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Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction

A proline, methylene technology, applied in physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, carbon-based compound preparation and other directions, can solve the problem of low catalytic efficiency, low product yield, The problem of large amount of catalyst is to achieve the effect of high catalytic efficiency, high yield and large-scale production.

Inactive Publication Date: 2015-12-23
SHANGHAI INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] Aiming at the above-mentioned technical problems in the above-mentioned prior art, the present invention provides the application of 4,5-methylene-L-proline as a catalyst in the direct asymmetric Aldol reaction, which solves the problems of the prior art In the Aldol reaction, the amount of catalyst used is large, the catalytic efficiency is low, and the technical problems of low product yield

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  • Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction
  • Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction
  • Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction

Examples

Experimental program
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Effect test

Embodiment 1

[0031] In this example, acetone and p-nitrobenzaldehyde are used as substrates, and trans-4,5-methylene-L-proline (I), cis-4,5-methylene-L-proline The activity of direct asymmetric Aldol reaction catalyzed by amino acid (Ⅱ) and L-proline was confirmed.

[0032] Experimental method: Add 4,5-methylene-L-proline catalyst or L-proline catalyst (0.15mmol), DMF (1mL) and acetone (2.5mmol) into the reactor, drop p-Nitrobenzaldehyde (0.5mmol), TLC tracking to the complete consumption of reaction raw materials, after the completion of the reaction, add saturated NH 4 Cl solution, extracted with ethyl acetate, anhydrous Na 2 SO 4 Dry, filter, remove the solvent under reduced pressure, and separate by thin layer chromatography (ethyl acetate / n-hexane is the developing solvent) acetone and Aldol products of p-nitrobenzaldehyde. The enantiomeric excess (ee value) was determined by chiral high pressure liquid chromatography analysis of the pure product.

[0033] The results are shown in...

Embodiment 2

[0038] In this example, using acetone and p-nitrobenzaldehyde as substrates, the amount of catalyst and different additives in the direct asymmetric Aldol reaction catalyzed by trans-4,5-methylene-L-proline (I) system research.

[0039] Experimental method: Add 4,5-methylene-L-proline catalyst (0.15mmol), DMF (1mL), additives and acetone (2.5mmol) into the reactor, add p-nitrobenzaldehyde dropwise at 0°C (0.5mmol), TLC traces to the complete consumption of reaction raw materials, after the completion of the reaction, add saturated NH 4 Cl solution, extracted with ethyl acetate, anhydrous Na 2 SO 4 Dry, filter, remove the solvent under reduced pressure, and separate by thin layer chromatography (ethyl acetate / n-hexane is the developing solvent) acetone and Aldol products of p-nitrobenzaldehyde. The enantiomeric excess (ee value) was determined by chiral high pressure liquid chromatography analysis of the pure product.

[0040] The results are shown in Table 2. It can be see...

Embodiment 3

[0046] This embodiment uses acetone and p-nitrobenzaldehyde as substrates, referring to the experimental method of Example 2, for the direct asymmetric Aldol reaction catalyzed by trans-4,5-methylene-L-proline (I) The main influencing factors such as solvent, reaction temperature and reaction time were systematically studied.

[0047] The results are shown in Table 3. It can be seen that when the solvent is DMF and the reaction temperature is -20°C, the yield and enantioselectivity are higher.

[0048]

[0049] Table 3 Effect of solvent and temperature on the direct asymmetric Aldol reaction catalyzed by trans-4,5-methylene-L-proline (Ⅰ)

[0050]

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Abstract

The invention provides an application of 4,5-methylene-L-proline as a catalyst in a direct asymmetric Aldol reaction. The invention further provides a method for carrying out the direct asymmetric Aldol reaction through catalysis of 4,5-methylene-L-proline. Acetone, aldehyde and 4,5-methylene-L-proline are weighed out, the direct asymmetric Aldol reaction happens to acetone and aldehyde, and direct asymmetric Aldol reaction products of acetone and aldehyde are generated. 4,5-methylene-L-proline is adopted as the chiral catalyst, and the direct asymmetric Aldol reaction of acetone and aldehyde is catalyzed. Compared with L-proline, the application has the advantages that the catalyst is high in catalytic efficiency, the products with the high yield and high enantioselectivity can be obtained, and 4,5-methylene-L-proline is economical and environmentally friendly, and large-scale production can be achieved easily.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a catalyst, specifically the application of 4,5-methylene-L-proline as a catalyst in direct asymmetric Aldol reaction. Background technique [0002] The Aldol reaction is considered to be one of the most useful C-C bond-forming reactions and is widely used in the synthesis of many complex natural or unnatural organic compounds. In particular, the direct asymmetric Aldol reaction between molecules is an important method for the synthesis of chiral drug intermediates. [0003] List et al. (J.Am.Chem.Soc.2000,122,2395-2396) reported the first proline-catalyzed intermolecular asymmetric direct Aldol reaction using acetone and p-nitrobenzaldehyde as models. [0004] This field has developed rapidly in recent years, and many research groups (R.Reddy, D.Magar, Chem.Eur.J.2010, 16, 7030; F.Giacalone, M.Gruttadauria, Eur.J.Org.Chem. 2010, 5696; G. Pousse, J. Rouden, Org. Let...

Claims

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Application Information

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IPC IPC(8): B01J31/04C07C201/12C07C205/45C07C45/72C07C49/245C07D307/12
Inventor 余焓于娜祝俊韩生张兴华
Owner SHANGHAI INSTITUTE OF TECHNOLOGY