Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof

A technology of phosphine ligands and macrocyclic amines, which is applied in the field of chiral macrocyclic phosphine amine ligands and its preparation, can solve the problems of low optical purity, improve enantioselectivity, improve stability and rigidity, and facilitate operation Effect

Inactive Publication Date: 2011-06-15
XIAMEN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But the optical purity of the corresponding

Method used

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  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof
  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof
  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof

Examples

Experimental program
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Example Embodiment

[0030] Example 1: Chiral cyclic P 2 N 4 Preparation of phosphine imine ligand (compound (R, R, R’, R’)-2)

[0031] The chiral cyclic P is given below 2 N 4 Synthetic route of type imine phosphine ligand (compound (R, R, R’, R’)-2):

[0032]

[0033] Add bis(2-formylphenyl)phenylphosphine (9.55g, 0.03mol) and (R,R)-1,2-cyclohexanediamine (3.43g, 0.03mol) into a 400mL round bottom flask, Chloroform (300 mL) was added under a nitrogen atmosphere, the reaction was stirred, and the temperature was rapidly raised to 40°C. After 3h, add anhydrous sodium sulfate (60g) and react at 40°C for 24h. Blow nitrogen to cool to room temperature. Remove sodium sulfate by filtration, wash twice with saturated aqueous ammonium chloride solution (100mL×2), then dry over anhydrous sodium sulfate, filter, evaporate the solvent under reduced pressure, recrystallize with chloroform and n-hexane to obtain yellow-green crystals (11.2 g). The crystal was analyzed by X-ray single crystal diffraction, and i...

Example Embodiment

[0038] Example 2: Chiral cyclic P 2 (NH) 4 Preparation of type amine phosphine ligand (compound (R, R, R’, R’)-3)

[0039] The chiral cyclic P is given below 2 (NH) 4 Synthetic route of type amine phosphine ligand (compound (R, R, R’, R’)-3):

[0040]

[0041] Combine (R, R, R’, R’)-2 (1.0g, 1.3mmol) and NaBH 4 (1.0g, 26.3mmol) was added to a 150mL three-necked flask, ethanol (50mL) was added under a nitrogen atmosphere, the temperature was raised to 40°C, and the reaction was stirred at this temperature for 12h to stop the reaction. After cooling to room temperature with nitrogen gas, it was extracted with dichloromethane (150 mL), and then washed with distilled water (120 mL×3 in common). It was then dried over anhydrous sodium sulfate, filtered, and evaporated to remove the solvent under reduced pressure, and dried under vacuum to obtain a milky white solid (R, R, R', R')-3 (0.80 g, yield 80%). Melting point: 191~193°C. 1 H NMR(400MHz, CDCl 3 ): δ 0.80-0.96 (m, 2H), 0.98-1.39 (...

Example Embodiment

[0046] Example 3

[0047] Compound (R, R, R’, R’)-3 is used as a chiral ligand for the asymmetric catalytic hydrogenation of ketones

[0048]

[0049] Add (R, R, R’, R’)-3(8.0mg, 0.01mmol), RhH(CO)(PPh 3 ) 3 (9.2mg, 0.01mmol) and NH 4 I (22.0mg, 0.15mmol) was added to the reaction tube, 20ml isopropanol was added in the air, after stirring for 30min at room temperature, 0.2M KOH / i PrOH solution (115ml, 0.23mmol), after stirring for 10min, then acetophenone (0.234ml, 2.0mmol) was added. That is, the molar ratio of each material added is ketone: Rh: ligand: NH 4 I:KOH=200:1:1:1:15:23. The mixed solution was stirred and reacted at 65°C for 3 hours. The reaction solution was analyzed by gas chromatography (chiral column: CP-Cyclodextrin-β-2,3,6-M-19,50m), the chemical yield and optical purity of the product (S)-phenylethanol were 97% and 86%ee.

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Abstract

The invention relates to a chiral macrocyclic aminophosphine ligand, in particular to a chiral macrocyclic aminophosphine ligand, and a preparation method and application thereof. (R,R,R',R')-2 is prepared by reacting di(2-formacylphenyl)phenylphosphine with (R,R)-cyclohexyl-1,2-diamine in the presence of a halogenated hydrocarbon and a dehydrating agent. (R,R,R',R')-3 is prepared by reacting the(R,R,R',R')-2 with NaBH4 in a solvent. (S,S,S',S')-4 is prepared by reacting the di(2-formacylphenyl)phenylphosphine with (S,S)-cyclohexyl-1,2-diamine in the presence of a halogenated hydrocarbon anda dehydrating agent. (S,S,S',S')-5 is prepared by reacting (S,S,S',S')-4 with NaBH4 in a solvent. The chiral cyclic aminophosphine ligand can be used for preparing catalysts of chiral aromatic alcohols.

Description

technical field [0001] The invention relates to a chiral macrocyclic phosphine amine ligand, in particular to a chiral macrocyclic phosphine amine ligand used in the field of asymmetric catalytic synthesis, a preparation method and application thereof. Background technique [0002] Since the two isomers [(R)-isomer and (S)-isomer] in the chiral drug molecule have different molecular recognition in the organism, there are significant differences in their pharmacological activity, metabolic process and toxicity , or even on the contrary, so how to obtain a single enantiomerically pure compound is a great challenge to chemists and the pharmaceutical industry. [0003] Asymmetric catalytic synthesis is one of the most efficient and important ways to prepare single enantiomer compounds. It only uses a small amount of chiral catalyst to generate a large amount of optically active products. Chiral catalysts usually consist of a metal center and a chiral ligand. The metal center e...

Claims

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Application Information

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IPC IPC(8): C07F9/50C07C33/22C07C29/143C07C33/34C07C33/46C07D333/16
Inventor 高景星沈伟艺李岩云董振荣余神銮
Owner XIAMEN UNIV
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