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C2 axisymmetric chiral bisoxazoline ligand compound containing imidazole salt ion pair group, and preparation and application thereof

A ligand compound, bisoxazoline technology, applied in the field of chiral bisoxazoline ligands, can solve problems such as unsatisfactory enantioselectivity and recyclability, and achieve easy preparation, good catalytic performance, selectivity Good results

Inactive Publication Date: 2011-05-04
BEIJING INSTITUTE OF TECHNOLOGYGY +1
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to solve the disadvantages of unsatisfactory enantioselectivity and recyclability when traditional bisoxazoline ligands are used as catalysts, and provide a kind of imidazolium salt-containing ion pair group C with high catalytic efficiency. 2 Axisymmetric chiral bisoxazoline compounds and their preparation and application

Method used

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  • C2 axisymmetric chiral bisoxazoline ligand compound containing imidazole salt ion pair group, and preparation and application thereof
  • C2 axisymmetric chiral bisoxazoline ligand compound containing imidazole salt ion pair group, and preparation and application thereof
  • C2 axisymmetric chiral bisoxazoline ligand compound containing imidazole salt ion pair group, and preparation and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0052] 5,5'-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]-1,9-bis-(1,2-dimethylimidazole)nonane p-toluenesulfonate Salt synthesis:

[0053] (1) Add 1.00g (3.25mmol) 5,5'-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]methane in 20ml of anhydrous under the protection of inert gas 4.48ml (2.90M, 2.00eq) n-butyllithium was added dropwise, and reacted for 1h under ice bath, and 1-iodo-4-tert-butyl was slowly added dropwise 3.68g (11.7mmol, 3.60eq) of dimethylsiloxybutane, the temperature was raised naturally after the dropwise addition, and the reaction was carried out for 12h. The reaction was stopped, quenched by adding water dropwise, the reaction solution was extracted 3 times with dichloromethane, the extract was washed 3 times with saturated brine and water respectively, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure, and the oily residue was washed with silica gel Purification by column chromatography (eluent petroleum ether / ethyl acetate 10:1) gav...

Embodiment 2

[0061] 5,5'-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]-1,9-bis-(1,2-dimethylimidazolium)nonane hexafluorophosphate Synthesis of salt:

[0062] The compound 5,5'-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]-1,9-bis-(1,2-dimethyl Imidazole)-nonane p-toluenesulfonate (0.292g, 0.300mmol) was dissolved in water (2ml), and a solution of potassium hexafluorophosphate (0.22g, 1.10mmol) in water (2ml) was added, stirred at room temperature for 6h, and the solution A white solid precipitated out in , filtered, washed the filter cake with water, and dried in vacuo to obtain 5,5'-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]-1,9-di- (1,2-dimethylimidazole)-nonane hexafluorophosphate 0.25 g, yield 86.2%. [α] D 20 =49.3(0.08, CH 3 OH), 1 H NMR (400MHz, DMSO-d 6 ): δ: 7.61~7.57(m, 4H), 7.44~7.26(m, 10H), 5.25~5.22(m, 2H), 4.66(t, J=8Hz, 2H), 4.16~4.07(m, 6H) , 3.73~3.69(m, 6H), 2.65(s, 6H), 2.20~2.08(m, 4H), 1.80~1.76(m, 4H), 1.43~1.41(m, 4H). 13 CNMR (100MHz, DMSO-d 6 ): δ: 169.43, 142.32, 139.31, 128.8...

Embodiment 3

[0064] 5,5′-bis[(4R)-4-tert-butyl-1,3-oxazolin-2-yl]-1,9-bis(1,2-dimethylimidazole)nonane-p-toluenesulfonate Salt preparation

[0065] (1) Replace 5,5'-bis[(4S) in Example 1 with 5,5'-bis[(4R)-4-tert-butyl-1,3-oxazolin-2-yl]methane -4-phenyl-1,3-oxazolin-2-yl] methane, all the other conditions are the same as in Example 1 (1) step, to obtain 5,5'-bis[(4R)-4-tert-butyl- 1,3-oxazolin-2-yl]-1,9-bis(tert-butyl-dimethyl-siloxy)nonane, yield 70.8%. [α] D 20 =-92.3 (c=0.15, MeOH). 1 H NMR (400MHz, CDCl 3 ): δ: 4.11~4.07(dd, J=8.4Hz and 1.6Hz, 2H), 4.02~3.98(dd, J=8.4Hz and 1.6Hz, 2H), 3.86~3.81(t, J=6.4Hz, 2H ), 3.59~3.56(m, 2H), 2.03~2.00(m, 2H), 1.98~1.87(m, 4H), 1.55~1.48(m, 8H), 1.30~1.22(m, 36H), 0.02(s , 18H). 13 C NMR (100MHz, CDCl 3 ): δ: 167.44, 75.62, 68.6, 63.2, 46.2, 34.3, 33.4, 32.8, 26.1, 20.6, 20.7, -5.0. ESI-MS (m / z) = 639.5M+1 + .Anal.Calc.for C 35 h 70 N 2 o 4 Si 2 : C, 65.77; H, 11.04; N, 4.38, Found: C, 65.75; H, 11.10; N, 4.32.

[0066] (2) 5,5'-b...

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Abstract

The invention relates to a C2 axisymmetric chiral bisoxazoline ligand compound containing an imidazole salt ion pair group, and preparation and application thereof. The structural general formula of the compound is disclosed in the specification. The process of the preparation method of the compound is disclosed in the specification. The compound can be made into a copper, zinc, magnesium, ferrum or nickel complex catalyst, and used for catalyzing asymmetric Diels-Alder reaction and asymmetric Henry reaction. The compound is easy to prepare, has favorable catalytic performance and recovery performance, and can react with metals to form a complex chiral catalyst; and the catalyst has high activity and selectivity, and the activity and selectivity do not degrade after the catalyst is recovered fifteen times.

Description

technical field [0001] The present invention specifically relates to a kind of imidazolium salt-containing ion pair group C 2 The axisymmetric chiral bisoxazoline ligand, its preparation and application in catalysis belong to the technical field of chiral ligand, synthesis and application in organic synthesis. Background technique [0002] In recent years, chiral bisoxazoline metal complexes have received extensive attention due to their good catalytic effects in various asymmetric reactions. Chiral bisoxazoline metal ligands have been widely used in many asymmetric reactions are very effective catalysts (Desimoni, G.; Faita, G.; K.A.; Chem. Rev. 2006, 106, 3561.). Chiral bisoxazoline ligands have good asymmetric catalytic effects in asymmetric cyclopropanation, Diels-Alder reaction, Henry reaction, Ene reaction, allyl alkylation reaction, aldol condensation reaction, etc. , but the catalyst is difficult to extract and separate after the catalytic reaction, which makes i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D413/14B01J31/22C07B53/00
Inventor 周智明郝小燕李鑫
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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