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Method for preparing optically active carbonyl compound

一种羰基化合物、光学活性的技术,应用在不对称催化有机合成领域,能够解决尚没有不饱和羰基化合物碳碳双键不对称氢化反应等问题

Active Publication Date: 2016-05-04
ZHEJIANG NHU CO LTD +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the biomimetic asymmetric catalyst technology is mainly used in the asymmetric hydrogenation of carbon-nitrogen double bonds of unsaturated imines, but there is no literature report on the asymmetric hydrogenation of carbon-carbon double bonds of unsaturated carbonyl compounds.

Method used

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  • Method for preparing optically active carbonyl compound
  • Method for preparing optically active carbonyl compound
  • Method for preparing optically active carbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1~16

[0056] The (results are listed in Table 1) general method of preparing optically active citronellal: in 250mL pressure reactor, under nitrogen protection condition, add metal catalyst [Ru(p-cymene)I 2 ] 2 (4.8mg, 0.005mol), chiral amine salt (0.01mol), dihydropyridine compound (0.05mol), geranial and neral mixture (a total of 15.2g, 0.1mol) and reaction solvent (110mL), will The reaction mixture was stirred at room temperature for 20 minutes; then the system was heated up to 55°C, and then the hydrogen in the reactor was replaced with 3 bar hydrogen, and the hydrogen was replaced repeatedly in this way, and then hydrogen was quickly filled into the reactor to 100 bar pressure reaction for 46 hours Finally, after the reaction of raw materials is detected by gas chromatography, stop the reaction and cool to room temperature, slowly discharge the hydrogen in the kettle, and replace the residual hydrogen in the kettle with nitrogen; the optical purity of the product (i.e. enantiom...

Embodiment 17~20

[0061] Embodiments 17-20 are carried out in the same manner as in Example 9, except that the metal catalyst is different; the results are listed in Table 2:

[0062] The reaction result of table 2 embodiment 17~20

[0063] Example

Embodiment 21~26

[0065] Embodiments 21-26 are carried out in the same manner as in Example 9, except that the acids used for the chiral amine salt are different; the results are listed in Table 3:

[0066] The reaction result of table 3 embodiment 21~26

[0067] Example

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PUM

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Abstract

The invention discloses a method for preparing an optically active carbonyl compound, which comprises the following step: under catalysis of a chiral amine salt and a transition metal catalyst, carrying out asymmetric catalytic hydrogenation reaction on alpha, beta-unsaturated aldehyde or alpha, beta-unsaturated ketone compound by taking hydrogen gas and a catalysis amount of dihydropyridine compound as a hydrogen source, so as to obtain the optically active carbonyl compound. The method has mild reaction conditions and simple operation, and the use amount of the dihydropyridine compound is the catalysis amount, so that a target product is easily separated and purified from a reaction system; and at the same time, the metal catalyst can be recycled, thereby meeting the economy requirement.

Description

technical field [0001] The invention belongs to the technical field of asymmetric catalytic organic synthesis, and specifically relates to a method for preparing an optically active carbonyl compound by using an α, β-unsaturated aldehyde or α, β-unsaturated ketone compound as a raw material through an asymmetric catalytic hydrogenation reaction. Background technique [0002] Optically active carbonyl compounds are important intermediates in the synthesis of medicines, flavors and fragrances, and pesticides. The selective asymmetric hydrogenation of carbon-carbon double bonds of α,β-unsaturated carbonyl compounds is an important way to obtain optically active carbonyl compounds. Chemists have developed different methods for selective asymmetric hydrogenation of carbon-carbon double bonds of α,β-unsaturated carbonyl compounds. These methods and their technical problems are as follows: [0003] (1) The homogeneous catalytic reaction using hydrogen as the hydrogen source, becau...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/62C07C47/21C07C47/225C07C47/232C07C47/24C07C47/277C07C47/27C07C49/203C07C49/21C07C49/217C07C49/223C07C49/603C07C49/683C07C49/613C07C201/12C07C205/44C07C67/303C07C69/738C07C69/73C07D333/22C07D307/46C07B53/00B01J31/22B01J31/02
CPCB01J31/0244B01J31/165B01J31/20B01J31/2414B01J2231/645C07B53/00C07B2200/07C07B2200/09C07C45/62C07C67/303C07C201/12C07D307/46C07D333/22C07C47/21C07C47/225C07C47/232C07C47/24C07C47/277C07C47/27C07C49/203C07C49/21C07C49/217C07C49/223C07C49/603C07C49/683C07C49/613C07C205/44C07C69/738C07C69/73B01J31/0237B01J31/0242B01J31/04B01J31/1805B01J31/2234B01J31/2295B01J31/2404B01J2531/821B01J2531/822B01J2531/827C07C2601/08C07C2601/14C07C2602/10Y02P20/584C07C47/02C07C47/19C07C47/198C07C47/23C07C69/716C07C49/403C07C49/175C07C49/213C07C49/215C07C49/427B01J23/462B01J23/464B01J23/468
Inventor 周有桂于明袁金桃赵雷朱先冬余光雄苏伟伟邵卫康石兴兴张印丰明陈志荣李浩然张玉红
Owner ZHEJIANG NHU CO LTD
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