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Preparation method of load type chiral ketone catalyst and application thereof

A technology of chiral ketones and catalysts, applied in the field of preparation of supported chiral ketones, can solve the problems of unpublished experimental results, no practical application value, low ee value, etc., and achieve low price, high ee value, and easy preparation process simple effect

Inactive Publication Date: 2012-07-18
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The asymmetric epoxidation reaction catalyzed by chiral ketones, due to the characteristics of fast reaction and mild conditions without using metal compounds that are restricted in drug synthesis, makes the research in this field very active. Among many chiral ketone catalysts, 1 ~4 The ee value of the product obtained by catalysis is very low, so it has no practical value
The ee value of the product obtained by catalysis of 5~7 increases greatly, but this series of catalysts all need quite expensive starting materials and multi-step reactions to prepare. Therefore, a higher catalyst dosage (usually a lot relative to the substrate less than 10%) bring disadvantages to their wide application
Cozzi tried to immobilize Shione 10 on MeOPEG 5000 above, but the experimental results have not been published (Cozzi, F. Advanced Synthesis & Catalysis 2006, 348, 1367-1390.)

Method used

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  • Preparation method of load type chiral ketone catalyst and application thereof
  • Preparation method of load type chiral ketone catalyst and application thereof
  • Preparation method of load type chiral ketone catalyst and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Embodiment 1, a kind of preparation method of supported chiral ketone catalyst is carried out in the following steps successively:

[0045] 1), preparation of chiral ketone:

[0046] Add D-glucose (11) 59.8g (332.0mmol) and Bn in 350mL ethanol 2 NH 64.0mL (332.0mmol), then add acetic acid 57.0mL (995.7mmol), reflux reaction for 3h, the reaction solution turns orange-yellow, and the viscosity increases, keep stirring continuously for 3 hours under heating and reflux; and the temperature of the oil bath should not be high At 90°C (the reaction is heated by an oil bath, in order to prevent the occurrence of side reactions, the temperature of the oil bath needs to be controlled below 90°C). After the reaction solution was cooled to 0°C, it was suction-filtered under reduced pressure, and the filter cake was continuously washed with ice ethanol until white, and dried in vacuo to obtain 95.5 g of white solid 1-dibenzylamino-1-deoxy-D-fructose (12). The yield was 80.5%.

[...

Embodiment 2

[0058] The epoxidation of embodiment 2, styrene

[0059] Add 52mg (0.5mmol) of styrene in the reaction flask, 50mg (0.025mmol, 5%mol) of the supported chiral ketone catalyst after activation, solvent DME-DMM (volume ratio 3: 1) 8mL, buffer solution 5mL (0.2 MK 2 CO 3 -AcOH, with 4×10 -4 M Na 2 EDTA aqueous solution, pH = 8.0), Bu 4 NHSO 4 (0.0075g, 0.02mmol), after the above reaction mixture was cooled to -10°C, Oxone solution (concentration of Oxone was 0.21M, mixed with 4×10 -4 M Na 2 EDTA aqueous solution) 4.2mL (that is, containing Oxone 0.548g, 0.882mmol) and K 2 CO 3 Solution (K 2 CO 3 The concentration is 0.48M, with 4×10 -4 M Na 2 EDTA aqueous solution) 4.2mL (that is, containing K 2 CO 3 0.278g, 2.01mmol) was added dropwise to the reaction system within 3h with a plunger pump. After completion of the dropwise addition, filter, and the obtained catalyst solid can be used for recycling, and the filtrate is extracted with n-pentane (5mL×3), and the organic...

Embodiment 3

[0060] The epoxidation of embodiment 3,2-chlorostyrene

[0061] Add 69.3 mg (0.5 mmol) of 2-chlorostyrene into the reaction flask, 50 mg (0.025 mmol, 5% mol) of the activated chiral ketone catalyst, 8 mL of solvent DME-DMM (volume ratio 3:1), buffer solution 5mL (0.2MK 2 CO 3 -AcOH, with 4×10 -4 M Na 2 EDTA aqueous solution, pH = 8.0), Bu 4 NHSO 4 (0.0075g, 0.02mmol), after the above reaction mixture was cooled to -10°C, Oxone solution (0.21M, with 4×10 -4 M Na 2 EDTA aqueous solution) 4.2mL (containing Oxone 0.548g, 0.89mmol) and K 2 CO 3 solution (0.48M, with 4×10 -4 MNa 2 EDTA aqueous solution) 4.2mL (contains K 2 CO 3 0.278g, 2.01mmol) was added dropwise to the reaction system within 3h with a plunger pump. After the addition was complete, it was extracted with n-pentane (5mL×3), and the organic phase was washed with brine and washed with anhydrous Na 2 SO 4 Drying, concentration, purification with flash column chromatography, specifically as follows: 5g 200...

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Abstract

The invention discloses a preparation method of load type chiral ketone catalyst, which comprises the step of carrying out surface modification on a carrier to obtain the carrier by means of surface modification, and also comprises the following steps of: 1) preparing chiral ketone: in solution, preparing the chiral ketone by midbody ketone and allyl chlorocarbonate under the catalysis of catalyst and the condition of acid-binding agent; and 2) carrying out solid load on the chiral ketone catalyst: carrying out reflux reaction on the chiral ketone, the carrier obtained by means of surface modification and the radical initiator in inert solvent, cooling a product into room temperature, filtering, washing the obtained solid by mixed solvent of dichloromethane and diethyl ether in a soxhlet extractor, and carrying out vacuum drying under room temperature to obtain the load type chiral ketone catalyst. The load type chiral ketone catalyst prepared by the invention is applicable to the asymmetric epoxidation reaction of olefin.

Description

technical field [0001] The invention relates to a method for preparing a loaded chiral ketone and its application in asymmetric epoxidation of olefins. Background technique [0002] As a class of compounds with very practical value, optically active epoxides are especially used as intermediates in the production of enantiomerically pure drugs. Therefore, the research on the synthesis of optically active epoxides has become a hot spot in the field of asymmetric synthesis in recent years. one. The asymmetric epoxidation reaction of alkenes is an important way to synthesize chiral epoxides. The tartrate-tetraisopropoxytitanium system developed by Sharpless et al. can perform high enantioselectivity on various allyl alcohol substrates. Epoxidation has been widely used in synthesis. The salen-Mn(II) complex catalysts reported by Jacobsen and Katsuki respectively have proved to have great potential in the asymmetric epoxidation of non-functional olefins. For metal-free catalyzed...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07B53/00C07D303/04C07D303/08C07D301/03
Inventor 陈新志计立周少东
Owner ZHEJIANG UNIV
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