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Method for asymmetric Michael addition under catalysis action of efficient supported catalyst

A catalyst and addition technology, applied in asymmetric synthesis, organic chemistry methods, chemical instruments and methods, etc., can solve the problems of difficult recovery of catalysts, large toxic and harmful solvents, etc.

Active Publication Date: 2015-05-13
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above method has defects such as the use of a large amount of toxic and harmful solvents, and the difficulty of using catalysts for recovery and application.

Method used

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  • Method for asymmetric Michael addition under catalysis action of efficient supported catalyst
  • Method for asymmetric Michael addition under catalysis action of efficient supported catalyst
  • Method for asymmetric Michael addition under catalysis action of efficient supported catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Take nitrostyrene (0.2mmol, 29.8mg), isobutyraldehyde (1mmol, 0.91mL) in a 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), Magnetic stirring was carried out at room temperature for 4 h, and the reaction progress was detected by TLC. After the reaction, it was extracted several times with ethyl acetate, the organic phases were combined, and passed through the column by wet method (eluent: petroleum ether: ethyl acetate = 5:1). product through 1 H NMR and HPLC analysis, yield 87%.

[0024] (R)-2,2-Dimethyl-4-nitro-3-phenylbutanal: The ee was determined by HPLC with Chiralpak OD-H column at 210nm(hexane / i-PrOH=80:20, flow rate 0.5mL / min, 20℃).t R (major)=31.8min,t R (minor)=38.5min, ee=97%. 1 H NMR (400MHz, CDCl 3 ):δ9.55(s,1H),7.31-7.37(m,3H),7.21-7.23(m,2H),4.85-4.91(m,1H),4.69-4.74(m,1H),3.79-3.83 (m,1H),1.15(s,3H),1.02(s,3H).

Embodiment 2

[0026] Take nitrostyrene (0.2mmol, 29.8mg), isobutyraldehyde (1mmol, 0.91mL) in a 5mL flask, add catalyst (0.03mmol, 23mg), DMAP (0.04mmol, 4.9mg), water (1mL), Magnetic stirring was carried out at room temperature for 7 h, and the reaction progress was detected by TLC. After the reaction, it was extracted several times with ethyl acetate, the organic phases were combined, and passed through the column by wet method (eluent: petroleum ether: ethyl acetate = 5:1). product through 1 H NMR and HPLC analysis, yield 83%, ee=97%.

Embodiment 3

[0028] Take nitrostyrene (0.2mmol, 29.8mg), isobutyraldehyde (2mmol, 0.91mL) in a 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), Magnetic stirring was carried out at room temperature for 4 h, and the reaction progress was detected by TLC. After the reaction, it was extracted several times with ethyl acetate, the organic phases were combined, and passed through the column by wet method (eluent: petroleum ether: ethyl acetate = 5:1). product through 1H NMR and HPLC analysis, yield 86%, ee=98%.

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Abstract

The invention relates to a method for asymmetric Michael addition of isobutyraldehyde and nitroolefin under the indoor temperature reaction conditions by adopting an efficient and environment-friendly chiral supported catalyst and a water solvent. The method comprises steps as follows: superparamagnetic nanoparticle supported and ionic atmosphere modified chiral micromolecules are taken as a catalyst, N, N-DMAP (dimethylaminopyridine) is taken as an accelerant, isobutyraldehyde and nitroolefin have a stereoselective Michael addition reaction under the normal pressure at the temperature of 25 DEG C, and the reaction yield and the ee value are not remarkably reduced after the supported catalyst is repeatedly used for five times. The method is simple to operate, the stereoselectivity of the catalyst is good, the recycling is simple, a catalytic reaction system has good reusability, the reaction condition is mild, and large-scale production is easy to realize.

Description

technical field [0001] The invention relates to a high-efficiency, green chiral small molecule modified with new superparamagnetic nano-loading and ion atmosphere under the condition of using water as a solvent, and N,N-lutidine (DMAP) as a catalyst Asymmetric Michael addition reaction method between isobutyraldehyde and nitroalkenes at 25°C and normal pressure. technical background [0002] Nitroalkanes play an important role in organic synthesis because of their ease of α-alkylation and conversion into other important functional groups (Czekelius C, Carreira E M. Angew. Chem. Int. Ed., 2005, 44, 612; Berner O M, Tedeschi L, Enders D. Eur. J. Org. Chem., 2002, 2002, 1877.). The conjugate addition of carbon-centered nucleophiles to nitroalkenes is the most common method for the preparation of chiral nitroalkanes. Among them, the most important one is the Michael addition reaction (Betancort J M, Barbas C F, Org. Lett., 2001, 3, 3737; Melchiorre P, K A, J. Org. Chem., 200...

Claims

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Application Information

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IPC IPC(8): C07B53/00C07C201/02C07C205/44C07D333/22B01J31/28
CPCY02P20/584
Inventor 应安国杨健国刘硕李志锋胡华南
Owner TAIZHOU UNIV