Chiral bidentate nitrogen-containing phosphine ligands and application thereof in asymmetric catalytic reaction

A technology of bidentate nitrogen and phosphine ligands is applied in the field of asymmetric catalysis synthesis, which can solve the problems of waste of ligands, high price, difficulty of optically pure axial chiral ligands, etc., and achieves avoidance of waste, short synthesis routes, and large industrial scale. The effect of applying value

Active Publication Date: 2017-05-10
WUHAN CATALYS TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above are some axis-stabilized ligands, these ligands have the following two limitations [11] (1) First, it is difficult and expensive to obtain optically pure axial chiral ligands; second, for axial chiral bisphosphin

Method used

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  • Chiral bidentate nitrogen-containing phosphine ligands and application thereof in asymmetric catalytic reaction
  • Chiral bidentate nitrogen-containing phosphine ligands and application thereof in asymmetric catalytic reaction
  • Chiral bidentate nitrogen-containing phosphine ligands and application thereof in asymmetric catalytic reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Synthesis of Ligand L1:

[0045]

[0046] L-phenylglycinol 1 (1.37g, 10mmol) was dissolved in 40mL of anhydrous THF, N 2 Protection, at -78°C, n-butyllithium (8mL, 2.5M n-pentane solution) was added dropwise, after the dropwise addition, stirred at -78°C for half an hour, then TBSCl (3.17g, 21.0mL) 20mL of THF solution was slowly added dropwise. After the dropwise addition was completed, it was slowly warmed to room temperature and then stirred overnight. After spinning THF away, N 2 Protection, under the condition of -78°C, add 50mL of anhydrous ether, add n-butyllithium (12mL, 2.5M n-pentane solution) dropwise, slowly rise to room temperature, stir at room temperature for 1 hour, then lower the temperature to - At 78°C, simple iodine (5.08g, 20.0mmol) was added, then raised to room temperature, and stirred at room temperature for 1 hour. After that with 10% Na 2 S 2 o 3 An aqueous solution (20 mL) was quenched, stirred for 10 minutes, extracted with ethyl ac...

Embodiment 2

[0065] Embodiment 2 Catalyst 6a catalyzes the asymmetric hydrogenation reaction of α-methylcinnamic acid:

[0066] In a glove box under an argon atmosphere, take catalyst 6a (3.6mg) and add it to a 5mL hydrogenation vial, then add the substrate α-methylcinnamic acid (32mg, 0.2mmol) and triethylamine (22mg, 0.2mmol) in sequence and 1 mL of dichloromethane. Put the hydrogenation vial into the hydrogenation reaction kettle, replace it with hydrogen three times and fill it with 30 atm H 2 , Reacted at room temperature for 4h. After the reaction was complete and hydrogen gas was released, the reaction mixture was passed through a short silica gel column. 1 The conversion rate (>99%) was determined by HNMR, and the enantioselectivity ee value (97%) of the reaction was determined by high performance liquid chromatography (HPLC).

Embodiment 3

[0067] Embodiment 3 Catalyst 6d catalyzes the asymmetric hydrogenation reaction of α-methylcinnamic acid:

[0068] In a glove box under an argon atmosphere, take catalyst 6d (3.6mg) and add it to a 5mL hydrogenation vial, then add the substrate α-methylcinnamic acid (32mg, 0.2mmol) and triethylamine (22mg, 0.2mmol) in sequence and 1 mL of dichloromethane. Put the hydrogenation vial into the hydrogenation reaction kettle, replace it with hydrogen three times and fill it with 30 atm H 2 , Reacted at room temperature for 4h. After the reaction was complete and hydrogen gas was released, the reaction mixture was passed through a short silica gel column. 1 The conversion rate (81%) was determined by HNMR, and the enantioselectivity ee value (81%) of the reaction was determined by high performance liquid chromatography (HPLC).

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Abstract

The invention relates to bidentate nitrogen-containing phosphine ligands and an application thereof in an asymmetric catalytic reaction. The novel bidentate phosphino-oxazoline ligands are ligands with biphenyl axis instability structures, and are successfully applied to efficient high-selectivity asymmetric hydrogenation of alpha-methylcinnamic acid and derivatives of alpha-methylcinnamic acid as well as similar reactions. The ligands of the type adopt a simple synthesis route, are low in cost, realize air stability, show high activity and high selectivity to the asymmetric hydrogenation of carbon-carbon double bond and have broad industrial application prospect.

Description

technical field [0001] The invention relates to a chiral bidentate nitrogen phosphine ligand and its application in asymmetric hydrogenation reaction and similar reactions, belonging to the field of asymmetric catalytic synthesis. Background technique [0002] With the increasing demand for chiral drugs, pesticides, spices and fine chemicals, asymmetric catalytic technology has achieved rapid development. The asymmetric catalytic hydrogenation of unsaturated compounds such as prochiral alkenes (C=C), ketones (C=O) and imines (C=N) has the advantages of high efficiency, high selectivity and high atom economy , has been a research hotspot in the field of asymmetric catalysis [1] . The core factor affecting the efficiency of asymmetric catalytic hydrogenation is the catalyst. The catalyst is composed of a metal center and a ligand. Due to the limitation of the periodic table of elements, the types of transition metals to choose from are limited. Therefore, the development of ...

Claims

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Application Information

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IPC IPC(8): C07F9/653B01J31/24C07B53/00C07C45/41C07C47/232
CPCB01J31/24C07B53/00C07C45/41C07F9/653C07C47/232
Inventor 张绪穆王茜董秀琴
Owner WUHAN CATALYS TECH CO LTD
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