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Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation

A chiral phosphine ligand, amino acid type technology, applied in asymmetric synthesis, organic compound/hydride/coordination complex catalyst, formation/introduction of carbonyl, etc.

Inactive Publication Date: 2010-07-14
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The published documents on amino acid amphoteric phosphine ligands all use monophosphine ligands, but chiral phosphine ligands with amino acid side chains have not been reported.

Method used

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  • Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation
  • Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation
  • Synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Synthesis of 2a

[0038] In a Schlenk flask equipped with a dropping funnel, reflux condenser and magnetic stirring, add 1.19 g (3.68 mmol) of N-Boc-L-aspartic acid-4-benzyl ester (Boc-Asp(OBz1)-OH) , 0.5g (3.68mmozl) 1-hydroxy-benzotriazole (HOBt) and 0.46g (3.68mmol) N,N-diisopropylcarbodiimide (DIC), then add 60mL of degassed CH 2 Cl 2 Stir to dissolve. Add 1.67 g (3.68 mmol) (2S, 4S)-2-diphenylphosphinomethyl-4-diphenylphosphinopyrrole (PPM) dropwise in 20 mL of CH 2 Cl 2 The solution was reacted at room temperature for 2 h under an argon atmosphere, and the solvent was dried under reduced pressure. Column chromatography (petroleum ether / ethyl acetate: 3:1) and vacuum drying gave 2.62 g of a white foamy solid with a yield of 93.6%.

[0039] [α] 20 D -25.0° (c 0.5, CH 2 Cl 2 ); 1 H NMR (CDCl 3 ): δ7.612~7.272(m, 25H), 5.354(d, J=8Hz, 1H), 5.036(s, 2H), 4.682(m, 1H), 4.103(m, 2H), 3.416(q, J =9.5Hz, 1H), 3.121(d, J=12Hz, 1H), 2.794~2.753(m, 2H), 2.557(dd, J...

Embodiment 2

[0049] Synthesis of 2b

[0050] In a Schlenk bottle equipped with a dropping funnel, reflux condenser and magnetic stirring, add 0.37 g (1.22 mmol) Boc-Glu(OtBu)-OH, 0.16 g (1.22 mmol) 1-hydroxyl-benzotriazole ( HOBt) and 0.15 g (1.22 mmol) N, N-diisopropylcarbodiimide (DIC), then add 30 mL of degassed CH 2 Cl 2 Stir to dissolve. Add 0.55 g (1.22 mmol) (2S,4S)-2-diphenylphosphinomethyl-4-diphenylphosphinopyrrole (PPM) dropwise in 15 mL of CH 2 Cl 2 The solution was reacted at room temperature for 2 h under an argon atmosphere, and the solvent was dried under reduced pressure. Column chromatography (petroleum ether / ethyl acetate: 3:1) and vacuum drying gave 0.83 g of white crystals, with a yield of 92.7%.

[0051] mp.175~176℃; 1 H NMR (CDCl 3 ): δ7.617~7.261(m, 20H), 5.379(d, 1H), 4.366(m, 1H), 4.155(m, 1H), 3.961(t, 1H), 3.456(m, 1H), 3.162( m, 1H), 2.826(m,), 2.296~2.204(m, 3H), 1.959~1.916(m, 2H), 1.854~1.792(m, 1H), 1.655~1.580(m, 1H), 1.407(s ,18H); 31 P NMR (CDCl...

Embodiment 3

[0056] Synthesis of 2c

[0057] In a Schlenk bottle equipped with a dropping funnel, reflux condenser and magnetic stirring, add 0.234 g (0.81 mmol) Boc-Asp-OtBu, 0.11 g (0.81 mmol) 1-hydroxy-benzotriazole (HOBt) and 0.10 g (0.81 mmol) N,N'-diisopropylcarbodiimide (DIC), then add 30 mL of degassed CH 2 Cl2 Stir to dissolve. Add 0.37 g (0.81 mmol) (2S, 4S)-2-diphenylphosphinomethyl-4-diphenylphosphinopyrrole (PPM) dropwise in 10 mL of CH 2 Cl 2 The solution was reacted at room temperature for 2 h under an argon atmosphere, and the solvent was dried under reduced pressure. Column chromatography (petroleum ether / ethyl acetate: 3:1) and vacuum drying gave 0.55 g of white crystals, with a yield of 94.0%.

[0058] mp.189~191℃; 1 H NMR (CDCl 3 ): δ7.610~7.290(m, 20H), 5.715(d, 1H), 4.330(m, 1H), 4.268~4.142(m, 1H), 3.517(t, 1H), 3.296(m, 1H), 3.090(m, 1H), 2.878~2.787(m, 2H), 2.280~2.213(m, 3H), 1.924(m, 1H), 1.440(s, 18H); 31 P NMR (CDCl 3 ): δ-6.150, -9.142, -22.246, -22.75...

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Abstract

The invention relates to synthesis of class of amino acid type amphoteric water-soluble chiral phosphine ligand and application thereof in asymmetric catalytic hydrogenation. The class of ligand takes chiral phosphine ligand PPM as the matrix, amino acid molecules are introduced into PPM molecules, chiral dual phosphine ligands and synthesis midbody thereof are provided, the ligand designed into the invention can be applied to various asymmetric synthetic reactions catalyzed by metals, comprising asymmetric catalytic hydrogenation, hydrogen transfer, hydroformylation and the like, and especially has higher activity and stereoselectivity in asymmetric catalytic hydrogenation of alpha-dehydrogenation amino acid and derivatives thereof.

Description

technical field [0001] The invention relates to an organic compound in the technical field of chemistry and chemical engineering and a preparation method thereof, in particular to the synthesis of a class of amino acid-type amphoteric water-soluble chiral phosphine ligand and its application in asymmetric catalytic hydrogenation. Background technique [0002] Asymmetric hydrogenation reaction is the first asymmetric catalytic reaction used in industry, and it is also one of the frontier fields of chemical research with the most literature reports and the most in-depth and extensive research. It has now become the core technology of chiral synthesis. The traditional homogeneous asymmetric hydrogenation reaction has the advantages of catalytic activity, high stereoselectivity, good reproducibility of reaction results, and mild reaction conditions. However, its unavoidable disadvantage is that the separation and recycling of chiral noble metal catalysts are difficult to solve. ...

Claims

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Application Information

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IPC IPC(8): C07F9/50B01J31/24C07B53/00C07B41/06C07B35/08C07B37/08C07C233/47C07C231/12
CPCY02P20/55
Inventor 金欣刘国兵
Owner QINGDAO UNIV OF SCI & TECH
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