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Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof

A trimethylsilyl trifluoromethane sulfonate, solid technology, applied in the field of medicinal chemical synthesis, can solve the problems of violation of sustainable development strategy, expensive reagents, environmental pollution, etc. effect of stress

Inactive Publication Date: 2012-12-19
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are many methods for selective protection, selective deprotection and glycosylation of carbohydrate compounds. So far, these methods have some defects as follows: either the reagents used are very expensive, or the toxicity is very high, which has caused great harm to the environment. Pollution, which seriously violates the current sustainable development strategy advocated

Method used

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  • Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof
  • Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof
  • Method for preparing solid supported trimethylsilyl trifluoromethanesulfonate and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1: Preparation of silica-supported trimethylsilyl trifluoromethanesulfonate (TMSOTf)

[0023] In a 500 mL round bottom flask, 45 g of 200-300 mesh silica gel was suspended in 200 mL of anhydrous ether, and 14.2 mL of trimethylsilyl trifluoromethanesulfonate (TMSOTf) was slowly added dropwise under vigorous stirring. After the dropwise addition was completed and stirred at room temperature for 1 h, the solvent was evaporated under reduced pressure to a fluid solid powder. After activation at 100°C for 24 hours, 1.25mmol / g silica-loaded trimethylsilyl trifluoromethanesulfonate can be prepared.

Embodiment 2

[0024] Example 2: Silica supported trimethylsilyl trifluoromethanesulfonate catalyzed peracetylation

[0025]

[0026] D-glucose 1 (18.0 g, 100 mmol) was suspended in Ac 2 O (55mL, 550mmol), add TMSOTf-SiO several times under ice bath 2 (0.4g, 0.5mmol). After 10 min, TLC (petroleum ether: ethyl acetate = 2:1) detected that the reaction was complete, and ethyl acetate was added for dilution. filtered with saturated NaHCO 3 Neutralize, collect the organic phase, anhydrous Na 2 SO 4 After drying, concentration, and column chromatography, compound 2 (38.9 g, 99 mmol) was obtained with a yield of 99%. According to mass spectrometry, the molecular weight of compound 2 was 309.2.

Embodiment 3

[0027] Example 3: Silica supported trimethylsilyl trifluoromethanesulfonate catalyzed isopropylidene ylation

[0028]

[0029] Suspend D-galactose 3 (1.8g, 10.0mmol) in dry acetone (50mL), add TMSOTf-SiO under reflux 2 (0.4g, 0.5mmol). After 10 min, TLC (petroleum ether: ethyl acetate = 2:1) detected that the reaction was complete, and triethylamine was added to terminate the reaction. After filtration, concentration, and column chromatography, compound 4 (2.1 g, 8.1 mmol) was obtained with a yield of 81%. 1 H NMR (400MHz, CDCl 3 ): δ1.33(s, 6H, 2×CH 3 ), 1.45 (s, 3H, CH 3 ), 1.53 (s, 3H, CH 3 ), 2.34(br, 1H, OH), 3.74(m, 1H), 3.81-3.84(m, 2H), 4.28(d, J7.8Hz, 1H), 4.33(d, J0.8Hz, 1H), 4.61 (d, J7.8Hz, 1H), 5.56 (d, J4.3Hz, 1H, H-1).

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Abstract

The invention belongs to the field of chemical synthesis of drugs and relates to a method for preparing solid supported trimethylsilyl trifluoromethanesulfonate TMSOTf and an application thereof. The method comprises the following steps of: suspending a solid supported reagent on a preparation solvent, violently stirring, slowly adding trimethylsilyl trifluoromethanesulfonate drop by drop, stirring at room temperature, steaming to remove the solvent at reduced pressure to obtain a fluid solid powder, and activating at the temperature of 100 DEG C for 24h to prepare the solid supported trimethylsilyl trifluoromethanesulfonate. The method provided by the invention can be used in carbohydrate chemistry acetylation, isopropylation, benzalation, selective removal of isopropylidene, selective removal of triphenylmethyl, selective removal of tetrahydropyran and selective removal of silyl-ethers or glycosylation operation. The method provided by the invention is simple and easy to operate, has low toxicity, can be used to significantly reduce the stress caused by chemical synthesis to the environment, is suitable for large-scale industrial production, and can provide support for large-scale synthesis and screening of carbohydrate drugs.

Description

technical field [0001] The invention belongs to the field of pharmaceutical chemical synthesis, and relates to a method for preparing solid-loaded trimethylsilyl trifluoromethanesulfonate (TMSOTf) and its application in sugar chemistry, especially for the important role of sugar compounds with biological activity. Synthesis of intermediates. Background technique [0002] Natural oligosaccharides or glycoconjugates have good biological activities in terms of physiology and pharmacology, and have attracted more and more attention. So far, there have been a lot of literature reports on the synthesis of carbohydrate compounds. The prior art discloses that the synthesis process of carbohydrate compounds is selective protection of hydroxyl, selective deprotection and corresponding glycosylation process. Among them, the full acetylation of monosaccharides, the isopropylidene of adjacent dihydroxyl groups, and the benzylation are frequently used as selective protection operations ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07H13/04C07H9/04C07H15/18C07H1/00C07J1/00
Inventor 李英霞颜世强丁宁张伟
Owner FUDAN UNIV