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Chiral rare earth complex and preparation method and application thereof

A rare earth complex and complex technology, applied in the preparation of imino compounds, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., can solve the problem of few successful examples of asymmetric catalysis, etc. Achieve the effect of fast catalytic reaction, convenient preparation and high activity

Inactive Publication Date: 2015-07-22
JILIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the catalysis of intramolecular hydroamination and cyclization reactions has been widely studied, from the first main group of lithium to the alkaline earth metal calcium to the eighth transition metal subgroup of iron, there are not many successful examples of asymmetric catalysis.

Method used

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  • Chiral rare earth complex and preparation method and application thereof
  • Chiral rare earth complex and preparation method and application thereof
  • Chiral rare earth complex and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Embodiment 1 prepares rare earth complex 1

[0036]

[0037] At -78°C, butyllithium hexane solution (1.0mL, 2.00mmol) was slowly added dropwise to ligand (0.3485g, 1.00mmol) in 30mL tetrahydrofuran solution, and after low temperature reaction for 1 hour, added YCl 3 (THF) 3.5 (0.4476g, 1.00mmol), naturally warmed to room temperature and continued to react for 4 hours, cooled to -78°C, slowly added dropwise a hexane solution of butyllithium (0.5mL, 1.00mmol), and naturally warmed to -10°C to react After 0.5 h, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.26 g of bright yellow crystal complex 1 with a yield of 47%. Elemental analysis, its molecular formula is C 30 h 43 N 4 OY (%): C, 63.82; H, 7.68; N, 9.92; O, 2.83; Y, 15.75.

Embodiment 2

[0038] Embodiment 2 prepares rare earth complex 2

[0039]

[0040] At -78°C, slowly add butyllithium hexane solution (1.0mL, 2.00mmol) dropwise to ligand (0.4046g, 1.00mmol) in 30mL tetrahydrofuran solution, and add YCl 3 (THF) 3.5 (0.4476g, 1.00mmol), naturally warmed to room temperature and continued to react for 4 hours, cooled to -78°C, slowly added dropwise a hexane solution of butyllithium (0.5mL, 1.00mmol), and naturally warmed to -10°C to react After 1 h, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.28 g of bright yellow crystals of complex 2 with a yield of 45%. Elemental analysis, its molecular formula is C 34 h 51 N 4 OY (%): C, 65.79; H, 8.28; N, 9.03; O, 2.58; Y, 14.32.

Embodiment 3

[0041] Embodiment 3 prepares rare earth complex 3

[0042]

[0043] At -78°C, slowly add butyllithium hexane solution (1.0mL, 2.00mmol) dropwise to ligand (0.4326g, 1.00mmol) in 30mL tetrahydrofuran solution, and add YCl 3 (THF) 3.5 (0.4476g, 1.00mmol), naturally warmed to room temperature and continued to react for 5 hours, cooled to -78°C, slowly added dropwise a hexane solution of butyllithium (0.5mL, 1.00mmol), naturally warmed to 10°C and reacted for 0.5 h, the solvent was removed in vacuo, the residue was extracted with toluene, and the toluene solution was concentrated to obtain 0.37 g of bright yellow crystal complex 3 with a yield of 44%. Elemental analysis, its molecular formula is C 44 h 71 ClLiN 4 o 3 Y (%): C, 63.26; H, 8.57; Cl, ​​4.24; Li, 0.83; N, 6.71; O, 5.75;

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Abstract

The invention discloses a chiral rare earth complex and a preparation method and application thereof, and belongs to the technical field of catalysts. The chiral rare earth complex is [NNNN]2<-> coordinated rare earth metal complex, and a complex system I and a complex system II are specifically provided. The chiral rare earth complex is prepared by mainly using chiral four-tooth amine-imine ligand or chiral tetrazo ligand and rare earth trichloride or rare earth triallyl compound as reactants. The chiral rare earth complex is used as a catalyst for catalyzing asymmetrical hydrogen amination cyclization reaction in enamine molecules. The chiral rare earth complex serving as a catalyst raw material is easily obtained and conveniently prepared with simple steps. The catalysts have high activity, low consumption, high catalytic reaction speed and high conversion rate, and the highest enantiomeric excess (ee) value of the catalysts can reach 100 percent. The systems formed by the catalysts are homogeneous and convenient to use.

Description

technical field [0001] The invention belongs to the technical field of catalysts, in particular to a chiral rare earth complex catalyst, which is used to catalyze intramolecular asymmetric hydrogenation. Background technique [0002] Hydroamination is a reaction that formally adds nitrogen-hydrogen bonds to carbon-carbon unsaturated bonds. The utilization rate of atoms is 100%, which is a kind of reaction conforming to atom economy and green chemistry. It is an important method for regioselective formation of carbon-nitrogen bonds and a very important transformation process in chemistry and biology. Especially since nitrogen-containing compounds almost cover most of the pharmaceutical compounds and many organic molecules with biological activity, they have attracted widespread attention both in the field of academic research and in industrial production. [0003] At present, the asymmetric synthesis of a large number of nitrogen-containing compounds is realized by using tra...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/00C07F19/00C07C251/24C07C249/02B01J31/22C07D207/06C07D209/54C07D211/12
Inventor 母瀛张彦雨姚伟
Owner JILIN UNIV