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Method for processing asymmetric hydroxylamination and dihydroxylation reaction by use of supported bi-cinchoni alkaloid ligand

An alkaloid, asymmetric technology, used in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., can solve problems such as difficulty in success, difficult recovery, and expensive osmium oxidant.

Inactive Publication Date: 2004-09-01
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, because the ligands and osmium oxidants used are relatively expensive and difficult to recycle, and osmium is a highly toxic substance, it is difficult to succeed in mass production of C13 side chains in industrial production.

Method used

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  • Method for processing asymmetric hydroxylamination and dihydroxylation reaction by use of supported bi-cinchoni alkaloid ligand
  • Method for processing asymmetric hydroxylamination and dihydroxylation reaction by use of supported bi-cinchoni alkaloid ligand
  • Method for processing asymmetric hydroxylamination and dihydroxylation reaction by use of supported bi-cinchoni alkaloid ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1 Ligand connection

[0036] Weigh polyethylene glycol (molecular weight 6000, 12g) and add it to a 100ml dry three-necked flask, under nitrogen protection, add tetrahydrofuran (50ml), then add n-BuLi (3ml) (2.5M in hexane), the addition is complete, Stir at room temperature for 30 minutes, then add Reflux at 78°C until the reaction is complete, then cool, add about 15ml of water, extract with dichloromethane, dry, concentrate, add a very small amount of dichloromethane to dissolve the residue under vigorous stirring, and add diethyl ether under stirring to obtain The white precipitate was stirred for 1 h, then filtered, and the solid was washed three times with a mixture of cold ethanol and ether (1:4), then twice with anhydrous ether, and dried in vacuo to obtain the immobilized ligand. Yield 68%.

Embodiment 2AA

[0037] Embodiment 2AA reaction

[0038] LiOH.H 2 O (1 mmol), ligand (10 or 20 mol%), K 2 OSo 2 (OH) 4 (0.04mmol), added to a solution of tert-butanol / water (1:1) (5ml and 5ml), stirred to obtain a clear solution, cooled to 5°C, added isopropyl cinnamate (1mmol) and CH 3 CONHBr (1 mmol) was stirred at 5°C for 10-15 hours before working up.

Embodiment 3

[0040] The same as example 2 above, but add CH first 3 CONHBr (1mmol), let it stir for 30 minutes, then add isopropyl cinnamate (1mmol), post-treatment with Example 2.

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Abstract

The invention relates to a process for carrying out asymmetrical hydroxylamine amination reaction and dual hydroxide reaction, wherein synthesized high polymer tethered Cinchonideine alkaloid ligand is utilized for raising yield and selectivity for the reaction product, the catalyst can be used repeatedly. The process is especially suitable for the mass production of Taxol synthesis and its C13 side chains, the used synthesized high polymer tethered Cinchonideine alkaloid ligand has the structural formula as disclosed in the specification, wherein PEG is polyoxyethylene glycols, R=H or OCH3.

Description

technical field [0001] The present invention is a method for asymmetric hydroxylation reaction and dihydroxylation reaction using the synthesized polymer immobilized biscinconyl alkaloid ligand, the method is especially suitable for synthesizing paclitaxel (Taxol) and its C13 side chain mass production. Background technique [0002] The cis-dihydroxylation reaction (AD) of alkenes has been reported a long time ago, and the oxidizing agents include osmium tetroxide and potassium permanganate, but the amount of oxidizing agents is stoichiometric. In 1992, Sharpless found that cinchonine alkaloids could be used as chiral inducing ligands to realize the asymmetric dihydroxylation of alkenes in a catalytic amount (K.B.Sharpless.J.Org.Chem.1992, 57, 2768-2771). Since then, many groups have carried out research on cis-dihydroxylation (AD) of olefins and achieved good results, which makes dihydroxylation now a very useful method in the synthesis of natural products, pharmaceuticals...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/02C07B43/04C07C29/00C07C69/732C07C213/00C07C215/02C07C229/34C07D401/14C08G65/00
Inventor 林国强刘汉泉杨细文徐明华
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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