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Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde

A catalyst, aliphatic aldehyde technology, applied in the preparation of organic compounds, chemical instruments and methods, catalysts for physical/chemical processes, etc., can solve the problems of high cost, many synthesis steps, unsuitable for large-scale industrial production, etc. Enantiomeric and enantioselective, effect of accelerating reaction rate

Active Publication Date: 2012-05-09
CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

These catalysts also have many deficiencies, as the synthesis of diphenylprolinol silicon ether generally involves the use of Grignard reagents, and the reaction needs to use a large amount of benzoic acid, tripeptides relate to polypeptide solid-phase resin synthesis, 2-(2-piperone Pyridine) There are many synthetic steps of pyridine, which lead to relatively difficult catalyst preparation and high cost, and are not suitable for large-scale industrial production

Method used

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  • Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde
  • Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde
  • Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde

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preparation example Construction

[0040]The present invention also provides a preparation method of nitro fatty aldehyde, comprising: a) mixing a compound represented by formula I and a compound represented by formula II in a solvent to obtain a mixed solution;

[0041] Wherein, R is a dialkylamine group or a cycloalkylamine group; R 1 and R 3 They are hydrogen, bromine, iodine, phenyl, 2,4,6-trimethylphenyl, trimethylsilyl or triphenylsilane, respectively.

[0042] b) Mix fatty aldehyde and nitroalkene in the mixed solution and react at 0°C until the nitroalkene completely disappears;

[0043] c) Quenching the reaction with hydrochloric acid, extracting the reaction product, drying and separating by chromatography to obtain nitro fatty aldehyde.

[0044] According to the present invention, the reaction substrates are aliphatic aldehydes and nitroalkenes, and the nitroalkenes are preferably aromatic nitroalkenes or aliphatic nitroalkenes, more preferably benzene, furan, thiophene and derivatives thereof with...

Embodiment 1

[0058] Mix 0.33 g, 1.3 mmol of BOP-Cl with 0.3 g, 1.3 mmol of N-tert-butoxycarbonyl-trans-4-hydroxy-L-proline and 0.3 mL, 2.2 mmol of triethylamine in 3 mL of dichloromethane mixed in a reaction flask to obtain a suspension, and the resulting suspension was stirred for 30 minutes under an ice bath, and then 1.3mmol of hexahydropyridine and 0.15mL, 1.1mmol of triethylamine were mixed in 1mL of dichloromethane, and dropped at the same temperature into the reaction bottle. After further stirring for 16 hours, the reaction temperature was slowly raised from 0°C to room temperature, the reaction solution was filtered, the filtrate was diluted with 10 mL of dichloromethane, washed with saturated aqueous sodium bicarbonate (5 mL×2) and brine (5 mL×2), The aqueous phase was further extracted with 10 mL of dichloromethane, combined with the organic phase, dried, filtered and concentrated with anhydrous sodium sulfate to obtain the intermediate N-Boc-proline derivative, the compound sho...

Embodiment 2～10

[0063] According to Table 1 R 3 , R 4 The listed substituents select the reaction raw materials, use the method of Example 1 to prepare nitro fatty aldehyde, the yield of the obtained product is 92%-96%, and the ratio of diastereomers is greater than 95 / 5, even greater than 99 / 1 , the enantiomeric excess value is greater than 95%, even greater than 99%, these performances can all show that the catalyst provided by the present invention has higher catalytic efficiency, and the prepared nitro fatty aldehyde has better performance.

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Abstract

The invention provides a catalyst for a Michael addition reaction, which is characterized by comprising a compound shown by the formula I and a compound shown by the formula II, wherein R represents for dialkyl amino or naphthene amino; R1 and R2 respectively represent for hydrogen, bromine, iodine, phenyl, 2, 4, 6-trimethylphenyl, trimethylsilyl or triphenysilyl. The catalyst provided by the invention can be used for catalyzing fatty aldehyde and nitroolefin to perform an asymmetrical Michael addition reaction to obtain a product with high yield, high diastereomer selectivity and high enantiomer selectivity. The invention also provides a preparation method of nitro fatty aldehyde.

Description

technical field [0001] The invention relates to the field of organic compound synthesis, in particular to a catalyst for Michael addition reaction and a preparation method of nitro fatty aldehyde. Background technique [0002] The Michael addition reaction is one of the most important carbon-carbon linkage reactions in organic chemistry, and the asymmetric Michael addition of aliphatic aldehydes to nitroalkenes is a key path in the synthesis of many important organic compounds such as pharmaceutical intermediates. Since Betancort and Barbas reported the first Michael addition reaction of asymmetric aldehydes and nitroalkenes using organocatalysts, a large number of catalysts with excellent enantioselectivity have emerged, such as diphenylprolinol silyl ethers and sulfonamides. pyrrolidine etc. However, these catalysts are generally used in amounts generally greater than 5 mol%, and the aldehyde is generally in large excess (ten equivalents). Palomo et al. designed a cataly...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07B37/02C07C201/12C07C205/44C07D333/22C07D307/46C07D207/16
Inventor 成燕琴卞证康传清高连勋
Owner CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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