Phosphoramidite monophosphine ligand and preparation method and application thereof

A phosphine amide type, monodentate phosphine ligand technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, etc., can solve the difficulty of monophosphine ligand synthesis And other issues

Active Publication Date: 2009-06-03
常熟紫金知识产权服务有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although a considerable number of chiral monophosphine ligands with excellent properties have been reported, the synthesis of many monophosphine ligands is relatively difficult.

Method used

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  • Phosphoramidite monophosphine ligand and preparation method and application thereof
  • Phosphoramidite monophosphine ligand and preparation method and application thereof
  • Phosphoramidite monophosphine ligand and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Preparation of (S)-N-6'-amino-4,6,2',4'-tetrakis(trifluoromethyl)-biphenyl-2-acetamide

[0021] Add (S)-4,4',6,6'-tetrakis(trifluoromethyl)biphenyl-2,2'-diamine (456mg, 1.0mmol) to a 25mL Schlenk bottle at room temperature 10mL of anhydrous dichloromethane, glacial acetic acid (0.6mL, 10.0mmol), acetic anhydride (142μL, 1.5mmol), stirred the reaction mixture overnight, then adjusted the pH to 7-8 with 2N NaOH solution, extracted with dichloromethane , combined the organic phases with saturated NaHCO 3 Washing, saturated brine washing, anhydrous Na 2 SO 4 After drying and removing the solvent, the crude product can be obtained by column chromatography as a white solid (S)-N-6'-amino-4,6,2',4'-tetrakis(trifluoromethyl)-biphenyl-2-ethane Amide 293 mg, yield 56%.

[0022] [α] 25 D =+162.0 (c 0.66, CHCl 3 ); IR(KBr)v 3584, 3431, 1702, 1530, 1491, 1445, 1370, 1276, 1177, 1129cm -1 ; 1 H NMR (CDCl 3 , TMS, 300MHz) 8.86(s, 1H), 7.84(s, 1H), 7.45(s, 1H), 7.27(s, 1H)...

Embodiment 2

[0024] Preparation of (R)-N-6'-amino-4,6,2',4'-tetrakis(trifluoromethyl)-biphenyl-2-acetamide

[0025] Add (R)-4,4',6,6'-tetrakis(trifluoromethyl)biphenyl-2,2'-diamine (456mg, 1.0mmol) to a 25mL Schlenk bottle at room temperature 10mL of anhydrous dichloromethane, glacial acetic acid (0.6mL, 10.0mmol), acetic anhydride (142μL, 1.5mmol), stirred the reaction mixture overnight, then adjusted the pH to 7-8 with 2N NaOH solution, extracted with dichloromethane , combined the organic phases with saturated NaHCO 3 Washing, saturated brine washing, anhydrous Na 2 SO 4 After drying and removing the solvent, the crude product can be obtained by column chromatography as a white solid (R)-N-6'-amino-4,6,2',4'-tetrakis(trifluoromethyl)-biphenyl-2-ethane Amide 306 mg, yield 58.5%.

[0026] [α] 25 D =-161.4 (c 0.66, CHCl 3 ); IR(KBr)v 3584, 3431, 1702, 1530, 1491, 1445, 1370, 1276, 1177, 1129cm -1 ; 1 H NMR (CDCl 3 , TMS, 300MHz) 8.86(s, 1H), 7.84(s, 1H), 7.45(s, 1H), 7.27(s, 1...

Embodiment 3

[0028] Preparation of (S)-N-ethyl-4,4',6,6'-tetrakis(trifluoromethyl)-biphenyl-2,2'-diamine

[0029] Under the condition of Ar, add 5.0 mL of (S)-N-(6′-amino-4,6,2′,4′-tetrakis(trifluoro Methyl)-biphenyl-2-acetamide (270mg, 0.54mmol) in tetrahydrofuran, refluxed for 1.0 hour, carefully added ice-water mixture to the reaction system, extracted unreacted hydride, and then 15% NaOH solution Adjust the pH to 7-8, remove the white solid by filtration, extract with dichloromethane, combine the organic phases with saturated NaHCO 3 Washing, saturated brine washing, anhydrous Na 2 SO 4 After drying and removing the solvent, the crude product can be obtained by column chromatography in yellow oily liquid (S)-N-ethyl-4,4',6,6'-tetrakis(trifluoromethyl)-biphenyl-2,2'- Diamine 190 mg, yield 75.2%.

[0030] [α] 25 D =+131.4 (c 0.72, CHCl 3 ); 1 H NMR (CDCl 3 , TMS, 300MHz) δ 7.42(s, 1H), 7.34(s, 1H), 7.22(s, 1H), 7.09(s, 1H), 3.85(br, 2H), 3.53(br, 1H), 3.20( m, 2H), 1.14(t, J=7....

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Abstract

A phosphoramidite monophosphine ligand has the structural formula thereof shown above, wherein R<1> or R<2> is selected from H, methyl or ethyl, and R<3> is selected from aryl or C1-C6 alkyl. The preparation method of the phosphoramidite monophosphine ligand comprises the following steps: adding dialkylphosphine chloride or diarylphosphine chloride of dichloromethane, triethylamine and C1-C6 alkane to a container containing enantiomer pure 4,4'6,6'-tetrakis-trifluoromethyl-biphenyl-2,2'-diamine (TF-BIPHAM) or enantiomer pure 3,3'-dibromo-4,4'6,6'-tetrakis-trifluoromethyl-biphenyl-2,2'-diamine in the presence of N2, stirring at room temperature for 12 to 72 h, removing solvent under reduced pressure, and purifying with column chromatography. The phosphoramidite monophosphine ligand is used in asymmetric [3+2] 1,3-dipolar cycloaddition of azomethine ylide, resulting in good effect and high enantiomeric selectivity of product (up to 99%).

Description

technical field [0001] The invention relates to a class of phosphonamidite monodentate phosphine ligands and a preparation method and use thereof. Background technique [0002] Chiral monophosphine ligands have a very wide range of applications in asymmetric catalysis. Although quite a number of chiral monophosphine ligands with excellent properties have been reported, the synthesis of many monophosphine ligands is difficult. [0003] The present invention conveniently synthesizes a series of phosphonamidite type monodentate phosphine ligands, and uses them in the 1,3-dipolar asymmetric 3+2 cycloaddition reaction of azomethine ylide, and obtains very good results Effect. Contents of the invention [0004] The purpose of the present invention is to provide a class of enantiomerically pure phosphonamidite type monodentate phosphine ligands, and provide their preparation method and use. Through the method provided by the invention, a series of monodentate phosphine ligands...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/46B01J31/24B01J31/28C07D207/10
Inventor 王春江梁刚陶海燕
Owner 常熟紫金知识产权服务有限公司
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