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, mild reaction conditions and low cost of raw materials

Inactive Publication Date: 2015-03-04
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] Embodiment one: adopt above-mentioned obtained [YL 2 ][{(THF) 3 Li} 2 (μ-Cl)] catalyzed asymmetric epoxidation of α,β-unsaturated ketones:

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

[0058] The product was separated on a silica gel column and washed with an 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 Chiralp...

Embodiment 2

[0059] Embodiment two: adopt the [YbL that above-mentioned makes 2 ][{(THF) 3 Li} 2 (μ-Cl)] catalyzed asymmetric epoxidation of α,β-unsaturated ketones:

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

[0061] The product was separated on a silica gel column and washed 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] Embodiment three: adopt the [SmL that above-mentioned makes 2 ][{(THF) 3 Li} 2 (μ-Cl)] catalyzed asymmetric epoxidation of α,β-unsaturated ketones:

[0063] In the reaction flask that has been treated with dehydration and deoxygenation, add 0.0625 grams (0.3 mmol) of chalcone and 0.048 grams (0.03 mmol) of catalyst under the protection of argon, add 1.9 milliliters of tetrahydrofuran, and set the temperature at 25 ° C After stirring in a constant temperature bath for 5 minutes, 0.065 ml of tert-butyl hydroperoxide (5.5 mmol / ml n-decane solution) was added, and the reaction was continued at 25°C for 4 h, and terminated with saturated aqueous sodium sulfite.

[0064] The product was separated on a silica gel column and rinsed with an 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 1.0mL / min, ee ...

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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 chiral epoxy compounds. Background technique [0002] Optically pure epoxides have a wide range of uses and are a good class of intermediates in organic synthesis. The epoxidation of alkenes with chiral catalysts is the simplest and most effective way to obtain such compounds. At present, there are many kinds of catalysts that can catalyze this kind of reaction. There are mainly two 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 iminium salt system, etc. [0003] Reports about the Sharpless system: [0004] In 1980, Sharpless et al. reported for the first time that Ti(OPr i ) 4 Composed of a catalytic system with chiral dialkyl tartrate, under the condition of tert-butyl hydroperoxide as an oxidant, it...

Claims

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Application Information

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