Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof

A technology for small molecules and heteropolyacids, which is applied in the field of chiral small molecule catalysts and their preparation, can solve the problems of reduced activity and selectivity, reduced activity, and cumbersome catalyst preparation.

Inactive Publication Date: 2010-12-08
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Catalyst preparation in the first mode is often cumbersome, and compared with unloaded small molecule catalysts, the activity and selectivity of supported catalysts are reduced to a greater extent (Cozzi, F.Adv.Synth.Catal.2006 , 348, 1367-1390. Luo, S.Z.; Peng, Y.Y.; Zhang, B.L.; Wang, P.G.; Cheng, J.-P.Curr.Org.Synth.2004, 1, 405-429.)
Catalyst preparation is relatively simple in the second mode, but the problem of activity and selectivity has not been well resolved (Kucherenko, A.S.; Struchkova, M.I.; Zlotin, S.G.Eur.J.OrgChem.2006, 2000.Gruttadauria, M. ; Riela, S.; Aprile, C.; Lo Meo, P.; D'Anna, F.; Noto, R. Adv. Synth. Catal. 2006, 348, 82. Gotov, B.; Toma, S.; Solcaniova, E. Chem. Commun. 2002, 2510.)
The activity of immobilized organic small molecule catalysts tends to further decrease and the dosage increases, resulting in a smaller amount of substrate / catalyst (S / C ratio) or even tends to 1, and the preparation cost of most immobilized catalysts far exceeds that of simple precursors molecular

Method used

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  • Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof
  • Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof
  • Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0060] Embodiment 1: synthetic A 1 -1

[0061]

[0062] N 2 Under cooling in a protective ice bath, slowly add 10.6 g of DCC (56.4 mmol) in 20 mL of dichloromethane solution in 30 mL of dichloromethane solution dissolved with 12.7 g (51.3 mmol) of N-Z protected proline, and stir for 30 minutes. Then slowly add dichloromethane solution containing 3.75 g (51.3 mmol) diethylamine dropwise, react at room temperature for 12 hours, add a small amount of water to consume excess DCC, filter to remove the white solid generated, and the filtrate is successively washed with 2% hydrochloric acid 20mL, 4% Wash with 20 mL of sodium bicarbonate, 20 mL of saturated saline, and 20 mL of distilled water, dry over anhydrous sodium sulfate, spin off the solvent, separate by column chromatography to obtain 7.5 g of a colorless viscous liquid, add it to a dry two-necked bottle, and add 0.4 g of Pd / C catalyst, pump vacuum, inject 30mL of anhydrous methanol, feed 10 atmospheres of hydrogen, rea...

Embodiment 2

[0064] Embodiment 2: synthetic A 1 -4

[0065]

[0066] Proline is amino-protected with Z-Cl, N-Z-protected proline B is condensed with hexahydropyridine under DCC to generate N-Z-protected prolinamide C, and H is catalyzed by Pd / C 2 Reduction deprotection of Z, the obtained compound D with LiA1H 4 Reduction to obtain small organic molecule A 1 -4.

[0067] Concrete synthetic steps are as follows:

[0068] N 2 Under cooling in a protective ice bath, slowly add 10.6 g of DCC (56.4 mmol) in 20 mL of dichloromethane solution in 30 mL of dichloromethane solution dissolved with 12.7 g (51.3 mmol) of N-Z protected proline B, and stir for 30 minutes , then slowly add dropwise a dichloromethane solution containing 4.36 grams (51.3 mmol) of hexahydropyridine, react at room temperature for 12 hours, add a small amount of water to consume excess DCC, filter and remove the white solid generated, and the filtrate is successively washed with 2% hydrochloric acid 20mL, 4 Wash with 2...

Embodiment 3

[0074] Embodiment 3: Synthesis A 1 -9

[0075]

[0076] E F

[0077] Using hydroxyproline as a raw material, through N-Boc protection and O-benzylation, E is obtained; E is condensed with diethylamine under the action of DCC in dichloromethane solvent to obtain compound F, and F is sequentially desorbed under acidic conditions. In addition to Boc protecting group and LiAlH 4 Reduction, to obtain small organic molecule A 1 -9.

[0078] Concrete synthetic steps are as follows:

[0079] Add 9.42 grams of E (30 mmol) to a 100 mL dry single-necked bottle, add 15 mL of dichloromethane to dissolve it, slowly add 15 mL of dichloromethane solution containing 6.49 grams (31.5 mmol) of DCC dropwise under ice bath, and react for 30 minutes after the addition is complete , slowly dropwise add 20mL dichloromethane solution containing 2.19 grams (30mmol) of diethylamine, it takes about 1 hour, after the addition is completed, it rises to room temperature, reacts...

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Abstract

The invention discloses a chiral small organic molecule catalyst loaded by heteropoly acid and the preparation and the application thereof. Chiral small organic molecule catalyst A is loaded on heteropoly acid POM through acid and alkali ion pairs, and the catalyst can be represented as n(POM), wherein n can be 3, 4 or 6. The invention creatively provides a small organic molecule catalyst loadmode, i.e. noncovalent load mode, the chiral small organic molecule and the solid heteropoly acid are adopted to form an organic-inorganic macromolecule catalyst assembly through acid-base effect, the small organic molecule in the assembly acts as the active and chiral induction center of the catalyst, the heteropoly acid is not only the carrier of the catalyst, but also the indispensable important component of the catalyst. The loaded catalyst has the advantages of simple preparation, biphasic catalysis property, high activity and good selectivity of homogencous catalyst, and conveniently realized recovery and cyclic utilization.

Description

technical field [0001] The invention relates to a catalyst and its preparation method and application, in particular to a heteropolyacid-supported chiral small molecule catalyst, its preparation method and application. Background technique [0002] Since 2000, asymmetric organic small molecule catalysts represented by proline have developed rapidly, becoming the third important asymmetric synthesis catalyst after transition metal catalysts and biological enzyme catalysts (Dalko, P.I.; Moisan, L 2004, 43, 5138. Berkessel, A.; Groger, H. Asymmetric Organocatalysis, Wiley-VCH, Weinheim, 2005. List, B.; Yang, J.W.Science 2006, 313, 1584), Common asymmetric organic small molecule catalysts are shown in formula I. Compared with chiral transition metal catalysts and enzyme catalysts, organic small molecule catalysts have remarkable characteristics such as simple structure, easy preparation, mild reaction conditions and no metal pollution. [0003] [0004] Formula I [0005] ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B53/00B01J31/02
Inventor 罗三中李九远徐辉张龙程津培
Owner INST OF CHEM CHINESE ACAD OF SCI
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