is removed through sour water solution, and activation obtains glucose trisaccharide
Donor, wherein n (glycosyl donor)：N (glycosyl acceptor) is 2:1.Synthetic reaction formula is as follows：
Preferably, the synthetic method of four saccharide acceptor of glucose is as follows：With glucose tri- chloroacetimidate and 4,6-
Bis--O- benzoyl glucose tri- chloroacetimidate of benzal base -2,3- is glycosyl donor, with tert-butyldimethyl silyl-α-D-
Glucopyranose is glycosyl acceptor, and under TMSOTf catalysis, coupling obtains corresponding trisaccharide after being stirred to react 2-6h at room temperature, will
4, the 6- benzal base of trisaccharide, which hydrolyzes, to be removed, and three saccharide acceptor of glucose is obtained, using trisaccharide as glycosyl acceptor, 4,6- benzal bases -2,3-
Two-O- benzoyl glucose tri- chloroacetimidates are glycosyl donor, under TMSOTf catalysis, after reaction 2-6h is stirred at room temperature
Coupling obtains corresponding tetrose, and 4, the 6- benzal base of tetrose is hydrolyzed and is removed, obtains four saccharide acceptors, wherein three chloroethene of glucose
Imide ester, 4,6- benzal base -2,3-, bis--O- benzoyl glucose tri- chloroacetimidate and tert-butyldimethyl silyl-α -
The molar ratio of D- glucopyranose is 1:1:1, trisaccharide and 4, bis--O- benzoyl glucose tribromo-acetyl of 6- benzal base -2,3-
The molar ratio of imines ester is 1:1.Synthetic reaction formula is as follows：
Preferably, the synthetic method of the target product is as follows：By equimolar three saccharide donor of glucose and glucose four
Saccharide acceptor is under the catalysis of TMSOTf, and coupling obtains seven sugar at room temperature, and seven sugar remove end position protecting group TBS through sour water solution, obtain
To compound, protecting group then is sloughed with alkali, obtains free 3, poly- seven sugar in 6 branching Portugals.Synthetic reaction formula is as follows：
Preferably, the Bz is：C6H5(C=O)-, TBS is：C6H15Si-。。
Compared with prior art, beneficial effects of the present invention：
1. of the invention 3, using extremely simple synthesis mode synthesis, the compound of synthesis has very poly- seven sugar in the Portugal of 6 branchings
The self-defence immune system and coordinate plant growth of good activated plant, and can be degradable in nature, not pollution ecology ring
Border,
2. design synthetic route of the invention is succinct, easy to operate, raw material availability is high in whole process, is a kind of efficient
Synthetic method, and synthesize compound can become new disease control means and plant protection strategy.
Specific embodiment
It below by the description to embodiment, is described in further detail, to help those skilled in the art to this hair
Bright inventive concept, technical solution have more complete, accurate and deep understanding.
Embodiment 1
The preparation of three saccharide donor of glucose：
1) by 3.705g, 5mmol benzoyl glucose tri- chloroacetimidate is dissolved in 30mL methylene chloride, obtains solution
A, by 0.735g, 2.5mmol tert-butyldimethyl silyl-α-D- glucopyranose is dissolved in 15mL methylene chloride, solution B is obtained, by B
Solution C is mixed to obtain with A, and the TMSOTf catalyst of 230 μ L, 2mmol is added into C, addsMolecular sieve reacts at 25 DEG C
After 4h, thin-layer chromatographic analysis shows that reaction is completed, and filters, and decompression evaporates solvent, uses column chromatography, with ethyl acetate/hexamethylene
Alkane (1/3) is eluted as leacheate, is collected respective components, is obtained pure trisaccharide, yield 91.3%；
2) by 7.250g, 5mmol trisaccharide is dissolved in 30mL DMF, and being heated to 70 DEG C is completely dissolved glucose, is added
2.9mL, 3.5mmol pyridine take out flask and are cooled to 25 DEG C, flask is placed in ice bath, 2.1mL, 17.85mmol benzene first is added dropwise
Acyl chlorides restores flask to 25 DEG C, the heating stirring in 70 DEG C of oil bath, reacts for 24 hours, thin-layer chromatographic analysis table
Bright reaction is completed, and extraction is added 10mL water into flask and 60mL methylene chloride, liquid separation, organic phase replace extraction with water phase, is closed
And organic phase, organic phase successively use 30mL, 2mol/L HCl, 30mL are saturated NaHCO3, 30mL saturation NaCl washing, finally to having
It is dry that anhydrous sodium sulfate is added in machine phase, filters, depressurizes rotary distillation, vacuum drying obtains target product, yield：93.2%；
3) by 3.565g, 2.15mmol trisaccharide is dissolved in 20mL, and in 1% hydrochloric acid-methanol solution, 2-3h is stirred at 25 DEG C, thin
Layer chromatography shows that reaction is completed, and decompression evaporates solvent, uses column chromatography, and uses ethyl acetate/hexamethylene (1/3) as leaching
Washing lotion elution, collects respective components, obtains trisaccharide, yield 83.9%.
4) by 7.720g, 5mmol trisaccharide is dissolved in 30mL methylene chloride, addition 1mL, 10mmol Tritox, 1.035g,
7.5mmol potassium carbonate stirs 5h at 25 DEG C, and thin-layer chromatographic analysis shows that reaction is completed, and decompression evaporates solvent, with column chromatography point
From using ethyl acetate/hexamethylene (1/3) as leacheate, collect respective components, obtain three saccharide donor of glucose, yield
84.1%.
Synthetic reaction formula is as follows：
Embodiment 2
The preparation of four saccharide acceptor of glucose
1) by 1.481g, 2mmol benzoyl glucose tri- chloroacetimidate is dissolved in 10mL methylene chloride, obtains molten
Liquid a, by 0.588g, 2mmol tert-butyldimethyl silyl-α-D- glucopyranose is dissolved in 10mL methylene chloride, obtains solution b,
By 1.241g, 2mmol 4, bis--O- benzoyl glucose tri- chloroacetimidate of 6- benzal base -2,3- is dissolved in 10mL dichloromethane
In alkane, solution c is obtained, solution a and solution b, solution c are mixed to get solution d, 80 μ L are added into solution d,
0.70mmolTMSOTf catalyst is addedMolecular sieve, after reacting 3h at 25 DEG C, thin-layer chromatographic analysis shows that reaction is completed,
It filters, decompression evaporates solvent, uses column chromatography, and ethyl acetate/hexamethylene (1/3) is used to elute as leacheate, collects corresponding
Component obtains pure trisaccharide, yield 89.7%.
2) trisaccharide is dissolved in 10mL by 1.330g, 1mmol, and 80% aqueous acetic acid reacts 1-1.5h, thin layer color at 25 DEG C
Spectrum analysis shows that reaction is completed, and decompression evaporates solvent, uses column chromatography, uses ethyl acetate/hexamethylene (1/3) as leacheate
Elution collects respective components, obtains three pure saccharide acceptors, yield 84.8%.
3) by 2.484g, 2mmol trisaccharide is dissolved in 20mL methylene chloride, obtains solution a, by 1.241g, 2mmol 4,6-
Bis--O- benzoyl glucose tri- chloroacetimidate of benzal base -2,3- is dissolved in 10mL methylene chloride, obtains solution b, will be molten
Liquid a and solution b are mixed to get solution c, and 80 μ L, 0.70mmol TMSOTf catalyst are added into solution c, react at 25 DEG C
2-2.5h, thin-layer chromatographic analysis show that reaction is completed, and decompression evaporates solvent, uses column chromatography, with ethyl acetate/hexamethylene
(1/2.5) it is eluted as leacheate, collects respective components, obtain pure tetrose, yield 81.1%.
4) by 3.400g, 2mmol tetrose is dissolved in 80% aqueous acetic acid of 20mL, and 1-2h, thin-layer chromatography are reacted at 25 DEG C
Analysis shows reaction is completed, decompression evaporates solvent, uses column chromatography, uses ethyl acetate/hexamethylene (1/2.5) as leacheate
Elution collects respective components, obtains four saccharide acceptor of glucose, yield 78.9%.
Synthetic reaction formula is as follows：
Embodiment 3
The synthesis of target compound
1) by 3.377g, three saccharide donor of 2mmol glucose, 3.224g, four saccharide acceptor of 2mmol glucose andMolecular sieve is molten
In 50mL anhydrous methylene chloride, 1.5h is stirred under nitrogen protection, and 50 μ L, 0.44mmol TMSOTf catalyst are then added dropwise,
4.5h is reacted at 25 DEG C, thin-layer chromatographic analysis shows to have reacted, and filters, and decompression evaporates solvent, uses column chromatography, uses acetic acid
Ethyl ester/hexamethylene (1/1.8) is eluted as leacheate, collects respective components, obtains seven pure sugar, yield 79.6%.
2) by 6.276g, seven sugar of 2mmol is dissolved in 35mL, and in 1% hydrochloric acid-methanol solution, 2-2.5h is reacted at 25 DEG C, thin
Layer chromatography show reaction complete, decompression evaporate solvent, use column chromatography, use ethyl acetate/hexamethylene (1/1.8) as
Leacheate elution, collects respective components, obtains seven pure sugar, yield 82.4%.
3) by 6.048g, seven sugar of 2mmol is dissolved in the sodium methoxide solution of saturation, stirs 78h, sephadex LH- after concentration
20 (methanol) post separations, obtain target product, yield 74.2%, the data of target product：ESMS m/z 1184 { M+NH4 }, FW=
1166.39。
Synthetic reaction formula is as follows：
The present invention is exemplarily described above in conjunction with specific embodiment, it is clear that the present invention implements not by upper
The limitation of mode is stated, if the improvement for the various unsubstantialities that the inventive concept and technical scheme of the present invention carry out is used, or
It is not improved the conception and technical scheme of the invention are directly applied to other occasions, protection scope of the present invention it
It is interior.Protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (5)
1. the synthetic method of poly- seven sugar in 3,6 branching Portugals of one kind, which is characterized in that three saccharide donor of synthesis of glucose first is (with Portugal
Grape four saccharide acceptors of sugar, then by three saccharide donor of glucose and glucose trisaccharide coupled receptors, then slough protecting group, obtain target production
Object.
2. according to claim 13, the synthetic method of poly- seven sugar in 6 branching Portugals, which is characterized in that the glucose three
The synthetic method of saccharide donor is as follows：Using the tri- chloroacetimidate of benzoyl glucose as glycosyl donor, with tert-butyl diformazan
Base silicon-α-D- glucopyranose is glycosyl acceptor, glycosyl donor and glycosyl acceptor is dissolved in methylene chloride respectively, then by two
Person's mixing, is added catalyst TMSOTf, after reaction 2-6h is stirred at room temperature, trisaccharide is prepared, by the hydroxyl benzoyl of trisaccharide
Protection, and end position protecting group is removed through sour water solution, activation obtains three saccharide donor of glucose, wherein n (glycosyl donor)：N (sugar
Base receptor) it is 2:1.Synthetic reaction formula is as follows：
3. according to claim 13, the synthetic method of poly- seven sugar in 6 branching Portugals, which is characterized in that the glucose four
The synthetic method of saccharide acceptor is as follows：With two-O- benzoyl grape of glucose tri- chloroacetimidate and 4,6- benzal base -2,3-
Sugared tri- chloroacetimidate is glycosyl donor, using tert-butyldimethyl silyl-α-D- glucopyranose as glycosyl acceptor, in TMSOTf
Under catalysis, coupling obtains corresponding trisaccharide after being stirred to react 2-6h at room temperature, and 4, the 6- benzal base of trisaccharide is hydrolyzed and is removed, is obtained
Three saccharide acceptor of glucose, using trisaccharide as glycosyl acceptor, 4,6- benzal base -2,3-, bis--O- benzoyl glucose tribromo-acetyl is sub-
Amine ester is glycosyl donor, and under TMSOTf catalysis, coupling obtains corresponding tetrose after reaction 2-6h is stirred at room temperature, by the 4 of tetrose,
The hydrolysis of 6- benzal base removes, and obtains four saccharide acceptors, wherein glucose tri- chloroacetimidate, 4,6- benzal base -2,3-, bis--O-
The molar ratio of benzoyl glucose tri- chloroacetimidate and tert-butyldimethyl silyl-α-D- glucopyranose is 1:1:1, three
The molar ratio of sugar and two-O- benzoyl glucose tri- chloroacetimidate of 4,6- benzal base -2,3- is 1:1.Synthetic reaction formula
It is as follows：
4. according to claim 13, the synthetic method of poly- seven sugar in 6 branching Portugals, which is characterized in that the target product
Synthetic method it is as follows：By equimolar three saccharide donor of glucose and four saccharide acceptor of glucose under the catalysis of TMSOTf, in room
The lower coupling of temperature obtains seven sugar, and seven sugar remove end position protecting group TBS through sour water solution, obtain compound, then slough protecting group with alkali,
Obtain poly- seven sugar in 3,6 free branching Portugals.Synthetic reaction formula is as follows：
5. according to the synthetic method of poly- seven sugar in any 3, the 6 branching Portugals claim 2-4, which is characterized in that the Bz
For：C6H5(C=O)-, TBS is：C6H15Si-。
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