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Preparation method of beta-full-protecting-group fluoroglycoside

A fully protected technology for fluoroglycosides, which is applied in the field of preparation of β-fully protected fluoroglycosides, can solve the problems of unsatisfactory product stereoselectivity, difficulty in separating fluoroglycoside isomers, and unsatisfactory yields. Achieve the effects of high yield, low production cost and convenient operation

Inactive Publication Date: 2012-07-25
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Some common synthetic methods use DAST as a fluorine reagent (W. Rosenbrook Jr., D.A. Riley, P.A. Lartey, Tetrahedron Lett. 1985, 26, 3.), and the yield of this method in the synthesis of fluoroglycosides Better, but not very ideal in terms of product stereoselectivity, and often obtain fluoroglycoside isomers in α and β-configurations that are difficult to separate
In addition, there are also reports using metal fluorides such as AgF as fluorine reagents to synthesize fluoroglycosides (M. Teichmann, G. Descotes, D. Lafont, Synthesis. 1993, 889.), this method can Synthesis of fluoroglycosides with better stereoselectivity, but the yield is often not ideal

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Dissolve 44 mg (0.13 mmol) of 2,3,4,6-O-tetraacetylgalactose in 1 mL of dichloromethane, then sequentially add 36 μL (0.26 mmol) of triethylamine and 26 μL (0.13 mmol) of 5-iodo- 3-Oxaperfluoropentanesulfonyl fluoride was used to synthesize the rearrangement product, and the reaction was complete in about 15 minutes. The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain 38 mg of the product as 2,3,4,6-O-tetraacetyl The yield of galactofluoroside was 86%.

[0014] The obtained product 2, 3, 4, 6-O-tetraacetylgalactosin was analyzed, and the test data were as follows ：

[0015] NMR data: 1 H NMR (500MHz, CDCl 3 ): β isomer δ5.35 (dd, 1H, J =52, 6Hz), 5.18 (m, 2H), 5.08 (m, 1H), 4.24 (dd, 1H), 4.19 (dd, 1H), 3.88 (t, 1H), 2.08~2.01(4s, 12H). 19 F NMR (300 MHz, CDCl 3 ) δ -136.6 (β).

[0016] Mass spectral data: ESI-MS (m / z): [M+Na + ]: 373.08

Embodiment 2

[0018] Dissolve 500mg (0.93mmol) 2,3,4,6-O-tetrabenzylglucose in 15mL tetrahydrofuran, then add 338μL (2.3mmol) 1,8-diazabicyclo-bicyclo(5,4, 0)-7-undecene (DBU) and 385 μL (1.85 mmol) 5-iodo-3-oxaperfluoropentanesulfonyl fluoride (ICF 2 CF 2 OCF 2 CF 2 SO 2 F) The reaction was carried out, and the reaction was complete in about 30 minutes. The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain 480 mg of the product as 2,3,4,6-O-tetrabenzylglucoside fluoroglycoside, with a yield of 96%.

[0019] The resulting product 2,3,4,6-O-tetrabenzylglucoside was analyzed, and the test data were as follows ：

[0020] NMR data: 1 H NMR (500 MHz, CDCl 3 ): δ 7.15~7.31 (m, 20H), 5.25 (dd, 1H, J = 53, 6.8 Hz), 4.98~4.45 (m, 8H), 3.72~3.57(m, 6H). 19 F NMR (300 MHz, CDCl 3 ) δ -138.6 (β).

[0021] Mass spectral data: ESI-MS (m / z): [M+Na + ]:565.25

[0022] After testing and analyzing the products obtained in the above exa...

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Abstract

The invention discloses a preparation method of a beta-full-protecting-group fluoroglycoside. The preparation method is characterized by comprising the steps of stirring and dissolving 1-hydroxy full-protecting sugar, 5-iodo-octafluoro-3-oxapentanesulfonyl fluoride and organic alkali in dichloromethane, toluene, tetrahydrofuran or diethyl ether according to the mole ratio of 1:0.8-5.0:0.8-5.0, then conducting synthesis reaction of a rearrangement product at the temperature of below 50 DEG C to 50 DEG C, after the complete reaction, reducing the pressure, concentrating and conducting column chromatography separation to obtain the full-protecting-group bluorine glycoside with Beta conformation. Compared with the prior art, the preparation method has the advantages that the productivity is high, the three-dimensional effect is good, the obtained products are all full-protecting-group fluoroglycosidewith Beta conformation, the process is simple, the operation is convenient, and the production cost is low; and the preparation method is a new environment-friendly, economical and high-efficiency synthesis method, and has a great value for promoting floxuridine to be applied to in carbohydrate chemistry.

Description

technical field [0001] The invention relates to the technical field of synthesis of pharmaceutical intermediates, in particular to a preparation method of β-full protecting group fluoroglycoside. Background technique [0002] Due to their good chemical and thermal stability, fluoroglycosides are widely used in the synthesis of some glycosides and natural products as donors for glycosylation reactions (K. C. Nicolaou, R. E. Dolle, D. P. Papahatjis, J. L. Randall, J. Am. Chem. Soc . 1984, 106, 4189.), so the synthesis of fluoroglycosides is very important. The use of 1-hydroxy fully protected sugar as a raw material is one of the important methods. Some common synthetic methods adopt DAST as fluorine reagent (W. Rosenbrook Jr., D.A. Riley, P.A. Lartey, Tetrahedron Lett . 1985, 26, 3.), this method has a good yield in the synthesis of fluoroglycosides, but the stereoselectivity of the product is not very ideal, and often obtains α and β-configurations of fluoroglycosides tha...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07H15/18C07H1/00
CPCY02P20/55
Inventor 张剑波王晓虎
Owner EAST CHINA NORMAL UNIV