Preparation method of chiral epoxy compound

A technology of epoxy compounds and rare earth compounds, applied in chemical instruments and methods, chemical/physical processes, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems that have not been seen yet, and reach the scope of substrate adaptation Wide range, simple synthesis, high catalytic activity

Inactive Publication Date: 2013-11-20
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] So far, there has been no report on the preparation of chiral epoxy compounds by using chiral bridged aryloxyalkoxy metal compounds as catalysts to catalyze the asymmetric epoxidation of α,β-unsaturated ketones

Method used

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  • Preparation method of chiral epoxy compound
  • Preparation method of chiral epoxy compound
  • Preparation method of chiral epoxy compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0056] Example 1: Using the above prepared [YL 2 ][{(THF) 3 Li} 2 (μ-Cl)] Catalyzes the asymmetric epoxidation reaction of α,β-unsaturated ketones:

[0057] In the reaction flask that has been dehydrated and deoxygenated, add chalcone (ie chalcone without substituents, the same as in Examples 2 to 5) 0.0625 g (0.3 mmol) and 0.048 g (0.03 mmol) of the catalyst under the protection of argon. Millimoles), add 2.0 ml of tetrahydrofuran, stir in a constant temperature bath set at 25°C for 5 minutes, add 0.065 ml of tert-butyl hydroperoxide (5.5 mmol / ml of n-decane solution), continue at 25°C After 4 hours of reaction, the reaction was terminated with saturated aqueous sodium sulfite solution.

[0058] The product was separated by silica gel column, and eluted with the eluent of ethyl acetate: petroleum ether=1:30 to obtain 57.80 mg of epoxidized chalcone with a yield of 95%. Enantioselectivity was determined by chiral HPLC, Daicel Chiralpak OJ column, eluent i-PrOH / hexane (10 / 90), flow...

Embodiment 2

[0059] Example 2: Using the above prepared [YbL 2 ][{(THF) 3 Li} 2 (μ-Cl)] Catalyzes the asymmetric epoxidation reaction of α,β-unsaturated ketones:

[0060] In a reaction flask that has undergone dehydration and deoxygenation, 0.104 g (0.5 mmol) of chalcone and 0.076 g (0.05 mmol) of catalyst are added under the protection of argon, and 3.2 ml of tetrahydrofuran is added. The temperature is set at 0°C. After stirring in a constant temperature bath for 20 minutes, add 0.11 ml of tert-butyl hydroperoxide (5.5 mmol / ml n-decane solution), continue the reaction at 0°C for 12 hours, and terminate with saturated sodium sulfite aqueous solution.

[0061] The product was separated by a silica gel column, and eluted with an eluent of ethyl acetate:petroleum ether=1:30 to obtain 78.4 mg of epoxidized chalcone with a yield of 70%. Enantioselectivity was determined by chiral HPLC, Daicel Chiralpak OJ column, eluent i-PrOH / hexane(10 / 90), flow rate 1.0mL / min, ee value 89%.

Embodiment 3

[0062] Example 3: Using the above-prepared [SmL 2 ][{(THF) 3 Li} 2 (μ-Cl)] Catalyzes the asymmetric epoxidation reaction of α,β-unsaturated ketones:

[0063] In the reaction flask after dehydration and deoxygenation, add chalcone 0.0625 g (0.3 mmol), catalyst 0.048 g (0.03 mmol), add 1.9 ml of tetrahydrofuran, set the temperature at 25 ℃ under the protection of argon After stirring in a constant temperature bath for 5 minutes, add 0.065 ml of tert-butyl hydroperoxide (5.5 mmol / ml of n-decane solution), continue the reaction at 25°C for 4 hours, and terminate with saturated sodium sulfite aqueous solution.

[0064] The product was separated by silica gel column, and eluted with the eluent of ethyl acetate: petroleum ether=1:30 to obtain 63.2 mg of epoxidized chalcone, with a yield of 94%. Enantioselectivity was determined by chiral HPLC, Daicel Chiralpak OJ column, eluent i-PrOH / hexane (10 / 90), flow rate 1.0 mL / min, ee value 15%.

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Abstract

The invention discloses a preparation method of a chiral epoxy compound. The preparation method is characterized by preparing the chiral epoxy compound by catalyzing alpha, beta-unsaturated ketone to be subjected to asymmetric epoxidation reaction by adopting a chiral bridging aryloxy alkoxy rare-earth compound as a catalyst; the general formula of the catalyst is [LnL2][{(THF)3Li}2(mu-Cl)], the chemical structural formula of the catalyst is as shown in the specification, wherein Ln is one of rare-earth metals, namely neodymium, samarium, ytterbium, yttrium and lutetium, and L=(S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-phenol. The method disclosed by the invention has the advantages of easiness for catalyst synthesis, convenience for separation and purification, low raw material cost and mildness in reaction condition; the chiral epoxy compound prepared through the method has the advantages of high catalytic activity, good enantioselectivity and wide substrate application range.

Description

Technical field [0001] The invention relates to the field of asymmetric catalysis, in particular to a preparation method of a chiral epoxy compound. Background technique [0002] Optically pure epoxides have a wide range of uses and are a kind of good organic synthesis intermediates. Using chiral catalysts to catalyze the epoxidation of olefins is the simplest and most effective way to obtain such compounds. At present, there are many kinds of catalysts that have catalytic effects on such reactions. There are two main categories of metal complexes and small organic molecules, including Sharpless system, chiral binaphthol system, chiral porphyrin system, chiral Salen complex system, chiral ketone system, chiral imine salt system, etc. [0003] Reports on the Sharpless system: [0004] In 1980, Sharpless et al. first reported that Ti(OPr i ) 4 And chiral dialkyl tartrate to form a catalytic system. Under the condition of tert-butyl hydroperoxide as oxidant, it can effectively cataly...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D301/19C07D303/32C07D407/06B01J31/22
Inventor 姚英明
Owner SUZHOU UNIV
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