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Bridged ring lactone compounds, a preparing method thereof and applications of the compounds in construction of beta-mannoside bonds

A technology of ester compounds and mannosidic bonds, applied in the preparation of sugar derivatives, chemical instruments and methods, sugar derivatives, etc., can solve time-consuming problems and achieve simple operation, high stereoselectivity, and mild reaction conditions Effect

Inactive Publication Date: 2016-11-30
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] β-mannoside compounds can be formed by epimeric conversion of the 2-C hydroxyl of β-glucose, but this method is time-consuming

Method used

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  • Bridged ring lactone compounds, a preparing method thereof and applications of the compounds in construction of beta-mannoside bonds
  • Bridged ring lactone compounds, a preparing method thereof and applications of the compounds in construction of beta-mannoside bonds
  • Bridged ring lactone compounds, a preparing method thereof and applications of the compounds in construction of beta-mannoside bonds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Taking the bridged lactone compound shown in the synthetic formula III-1 as an example, its synthetic route and specific synthetic method are as follows:

[0024]

[0025] 1. 1.1067g (3.52mmol) ethylthio-3-benzyl-1-thio-α-mannose shown in formula I-1, 397mg (1.056mmol) tetraacetonitrile copper trifluoromethanesulfonate, Add 54.9mg (0.352mmol) of 2,2-bipyridine and 15mL of acetonitrile into a 50mL round-bottomed flask, vacuum three times for oxygen; add 71.5mg (0.457mmol) of tetramethylpiperidine oxide, Dissolve N-methylimidazole in 1 mL of acetonitrile, put the resulting solution into a round-bottomed flask, react in the dark at room temperature for 10 hours in an oxygen atmosphere, filter, spin dry the solvent with a rotary evaporator, and measure the volume ratio of ethyl acetate to petroleum ether The mixed solution of 3:1 was used as the eluent for column chromatography separation to obtain the compound of formula II-1 with a yield of 82%, and the structural char...

Embodiment 2

[0028] Taking the bridged ring lactone compound shown in the synthetic formula III-2 as an example, its synthetic method is as follows:

[0029]

[0030] Step 1 of this embodiment is the same as step 1 of Embodiment 1. In step 2 of Example 1, the pivaloyl chloride used is replaced with equimolar naphthoyl chloride, and the reaction time is shortened to 2 hours. Other steps are the same as in Example 1 to obtain the bridged ring lactone shown in formula III-2 Compound, its yield is 85%, structural characterization data is: 1 H NMR (400MHz, CDCl 3 )δ8.17-8.10(m,2H),7.67-7.59(m,1H),7.54-7.45(m,2H),7.35-7.26(m,5H),5.36(d,J=2.8Hz,1H) ,5.27(dt,J=2.3,1.2Hz,1H),4.92–4.86(m,1H),4.74-4.62(m,2H),4.61(dd,J=2.2,0.7Hz,1H),4.21(s ,1H),2.78(q,J=7.4Hz,2H),1.34(t,J=7.4Hz,3H).; 13 C NMR (101MHz, CDCl 3 )δ166.71, 164.96, 136.41, 133.64, 130.07, 129.02, 128.54, 128.49, 128.18, 127.93, 80.52, 77.36, 77.32, 77.00, 76.68, 74.67, 74.19, 71.84, 71.37; Na + ])C 22 h 22 NaO 6 The theoretical...

Embodiment 3

[0032] Taking the bridged ring lactone compound shown in the synthetic formula III-3 as an example, its synthetic method is as follows:

[0033]

[0034] Step 1 of this embodiment is the same as step 1 of Embodiment 1. In step 2, 123.9mg (0.399mmol) of compound II-1 was azeotroped with toluene three times to remove water, then it was dissolved with 2.1mL of anhydrous dichloromethane under argon protection and stirring in an ice bath, and 104.5mg (0.478mmol) di-tert-butyl dicarbonate, 4.8mg (0.040mmol) 4-dimethylaminopyridine, after reacting at room temperature for 1 hour, the reaction was complete through TLC point plate detection, concentrated, column chromatography (eluent was Petroleum ether and ethyl acetate volume ratio is the mixed solution of 3:1), obtains the bridged ring lactone compound shown in formula III-3, and its productive rate is 86%, and structural characterization data is: 1 H NMR (400MHz, CDCl 3 )δ7.39-7.30 (m, 5H), 5.26 (d, J = 2.6Hz, 1H), 4.84 (d, J ...

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Abstract

Bridged ring lactone compounds, a preparing method thereof and applications of the compounds in construction of beta-mannoside bonds are disclosed. The general structure formula of the compounds is shown in the description, wherein R1 represents alkyl or an aromatic group, R2 represents a silicon group, an acyl group or an ester group which have high steric hindrance and R3 represents a commonly used protecting group. Two hydroxy groups at 2 and 6 sites of mannosyl are subjected to aerobic catalysis through a monovalent copper catalyst and a nitryl free radical to synthesize the bridged ring lactone compounds. Reaction conditions are mild and operations are simple. The prepared bridged ring lactone compounds can be adopted as glycosyl donors and subjected to glycosylation with receptors to obtain beta-mannoside compounds with high stereoselectivity, thus providing a novel process for constructing the beta-mannoside bonds.

Description

technical field [0001] The invention belongs to the technical field of sugar synthesis, and in particular relates to constructing a bridged lactone through a copper nitroxyl catalyst, and using the compound as a glycosyl donor to obtain a β-mannoside bond with high stereoselectivity in a glycosylation reaction. Background technique [0002] Proteins, nucleic acids, and carbohydrates are the three most important types of biomacromolecules. In life activities, carbohydrates play the roles of structural substances, energy substances and information transmission substances. Although carbohydrates and glycoconjugated complexes have been recognized as fundamental biological systems of action, access to these molecules has so far remained difficult. β-mannoside and its derivatives are widely present in organisms and on the surface of cells, and play very important biological functions. It is also widely present in plants and a variety of antibiotics (such as cheinomycin), which h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/08C07H17/04C07H1/00
CPCY02P20/55C07D493/08C07H1/00C07H17/04
Inventor 柴永海陈龙盛靖园祖瑜佳张琦
Owner SHAANXI NORMAL UNIV
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