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Application of a Chiral Tridentate Phosphine Nitrogen Oxygen Ligand and Its Related Ligands in Asymmetric Catalytic Reactions

An asymmetric reaction technology, applied in catalytic reactions, organic compound/hydride/coordination complex catalysts, preparation of organic compounds, etc., can solve the problems of complex and expensive ligand synthesis, and achieve easy purification, Strong nucleophilicity, suitable for large-scale synthesis and preparation

Active Publication Date: 2019-05-24
WUHAN CATALYS TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2011, Professor Zhou Qilin added an additional pyridine coordination group to the chiral spirocyclic phosphine amine ligand SpiroAP, and the obtained SpiroPAP ligand showed super high activity for the asymmetric hydrogenation reaction of simple ketones [12] , but the synthesis of the ligand is complex and expensive
In 2013, Professor Zhang Shengyong designed and synthesized a class of ferrocene-based chiral tridentate ligands based on SpiroPAP ligands. This ligand showed high activity in the asymmetric hydrogenation of aromatic ketones, but only obtained medium ee value [13]

Method used

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  • Application of a Chiral Tridentate Phosphine Nitrogen Oxygen Ligand and Its Related Ligands in Asymmetric Catalytic Reactions
  • Application of a Chiral Tridentate Phosphine Nitrogen Oxygen Ligand and Its Related Ligands in Asymmetric Catalytic Reactions
  • Application of a Chiral Tridentate Phosphine Nitrogen Oxygen Ligand and Its Related Ligands in Asymmetric Catalytic Reactions

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Synthesis of ligand L4:

[0058]

[0059] (S)-Ugi-amine 1 (2.57g, 10mmol) dissolved in 20mL of anhydrous ether, N 2 Protected, tert-butyllithium (6.9 mL, 1.6M n-pentane solution) was added dropwise under the condition of -78°C, after the addition, stirred at -78°C for half an hour, and then brought to room temperature for lithiation for 1 hour. Diphenylphosphine chloride (4.41g, 20mmol) was slowly dropped at 0°C. After the addition is complete, reflux and react for 2h. Under ice-water bath, the reaction was quenched with saturated sodium bicarbonate solution, the aqueous phase was extracted with ether, the organic phases were combined, washed with water, dried over anhydrous sodium sulfate, concentrated, column chromatography, ethanol recrystallized to obtain 2.92g orange solid, yield 66 %.

[0060]

[0061] N 2 Under the atmosphere, 2 (2.2g, 5mmol) and 3.2mL of anhydrous acetic anhydride were added to the reaction tube, and the reaction was refluxed at 100°C for 2h. Afte...

Embodiment 2

[0066] Synthesis of ligand L8:

[0067]

[0068] (S)-Ugi-amine 1 (2.57g, 10mmol) dissolved in 20mL of anhydrous ether, N 2 Protected, tert-butyllithium (6.9 mL, 1.6M n-pentane solution) was added dropwise under the condition of -78°C, after the addition, stirred at -78°C for half an hour, and then brought to room temperature for lithiation for 1 hour. Diphenylphosphine chloride (4.41g, 20mmol) was slowly dropped at 0°C. After the addition is complete, reflux and react for 2h. Under ice-water bath, the reaction was quenched with saturated sodium bicarbonate solution, the aqueous phase was extracted with ether, the organic phases were combined, washed with water, dried over anhydrous sodium sulfate, concentrated, column chromatography, ethanol recrystallized to obtain 2.92g orange solid, yield 66 %.

[0069]

[0070] N 2 Under the atmosphere, 2 (2.2g, 5mmol) and 3.2mL of anhydrous acetic anhydride were added to the reaction tube, and the reaction was refluxed at 100°C for 2h. Afte...

Embodiment 3

[0077] Synthesis of ligand L17:

[0078]

[0079] In a 20mL reaction tube, add 0.4563g (1mmol) acetate 3 and 0.7460g (5mmol) (1S,2R)-(-)1-amino-2-indanol, replacing N 2 Then, 10 mL of anhydrous methanol was added, the reaction was carried out at reflux overnight, rotary evaporation was concentrated, and 0.428 g of a pale yellow solid was obtained by column chromatography with a yield of 78%.

[0080] 1 H NMR(400MHz, CDCl 3 )δ7.61-7.50(m,2H),7.44-7.34(m,3H),7.25-7.14(m,5H),7.11-7.02(m,2H),6.86-6.75(m,1H),6.35- 6.23(d,J=7.6Hz 1H),4.58-4.53(m,1H),4.41-4.31(m,2H),4.24-4.18(m,1H),4.04(d,J=5.2Hz,1H), 3.99(s,5H),3.90-3.85(m,1H),2.92-2.82(dd,J=5.2Hz,16.4Hz,1H),2.81-2.73(dd,J=1.6Hz,16.4Hz,1H), 1.58(d,J=6.4Hz,3H); 31 P NMR(162MHz, CDCl 3 )δ-26.11(s).

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Abstract

The invention relates to PNHO tridentate ligands and application of related ligands in asymmetric hydrogenation and similar reactions. The novel tridentate nitrogen-phosphine-oxygen ligands are first tridentate nitrogen-phosphine-oxygen ligands containing ferrocenyl planar chiral phosphine, and are successfully applied to high-efficiency high-selectivity asymmetric hydrogenation and other similar reactions of simple aromatic ketone, alpha-hydroxyketone and beta-ketone ester. Compared with other dominant tridentate ligands, the ligands provided by the invention have the advantages of simple synthesis route and low cost, can easily implement large-scale synthesis, are stable in air, and have high activity and high selectivity in asymmetric hydrogenation reactions of carbon-oxygen double bonds.

Description

Technical field [0001] The invention relates to the application of a chiral tridentate nitrogen phosphine oxygen ligand and its related ligands in asymmetric hydrogenation reactions and similar reactions, and belongs to the field of asymmetric catalysis. Background technique [0002] With the increasing demand for optically pure chiral drugs, pesticides, perfumes and other fine chemicals, asymmetric catalysis technology has achieved considerable development. Direct use of hydrogen for catalytic asymmetric hydrogenation of unsaturated compounds such as prochiral olefins, ketones and imines has always been a research hotspot in the field of asymmetric catalysis due to its high efficiency, high selectivity, and high atom economy. [1] . The core factor that determines the efficiency of asymmetric hydrogenation is the effective combination of metals and ligands. However, due to the periodic table of elements, the choice of transition metals is limited. Therefore, the design and develo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/02C07F19/00B01J31/24C07C29/145C07C33/22C07C33/46C07C41/26C07C43/23
CPCB01J31/2404B01J31/2447B01J2231/342B01J2531/0266B01J2531/827B01J2531/842C07C29/145C07C33/22C07C33/46C07C41/26C07C43/23C07F17/02
Inventor 张绪穆余建飞
Owner WUHAN CATALYS TECH CO LTD
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