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Method for preparing polyether with trans-condensed polycyclic ether skeleton structure by one-step method

A polycyclic ether and skeleton technology, applied in organic chemistry, bulk chemical production, etc., can solve the problems of low yield and inability to synthesize polyether, and achieve the effects of high yield, fast reaction and mild reaction conditions

Inactive Publication Date: 2021-12-17
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2000, the Murai research group in Japan developed a lanthanum salt-catalyzed intramolecular endo, endo-selective tandem epoxy ring-opening and cyclization reaction of homochiral polyepoxide precursor compounds. The introduction of methoxymethyl groups into the exo cyclization sites of the epoxy group can obtain better endo selectivity, but the yield of the polyether product containing three trans-fused six-membered rings is only 9% (Synlett 2000, pp 335-338)
[0017] Among the three reports, the yields of the first two cases were low, and these three reports could only produce polyethers with all six-membered rings or all polyethers with seven-membered rings, while the biologically active marine polyether toxin brevenal molecule Has a 7 / 7 / 6 / 7 / 6 five-ring structure mixed with six-membered cyclic ethers and seven-membered cyclic ethers
In addition, many biologically active marine polyether toxins contain eight-membered cyclic ethers or nine-membered cyclic ethers, and the existing endo, endo-selective tandem epoxy ring-opening and cyclization methods cannot be used to synthesize molecules containing eight-membered cyclic ethers. Polyethers of cyclic or nine-membered cyclic ethers

Method used

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  • Method for preparing polyether with trans-condensed polycyclic ether skeleton structure by one-step method
  • Method for preparing polyether with trans-condensed polycyclic ether skeleton structure by one-step method
  • Method for preparing polyether with trans-condensed polycyclic ether skeleton structure by one-step method

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076]

[0077]The diastereomeric mixture (48.4mg, 0.2mmol) of the diepoxy alcohol obtained by the asymmetric epoxidation of Shi, according to the hydrogen nuclear magnetic spectrum analysis wherein the content of all (R, R) diepoxy alcohol is 89%, That is, 0.178mmol) was dissolved in perfluoro-tert-butanol (2mL), and 1-ethyl-3-methylimidazolium tetrafluoroborate (40mg, 0.2mmol) was added thereto, and the reaction was stirred at 40°C for 15 hours . Add water (5mL) after completion of the reaction to quench the reaction, the reaction mixture is extracted three times with dichloromethane, 10mL each time, the organic phases of the three extractions are combined, the organic phase is washed once with water (10mL), and then washed once with saline (10mL) , then dried with anhydrous magnesium sulfate, concentrated by filtration, and carried out silica gel column chromatography using 35-50% ethyl acetate / petroleum ether as eluent to separate and obtain a white solid (23.7 mg, yiel...

Embodiment 2

[0083]

[0084] By the diastereomer mixture (59.6mg, 0.2mmol) of the triepoxyalcohol obtained by Shi asymmetric epoxidation, according to proton nuclear magnetic spectrum analysis wherein all are the content of the triepoxyalcohol substrate of (R, R) 83%, namely 0.166mmol) was dissolved in perfluoro-tert-butanol (2mL), and 1-ethyl-3-methylimidazolium tetrafluoroborate (40mg, 0.2mmol) was added thereto, stirred at 40°C React for 15 hours. Add water (5mL) after completion of the reaction to quench the reaction, the reaction mixture is extracted three times with dichloromethane, each 10mL, the organic phases of the three extractions are combined, the organic phase is washed once with water (10mL), and then washed once with brine (10mL) , then dried with anhydrous magnesium sulfate, concentrated by filtration, and carried out silica gel column chromatography using 35-50% ethyl acetate / petroleum ether as eluent, and separated to obtain a white solid (28.2mg, yield 57%) that has ...

Embodiment 3

[0090]

[0091] The diastereomeric mixture (73.6mg, 0.2mmol) of tetraepoxyalcohol obtained by asymmetric epoxidation of Shi, according to proton nuclear magnetic spectrum analysis wherein all are (R, R) the content of the tetraepoxyalcohol substrate is 75 %, namely 0.15mmol) was dissolved in perfluoro-tert-butanol (2mL), and 1-ethyl-3-methylimidazolium tetrafluoroborate (40mg, 0.2mmol) was added thereto, and the reaction was stirred at 40°C 15 hours. Add water (5mL) after completion of the reaction to quench the reaction, the reaction mixture is extracted three times with dichloromethane, 10mL each time, the organic phases of the three extractions are combined, the organic phase is washed once with water (10mL), and then washed once with saline (10mL) , then dried with anhydrous magnesium sulfate, concentrated by filtration, and carried out silica gel column chromatography using 35-50% ethyl acetate / petroleum ether as eluent, and separated to obtain a white solid (22.1mg, y...

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Abstract

The invention provides a synthesis method for preparing polyether with a trans-condensed polycyclic ether skeleton by a one-step method. Polyether with 2-5 rings and a trans-fused polycyclic ether skeleton is synthesized from a long-chain isochiral polyepoxy compound as a raw material through one-step intramolecular endo and endo-selective series epoxy ring-opening cyclization reaction, and each cyclic ether in a polyether molecule can be a six-membered cyclic ether, a seven-membered cyclic ether or an eight-membered cyclic ether. The trans-condensed polycyclic ether is of a common skeleton structure in more than 50 marine polyether toxin molecules, so that a new possible way is provided for industrial synthesis of polyether with a trans-condensed polycyclic ether skeleton, and the social benefit and the economic benefit are remarkable.

Description

technical field [0001] The invention relates to a method for preparing polyether with trans-fused polycyclic ether skeleton structure in one step. Background technique [0002] In 1981, the structure of the first marine polyether toxin brevetoxin B (brevetoxin B) produced by marine algae was determined to be a polyether compound with 11 trans-fused cyclic ethers (J.Am.Chem .Soc.1981,103,pp6773-6775), in the following years, scientists have successively discovered more than 50 marine polyether toxins from marine algae. The structural identification of these marine polyether toxins shows that these compounds have similar trans-fused polycyclic ether skeleton structures in the molecules, that is, the molecules contain multiple trans-syn-trans relative stereo configurations fused and The cyclic ethers formed (the sizes of cyclic ethers are five-membered cyclic ethers, six-membered cyclic ethers, seven-membered cyclic ethers, eight-membered cyclic ethers, and nine-membered cycli...

Claims

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Application Information

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IPC IPC(8): C07D493/04C07D493/14C07D493/22
CPCC07D493/04C07D493/14C07D493/22C08G65/00Y02P20/55
Inventor 渠瑾李风兴
Owner NANKAI UNIV