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Method for stereoselectively synthesizing beta-2-deoxyglycoside bond

A stereoselective, deoxyglycosidic bond technology, applied in the field of stereoselective synthesis of β-2-deoxyglycosidic bonds, can solve the problems of poor substrate applicability and poor stereoselectivity of β-2-deoxyglycosidic bonds, etc. , to achieve the effect of a wide range of substrates, easy availability of raw materials and less side reactions

Inactive Publication Date: 2019-06-21
SICHUAN UNIVERSITY OF SCIENCE AND ENGINEERING
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a method for the stereoselective synthesis of β-2-deoxyglycosidic bonds, which solves the poor stereoselectivity and low The problem of poor applicability

Method used

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  • Method for stereoselectively synthesizing beta-2-deoxyglycoside bond
  • Method for stereoselectively synthesizing beta-2-deoxyglycoside bond
  • Method for stereoselectively synthesizing beta-2-deoxyglycoside bond

Examples

Experimental program
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Effect test

Embodiment 1

[0041] 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactose (81 mg, 0.19 mmol), glycosyl acceptor 2,3,4-tri- O-benzyl-α-D-glucopyranoside (134 mg, 0.29 mmol) and freshly activated 4A molecular sieves (220 mg) in dry CH 3 CN:CH 2 Cl 2 (v:v=2:1, 2.9 mL) was cooled to -50 °C. The suspension was stirred for 15 minutes, then NIS (86 mg, 0.38 mmol) and TMSOTf (52 μL, 0.29 mmol) were added. The reaction mixture was stirred at the same temperature for 2 hours. The reaction mixture was gradually warmed to 0 °C and washed with Et 3 N quenching. The mixture was washed with CH 2 Cl 2 dilute and add Na 2 S 2 o 3 , filtered through celite and concentrated in vacuo. The crude material was flash purified by column chromatography (10:1, petroleum ether-EtOAc) to give compound 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-2-deoxy-2 -Iodo-β-D-galactopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside as a light syrup (159 mg, 82.3%) . R f 0.45 (4:1, petroleumether–E...

Embodiment 2

[0043] 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactose (52 mg, 0.12 mmol), glycosyl acceptor 2,3,4-tri- O-benzoyl-α-D-mannopyranoside (90 mg, 0.18 mmol) and freshly activated 4A molecular sieves (140 mg) in dry reagent (V CH3CN :V CH2Cl2 =2:1, 1.8mL) and cooled to -50°C. The suspension was stirred for 15 minutes, then NIS (55 mg, 0.24 mmol) and TMSOTf (33 μL, 0.18 mmol) were added. The reaction mixture was stirred at the same temperature for 2 hours. The reaction mixture was gradually warmed to 0 °C and washed with Et 3 N quenching. The mixture was washed with CH 2 Cl 2 dilute and add Na 2 S 2 o 3 , filtered through celite and concentrated in vacuo. The crude material was flash purified by column chromatography (3:1, petroleum ether-EtOAc) to give the product 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-2-deoxy-2 -Iodo-β-D-galactopyranose-(1→6)-2,3,4-tri-O-benzoyl-α-D-mannoside (110 mg, 85.1%). R f 0.4 (petroleum ether:ethyl acetate=3:1). 1 H ...

Embodiment 3

[0045] 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactose (49 mg, 0.12 mmol), glycosyl acceptor 2,3,4-tri- O-benzyl-α-D-galactopyranoside (80 mg, 0.17 mmol) and freshly activated 4A molecular sieves (130 mg) in dry reagent (V CH3CN :V CH2Cl2 =2:1, 1.7mL) and cooled to -50°C. The suspension was stirred for 15 minutes, then NIS (52 mg, 0.23 mmol) and TMSOTf (31 μL, 0.17 mmol) were added. The reaction mixture was stirred at the same temperature for 2 hours. The reaction mixture was gradually warmed to 0 °C and washed with Et 3 N quenching. The mixture was washed with CH 2 Cl 2 dilute and add Na 2 S 2 o 3 , filtered through celite and concentrated in vacuo. The crude material was flash purified by column chromatography (3:1, petroleum ether-EtOAc) to give the product 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-2-deoxy-2 -Iodo-β-D-galactopyranose-(1→6)-2,3,4-tri-O-benzyl-α-D-galactoside (102 mg, 87.4%). R f 0.4 (petroleum ether:ethyl acetate=3:1). 1 ...

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Abstract

The invention discloses a method for stereoselectively synthesizing a beta-2-deoxyglycoside bond. The method comprises the following steps: performing glycosylation on 3,4-O-isopropylidene-6-O-tert-butyl diphenylmethyl silicone-D-galactosene serving as a donor, a saccharide receptor and a molecular sieve under the condition of the existence of an accelerant, wherein an isopropyl acetal protectivegroup is mounted on a 3-site hydroxyl and a 4-site hydroxyl of the 3,4-O-isopropylidene-6-O-tert-butyl diphenylmethyl silicone-D-galactosene and a TBDPS is mounted on the 6-site of the 3,4-O-isopropylidene-6-O-tert-butyl diphenylmethyl silicone-D-galactosene; through the synergistic effect of the protective groups, sugar ring conformation of the donor is controlled, and the stereoselective synthesis of a beta-configuration is realized. According to the method, the stereoselectivity of the glycosylation can be controlled effectively and stereoselectively; the method is wide in substrate application range and convenient to operate; raw materials are easy to obtain; side reactions of the glycosylation are few; a target product is high in yield and optical purity; a new design thought is provided for the research of the glycosylation.

Description

technical field [0001] The invention belongs to the technical field of synthesis of natural oligosaccharide chains, and in particular relates to a method for stereoselective synthesis of β-2-deoxyglycosidic bonds. Background technique [0002] 2-deoxyglycoside refers to the glycoside in which the 2-hydroxyl of the glycosyl unit in the glycoside is replaced by a hydrogen atom. Erythromycin and enediynes) and cardiac glycosides, C21 steroidal saponins and other carbohydrate compounds sugar chain important structural units. 2-deoxyglycosides are active ingredients of many natural products and anti-tumor drugs. In view of their important biological functions and pharmacological and biological activities, the synthesis of natural 2-deoxyglycosides and their derivatives and the exploration of their biological significance are important for deoxysugar new drugs. Development has great guiding significance. [0003] The natural product 2-deoxyglycosides is extracted in a limited am...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/18C07F7/20
CPCY02P20/55
Inventor 陈越
Owner SICHUAN UNIVERSITY OF SCIENCE AND ENGINEERING
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