CN101555262A - Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O - Google Patents

Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O Download PDF

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CN101555262A
CN101555262A CNA2008101035286A CN200810103528A CN101555262A CN 101555262 A CN101555262 A CN 101555262A CN A2008101035286 A CNA2008101035286 A CN A2008101035286A CN 200810103528 A CN200810103528 A CN 200810103528A CN 101555262 A CN101555262 A CN 101555262A
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杜宇国
魏国华
张磊
蔡超
程水红
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The invention provides a method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O, which is shown as a formula I. The method can play an important role in carbohydrate medicine synthesis.

Description

Iron(III) chloride hexahydrate (FeCl 36H 2O) method of selectively removing saccharide compound anomeric carbon acyl group
Technical field
The present invention relates to the synthetic and Application Areas of important intermediate of the saccharide compound of biologically active.
Background technology
Natural oligosaccharides or the sugar compound that stops has good biological activity (Schmidt, R.R. aspect physiology and the pharmacology; Kinzy, W.Adv.Carbohydr.Chem.Biochem.1994,50,21-23), the concern that is subjected to is more and more closer.Up to the present, about synthesizing of saccharide compound a large amount of bibliographical informations has been arranged.In these synthesis strategies, a very important step be exactly regioselectivity remove anomeric carbon-oxygen-acyl group, then the anomeric carbon oxy-compound that obtains is converted into active reaction donor and is used for the synthetic of oligosaccharides.For this reason, there has been a lot of method reports can realize this purpose, for example, ammonia (Mikano, M.Carbohydr.Res.1989,191,150-153), benzylamine (Conchie, J.; Levvy, G.A.Methods Carbohydr.Chem 1963,2,345-347), acetic acid hydrazine (Excoffier, G.; Gagnaire, D.; Utille, J.-P.Carbohydr.Res.1975,39,368-373), stannic oxide compounds (Watanbe, K.; Itoh, K.; Araki, Y.; Ishido, Y.Carbohydr.Res.1986,154,165-176; Nudelman, A.; Herzig, J.; Gottlieb, H.E.; Keinan, E.; Sterling, J.Carbohydr.Res.1987,162,145-152), (Sambaiah, T. such as mercury compounds; Fanwick, P.E.; Cushman, M.Synthesis 2001,1450-1452).These methods or reagent costliness very, or toxicity is very big to very serious of the pollution of environment, has been run counter to the present sustainable development strategy of advocating.Consider the defective of aforesaid method, we have invented FeCl 36H 2O/ acetonitrile reaction system can obtain the anomeric carbon oxy-compound efficiently.This method is simple to operation, low price, and toxicity is low, has further reduced the pollution of chemosynthesis to environment, is applicable to large-scale industrial production, for the extensive synthetic and screening of carbohydrate medicine provides strong support.
Summary of the invention
The object of the present invention is to provide a kind of method of energy selectively removing saccharide compound anomeric carbon acyl group, and can be applicable to large-scale industrial production, can provide strong support for the extensive synthetic and screening of carbohydrate medicine.
Summary of the invention
The present invention discloses a kind of with Iron(III) chloride hexahydrate (FeCl 36H 2O) method of selectively removing saccharide compound anomeric carbon acyl group, shown in general formula I, this method plays an important role in carbohydrate medicine synthetic.
Figure A20081010352800051
General formula I
In the general formula I:
R can be CH 3CO, C 6H 5CO, (CH 3) 3CCO, NO 2, C 13H 9CH 2OCO, CH 3SO 2, C 7H 6SO 2, C 3H 5OCO, BrC 6H 4CO, ClCH 2CO.
R 1Can be H, OH, CH 3O, C 3H 5O, C 3H 3O, C 6H 5CH 2O, CH 3OC 6H 4CH 2O, OSO 3 -, CH 3COO, C 6H 5COO, (CH 3) 3CCOO, ONO 2, BrC 6H 4COO, ClCH 2COO, CH 2COOCH 2CH 2COO, C 13H 9CH 2OCOO, C 3H 5OCOO, N 3, CH 3SO 3, C 7H 6SO 3, CH 3CONH, C 6H 5CONH, Cl 3CCH 2OCONH, Cl 3CCONH, C 8H 4O 2N, C 3H 5OCONH, F 3CCH 2OCONH, NO 2C 6H 4CONH or other sugar unit.
R 2Can be H, OH, CH 3O, C 3H 5O, C 3H 3O, C 6H 5CH 2O, CH 3OC 6H 4CH 2O, OSO 3 -, CH 3COO, C 6H 5COO, (CH 3) 3CCOO, ONO 2, CH 2COOCH 2CH 2COO, C 13H 9CH 2OCOO, C 3H 5OCOO, N 3, CH 3SO 3, C 7H 6SO 3, or other sugar unit.
R 3Can be H, CH 3, CH 2OH, CH 2OCH 3, CH 2OC 3H 3, CH 2OC 3H 5, CH 2OSO 3 -, COOCH 3, COOH, COONa, COOCH 2C 6H 5, COOC 3H 5, COOCH 3CH 2OOCCH 3, CH 2OOCCH 3, CH 2OOCCH 2Cl, CH 2OOCC 6H 5, CH 2OOCC 6H 4Br, CH 2OOCCH 2CH 2OOCCH 3, CH 2OOCC (CH 3) 3, CH 2OOCOCH 2C 13H 9, CH 2N 3, CH 2OC 3H 5, CH 2OCH 2C 6H 5, CH 2OCH 2C 6H 4OCH 3, CH 2OSO 2CH 3, CH 2OSO 2C 7H 6Or other sugar unit.
Method of the present invention is simple to operation, low price, and toxicity is low, has further reduced the pollution of chemosynthesis to environment, is applicable to large-scale industrial production, for the extensive synthetic and screening of carbohydrate medicine provides strong support.
Embodiment
Specific rotation records with the automatic polarimeter of Perkin-Elmer 241MC in the time of 25 ℃. 1H NMR by BrukerARX 400 at CDCl 3In record, be interior mark with tetramethylsilane.Mass spectrum adopts VG PLATFORM mass spectrograph, with ESI technology sample introduction.Thin-layer chromatography (TLC) is by HF 254Sulfuric acid methanol solution or ultraviolet (UV) detector with 30% (v/v) on the silica-gel plate detect.Column chromatography adopts 100-200 purpose silica gel, with ethyl acetate-sherwood oil (60-90 ℃) as leacheate, solution underpressure distillation the time less than 60 ℃, but below the compound that do not specify all be commercially available or the material of reference literature preparation.
Embodiment 1:
Figure A20081010352800061
(1.0mmol) is dissolved in CH with saccharide compound 1 3Among the CN, in reaction solution, add FeCl then 36H 2O (1.0mmol), reflux is about 1 hour.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 2 (0.9mmol, 90%), and the molecular weight of mass spectroscopy compound 2 is 348.
Embodiment 2:
Figure A20081010352800071
(1.0mmol) is dissolved in CH with saccharide compound 3 3Among the CN, in reaction solution, add FeCl then 36H 2O (1.0mmol), reflux is about 0.2 hour.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 4 (0.95mmol, 95%), and the molecular weight of mass spectroscopy compound 4 is 290.
Embodiment 3:
Figure A20081010352800072
(1.0mmol) is dissolved in CH with saccharide compound 5 3Among the CN, in reaction solution, add FeCl then 36H 2O (2.0mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 6 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 6 is 636.
Embodiment 4:
Figure A20081010352800073
(1.0mmol) is dissolved in CH with saccharide compound 7 3Among the CN, in reaction solution, add FeCl then 36H 2O (2.0mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 8 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 8 is 924.
Embodiment 5:
Figure A20081010352800081
(1.0mmol) is dissolved in CH with saccharide compound 9 3Among the CN, in reaction solution, add FeCl then 36H 2O (2.0mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 10 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 10 is 1070.
Embodiment 6:
(1.0mmol) is dissolved in CH with saccharide compound 11 3Among the CN, in reaction solution, add FeCl then 36H 2O (1.5mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 12 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 12 is 479.
Embodiment 7:
Figure A20081010352800091
(1.0mmol) is dissolved in CH with saccharide compound 13 3Among the CN, in reaction solution, add FeCl then 36H 2O (1.5mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 14 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 14 is 572.
Embodiment 8:
Figure A20081010352800092
(1.0mmol) is dissolved in CH with saccharide compound 15 3Among the CN, in reaction solution, add FeCl then 36H 2O (2mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 16 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 16 is 1420.
Embodiment 9:
Figure A20081010352800093
(1.0mmol) is dissolved in CH with saccharide compound 17 3Among the CN, in reaction solution, add FeCl then 36H 2O (2mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then 3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 18 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 18 is 331.

Claims (7)

1. the invention provides a kind of method of selectively removing saccharide compound anomeric carbon acyl group, the saccharide compound that is suitable for has the compound of following general formula,
General formula I
In the general formula I:
R can be CH 3CO, C 6H 5CO, (CH 3) 3CCO, NO 2, C 13H 9CH 2OCO, CH 3SO 2, C 7H 6SO 2, C 3H 5OCO, BrC 6H 4CO, ClCH 2CO.
R 1Can be H, OH, CH 3O, C 3H 5O, C 3H 3O, C 6H 5CH 2O, CH 3OC 6H 4CH 2O, OSO 3 -, CH 3COO, C 6H 5COO, (CH 3) 3CCOO, ONO 2, BrC 6H 4COO, ClCH 2COO, CH 2COOCH 2CH 2COO, C 13H 9CH 2OCOO, C 3H 5OCOO, N3, CH 3SO 3, C 7H 6SO 3, CH 3CONH, C 6H 5CONH, Cl 3CCH 2OCONH, Cl 3CCONH, C 8H 4O 2N, C 3H 5OCONH, F 3CCH 2OCONH, NO 2C 6H 4CONH or other sugar unit.
R 2Can be H, OH, CH 3O, C 3H 5O, C 3H 3O, C 6H 5CH 2O, CH 3OC 6H 4CH 2O, OSO 3 -, CH 3COO, C 6H 5COO, (CH 3) 3CCOO, ONO 2, CH 2COOCH 2CH 2COO, C 13H 9CH 2OCOO, C 3H 5OCOO, N 3, CH 3SO 3, C 7H 6SO 3, or other sugar unit.
R 3Can be H, CH 3, CH 2OH, CH 2OCH 3, CH 2OC 3H 3, CH 2OC 3H 5, CH 2OSO 3 -, COOCH 3, COOH, COONa, COOCH 2C 6H 5, COOC 3H 5, COOCH 3CH 2OOCCH 3, CH 2OOCCH 3, CH 2OOCCH 2Cl, CH 2OOCC 6H 5, CH 2OOCC 6H 4Br, CH 2OOCCH 2CH 2OOCCH 3, CH 2OOCC (CH 3) 3, CH 2OOCOCH 2C 13H 9, CH 2N 3, CH 2OC 3H 5, CH 2OCH 2C 6H 5, CH 2OCH 2C 6H 4OCH 3, CH 2OSO 2CH 3, CH 2OSO 2C 7H 6Or other sugar unit.
2. method according to claim 1 is characterized in that FeCl 36H 2The consumption of O is the 0.1-20 molar equivalent of reaction substrate.
3. method according to claim 1 is characterized in that, temperature of reaction is between 0 ℃-200 ℃.
4. method according to claim 1 is characterized in that, the reaction times is between 5 minutes-200 hours.
5. method according to claim 1 is characterized in that, can with iron trichloride (FeCl 3) form the reagent and the method for hydration mixture.
6. method according to claim 1 is characterized in that, iron trichloride (FeCl 3) with contain the solvent and the reagent of water.
7. method according to claim 1 is characterized in that, can form the reagent and the method for iron(ic) chloride.
CNA2008101035286A 2008-04-08 2008-04-08 Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O Pending CN101555262A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11401339B2 (en) 2018-08-23 2022-08-02 Seagen Inc. Anti-TIGIT antibodies

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11401339B2 (en) 2018-08-23 2022-08-02 Seagen Inc. Anti-TIGIT antibodies

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Application publication date: 20091014