Dual functions ligand compound of chirality dioxazoline, preparation and application

A ligand compound, bisoxazoline technology, applied in organic compound/hydride/coordination complex catalysts, chemical/physical processes, organic chemistry, etc., can solve bifunctional chiral bisoxazoline ligand reports There are few problems, such as few reports on the application of cyanosilylation reaction, etc., to achieve the effect of easy acquisition, easy preparation and good selectivity.

Inactive Publication Date: 2005-06-15
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The design, synthesis and asymmetric catalysis of new chiral bisoxazoline ligands have aroused great interest of many scientists, although these ligands are in asymmetric cyclopropanation reaction, Diels-Alder reaction, allyl alkylation reaction, hydrogen Good asymmetric catalytic effects have been ach

Method used

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  • Dual functions ligand compound of chirality dioxazoline, preparation and application
  • Dual functions ligand compound of chirality dioxazoline, preparation and application
  • Dual functions ligand compound of chirality dioxazoline, preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Synthesis of N-(3,3-dicyanopropyl)hexahydropyridine:

[0050] Add absolute ethanol (30 mL) and sodium (1.0 g, 43.5 mmol) into a 100 mL round bottom flask, and stir for 1 h. Then malononitrile (2.75 mL, 43.3 mmol) and potassium iodide (0.6 g, 3.6 mmol) were added and stirring was continued for 0.5 h. Then N-chloroethylhexahydropyridine hydrochloride (8.43 g, 45.8 mmol) was added and the reaction mixture was refluxed for 24 h. Water (10 mL) was added to the reactant, and extracted with chloroform (20 ml×2). The combined organic layers were washed with anhydrous Na 2 SO 4 After drying and concentrating, the crude product was obtained. Silica gel column chromatography (petroleum ether / chloroform 1:4) gave 3.82 g of N-(3,3-dicyanopropyl)hexahydropyridine, with a yield of 50%. IR: 2938, 2854, 2806, 2256, 1470, 1455, 1444, 1379, 1353, 1156, 1126, 1039cm -1 ; 1 H NMR (300MHz, CDCl 3 ): δ4.18(t, J=7.3Hz, 1H), 2.53(t, J=7.1Hz, 2H), 2.39(s, 4H), 2.13-2.18(m, 4H), 1.54-1.59(...

Embodiment 2

[0052] Synthesis of 1,1-bis[(4S)-4-phenyl-1,3-oxazolin-2-yl]-3-(1-piperidinyl)propane (1a):

[0053] Add anhydrous zinc chloride (50mg, 0.37mmol) into a 100mL two-neck flask, heat to melt, and cool to room temperature under nitrogen protection. Then chlorobenzene (20ml) and N-(3,3-dicyanopropyl)piperidine (0.55g, 3.1mmol) and L-phenylglycinol (0.93g, 6.82mmol) were added, and the mixture was refluxed for 24h. The solvent was distilled off under reduced pressure to obtain an oil, to which dichloromethane (20 mL) was added. The solution was extracted with water (20 mL×3), and the aqueous phase was extracted with dichloromethane (20 ml). The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the oily residue was purified by silica gel column chromatography (eluent petroleum ether / chloroform 4:1) to obtain 1,1-bis[(4S)-4-phenyl-1,3-oxazoline -2-yl]-3-(1-piperidinyl)propane 0.59 g (46%). [α] D 20 = -...

Embodiment 3

[0055] Synthesis of 1,1-bis[(4S)-4-isobutyl-1,3-oxazolin-2-yl]-3-(1-piperidinyl)propane (1a):

[0056] Replace the L-phenylglycine alcohol in the embodiment two with L-leucinol, all the other are the same as the embodiment two, obtain 1,1-bis[(4S)-4-isobutyl-1,3-oxazoline- 2-yl]-3-(1-piperidinyl)propane, yield 48%.[α] D 20 = -30.3° (c0.7, CH 3 Oh)

[0057] IR: 2956, 2870, 1749, 1656, 1542, 1468, 1367, 1256, 1067cm -1 . 1 H NMR (CDCl 3 ): δ4.21-4.27(m, 2H), 4.02-4.07(m, 2H), 3.72-3.78(m, 2H), 3.36-3.40(t, J=7.1Hz, 1H), 2.20-2.29(m , 4H), 1.98-2.03(m, 2H), 1.61-1.65(m, 2H), 1.47-1.52(m, 6H), 1.32(m, 2H), 1.15-1.22(m, 2H), 0.81-0.85 (m, 12H). 13 C NMR (50MHz, CDCl 3 ): 22.53, 22.59, 22.78, 22.83, 24.34, 25.24, 25.88, 26.91, 37.69, 45.30, 45.39, 54.41, 56.50, 64.43, 64.47, 73.15, 73.25, 164.37, 164.42. MS (EI): 37 + , 2), 279(35), 249(12), 209(20), 168(18), 98(100).

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Abstract

A bifunctional chiral bioxazoline ligand used as the catalyst for asymmetrical reactions, such as cyanosiliconizing reaction, is prepared from propylbinitrile or its derivative through substitution reaction and cyclizing reaction on chiral aminoalcohol, or from the bioxazoline methane through substitution reaction.

Description

Technical field: [0001] The invention belongs to the technical field of organic compounds and asymmetric synthesis, and specifically relates to a bifunctional chiral bisoxazoline ligand compound with good catalytic performance and its preparation and application. Background technique: [0002] Oxazolines and their derivatives are very important intermediates in organic synthesis, and are widely used in the fields of medicine, pesticides and materials science. In recent years, chiral bisoxazoline ligands with different structural types have emerged, and chiral bisoxazoline metal complexes have attracted extensive attention due to their good catalytic effects in various asymmetric reactions. (Ghosh, A.K.; Mathivanan, P.; Cappiello, J. Tetrahedron: Asymmetry 1998, 9, 1.; Johnson, J.S.; Evas, D.A. Acc. Chem. Res. 2000, 33, 325.). The chirality in chiral bisoxazoline ligands comes from a variety of very readily available natural and unnatural optically active amino acids or chir...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07D263/14
Inventor 杜大明罗梅吕少峰
Owner PEKING UNIV
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