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Method for improving beta-glucosidic bond stereoselectivity through bis(trifluoromethane sulfonimide) reagent activation glycosylation reaction

A technology of trifluoromethanesulfonimide and glycosylation reaction, which is applied in the field of β-glycosidic bonds, can solve the problems of low stereoselectivity of glycoside formation reaction and insufficient mild reaction conditions, and achieve high stereoselectivity and reaction The effect of mild conditions and high product yield

Inactive Publication Date: 2016-05-04
SHAANXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0003] The technical problem to be solved by the present invention is to overcome some limitations existing in the existing glycosidic bond construction methods, such as the disadvantages of low stereoselectivity of the glycoside formation reaction and insufficient mild reaction conditions, thereby providing a method using bistrifluoromethanesulfonyl Method for activating glycosylation reaction with imine reagent to improve stereoselectivity of β-glycosidic bond

Method used

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  • Method for improving beta-glucosidic bond stereoselectivity through bis(trifluoromethane sulfonimide) reagent activation glycosylation reaction
  • Method for improving beta-glucosidic bond stereoselectivity through bis(trifluoromethane sulfonimide) reagent activation glycosylation reaction
  • Method for improving beta-glucosidic bond stereoselectivity through bis(trifluoromethane sulfonimide) reagent activation glycosylation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Taking the glycosyl coupling product shown in the synthesis formula III-1 as an example, the reaction equation is as follows:

[0014]

[0015] Dissolve 83 mg (0.12 mmol) of the glycosyl donor represented by formula I-1 and 30 mg (0.08 mmol) of the glycosyl acceptor represented by formula II-1 in 0.62 mL of dichloromethane, and stir at 0°C for 10 minutes , drop 0.18mLTMSNTf 2 (1.8 μ L, 0.008 mmol) of dichloromethane solution, continue to react for 1 hour at 0° C., quench the reaction with triethylamine, spin dry, and column separation (the volume ratio of eluent is sherwood oil and ethyl acetate is 5: 1), to obtain the glycosyl coupling product shown in formula III-1, the total yield is 94%, α:β=1.5:1, and the structural characterization data of the product are as follows:

[0016] 1 HNMR (600MHz, CDCl 3 )δ: 8.02-7.98 (m, 2H), 7.57 (t, J=7.2Hz, 1H), 7.48-7.39 (m, 5H), 7.36-7.26 (m, 11H), 7.24-7.16 (m, 6H) , 7.13-7.02(m, 5H), 5.51(t, J=9.6Hz, 0.37H), 5.42(t, J=9.6...

Embodiment 2

[0021] Taking the glycosyl coupling product shown in the synthetic formula III-2 as an example, the reaction equation is as follows:

[0022]

[0023] Dissolve 76 mg (0.12 mmol) of the glycosyl donor represented by formula I-2 and 30 mg (0.08 mmol) of the glycosyl acceptor represented by formula II-1 in 0.62 mL of dichloromethane, and stir at -30°C for 10 minutes, drop 0.18mLTMSNTf 2 (1.8 μ L, 0.008 mmol) in dichloromethane solution, continue to react at -30 ° C for 1 hour, quench the reaction with triethylamine, spin dry, and column separation (the volume ratio of petroleum ether and ethyl acetate as the eluent is 4 :1 mixed solution), obtain formula III-2 compound, its total yield is 97%, α:β=1:10.1, the structural characterization data of product are as follows:

[0024] α-configuration product: 1 HNMR (600MHz, CDCl 3)δ: 8.00-7.99 (m, 2H), 7.59 (t, J = 7.2Hz, 1H), 7.45 (t, J = 7.8Hz, 2H), 7.41 (d, J = 7.2Hz, 2H), 7.37 ( t, J=7.8Hz, 2H), 7.34-7.27(m, 6H), 7.24-7.16(m,...

Embodiment 3

[0030] Taking the glycosyl coupling product shown in the synthesis formula III-3 as an example, the reaction equation is as follows:

[0031]

[0032] Dissolve 76 mg (0.12 mmol) of the glycosyl donor represented by formula I-2 and 21 mg (0.08 mmol) of the glycosyl acceptor represented by formula II-2 in 0.62 mL of dichloromethane, and stir at -30°C for 10 minutes, drop 0.18mLTMSNTf 2 (1.8 μ L, 0.008 mmol) in dichloromethane solution, continue to react at -30 ° C for 1 hour, quench the reaction with triethylamine, spin dry, and column separation (the volume ratio of petroleum ether and ethyl acetate as the eluent is 4 :1 mixed solution), to obtain the glycosyl coupling product shown in formula III-3, its total yield is 83%, α:β=1:10, the structural characterization data of the product are as follows:

[0033] α-configuration product: 1 HNMR (600MHz, CDCl 3 )δ: 7.36-7.22 (m, 14H), 5.52 (d, J = 4.8Hz, 1H), 5.31 (dd, J = 10.2, 3.6Hz, 1H), 5.10 (d, J = 3.6Hz, 1H), 4.92(d, J=...

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Abstract

The invention discloses a method for improving beta-glucosidic bond stereoselectivity through a bis(trifluoromethane sulfonimide) reagent activation glycosylation reaction. According to the method, under the action of a catalytic amount of bis(trifluoromethane sulfonimide) reagent, a glycosyl donor with a leaving group being the trichloroacetic imidic acid ester group or acetylenic acid ester group is subjected to coupling with different glycosyl receptors, the using amount of the bis(trifluoromethane sulfonimide) reagent is small, the reaction condition is mild, the product yield is high, and a beta-glycosylation product can be obtained in a high-stereoselectivity mode.

Description

technical field [0001] The present invention relates to the glycosylation reaction of a glycosyl donor and a glycosyl acceptor with trichloroacetimidate or alkynoate as a leaving group under the activation of a bistrifluoromethanesulfonimide reagent, thereby A method for obtaining highly stereoselective β-glycosidic linkages. Background technique [0002] As one of the three types of biological macromolecules, sugar is involved in the main aspects of the life process and is one of the most important material bases for maintaining the normal operation of the body. They are not only the structural substances and energy substances of organisms, but also participate in the process of information transmission between cells, body growth, reproduction, immune response and so on. The number of saccharides obtained through natural extraction is limited and has structural heterogeneity, which greatly restricts the research and application of saccharides in the fields of life science ...

Claims

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Application Information

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IPC IPC(8): C07H15/18C07H1/00
CPCY02P20/55C07H15/18C07H1/00
Inventor 柴永海盛靖园祖瑜佳张琦
Owner SHAANXI NORMAL UNIV
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