Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof

A technology of chiral bisphosphine ligands and ionic liquids, applied in the field of organic compounds and their preparation, can solve the problems of catalyst loss, catalytic activity and selectivity decline, and achieve the effect of high reactivity

Active Publication Date: 2012-09-26
山东格新精工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although ionic liquids have been successfully applied in asymmetric hydrogenation reactions, there are still relatively large limitations
For example, since the catalyst is only dissolved in the ionic liquid, the loss of the catalyst to the organic phase is unavoidable during recycling, resulting in a decrease in catalytic activity and selectivity

Method used

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  • Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof
  • Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof
  • Imidazole ionic liquid supported chiral phosphine ligands and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Synthesis of Chiral Bisphosphine Ligand 1a

[0029]In a Schlenk bottle, (2S, 4S)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine ( 2a , 0.56g, 0.0012mmol), 1-methyl-3-carboxymethylimidazolium tetrafluoroborate ( 3a , 0.28g, 0.0012mmol) and DIC (0.16g, 0.0012mmol) were dissolved in 10mL of deoxygenated dichloromethane, stirred at room temperature for 10h under the protection of argon, and monitored the end of the reaction with TLC. The solvent was then removed under reduced pressure, and the residue was subjected to column chromatography (degassed silica gel, EtOAc / MeOH / H 2 O=15 / 6 / 2) were separated to obtain 0.48g white solid 5 , yield 58.5%. mp : 149~150℃; [α] 20 D : -34.8 ( c 0.25, MeOH); 1 H NMR (500.0 MHz, CD 3 CN): δ=8.30 (s, 1H, NC H =N), 7.32-7.54 (m, 21H, Ph-H and NC H =CHNCH 3 or NCH=C H NCH 3 ), 7.21 (t, J= 1.6 Hz, 1H, NCH=C H NCH 3 or NC H =CHNCH 3 ), 4.89 (d, J= 16.8Hz, 1H, COC H HN), 4.61 (d, J= 16.8Hz, 1H, COCH H N),...

Embodiment 2

[0031] Synthesis of Chiral Bisphosphine Ligand 1b

[0032] The preparation method is the same as in Example 1. Yield 55.3%; 1 H NMR (500.0 MHz, CD 3 CN): δ=8.38 (s, 1H, NC H =N), 7.32-7.55 (m, 21H, Ph-H and NC H =CHNCH 3 or NCH=C H NCH 3 ), 7.23 (t, J= 1.6 Hz, 1H, NCH=C H NCH 3 or NC H =CHNCH 3 ), 4.87 (d, J= 17.0Hz, 1H, COC H HN), 4.61 (d, J= 17.0Hz, 1H, COCH H N), 4.13 (m, 1H, CONC H ), 3.87 (s, 3H, NC H 3 ), 3.69 (t, J= 10.0 Hz, 1H, CONC H H), 3.41 (q, J= 10.0Hz, 1H, CONCH H ), 3.07 (m, 1H, Ph 2 PC H ), 2.95 (td, J =13.0Hz, J= 3.3Hz, 1H, Ph 2 PC H H), 2.21-2.26 (overlapped m, 2H, Ph 2 PCH H and Ph 2 PCHC H H), 1.89 (m, 1H, Ph 2 PCHCH H ); 13 C NMR (125.7MHz, CD 3 CN): Δ = 163.51, 139.94, 138.64, 138.11, 138.04, 137.55, 134.31, 133.75, 133.57, 130.30, 129.75, 129.53, 123.93, 51.85, 37.81, 35.8, 35.81, 35.81, 35.81, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 35.8, 3...

Embodiment 3

[0034] Synthesis of Chiral Bisphosphine Ligand 1c

[0035] The preparation method is the same as in Example 1. Yield 61.3%; 1 H NMR (500.0 MHz, CD 3 CN): δ=8.33 (s, 1H, NC H =N), 7.32-7.51 (m, 21H, Ph-H and NC H =CHNCH 3 or NCH=C H NCH 3 ), 7.22 (t, J= 1.6 Hz, 1H, NCH=C H NCH 3 or NC H =CHNCH 3 ), 4.88 (d, J= 16.8Hz, 1H, COC H HN), 4.62 (d, J= 16.8Hz, 1H, COCH H N), 4.13 (m, 1H, CONC H ), 3.89 (s, 3H, NC H 3 ), 3.66 (t, J =10.0Hz, 1H, CONC H H), 3.39 (q, J= 10.0Hz, 1H, CONCH H ), 3.07 (m, 1H, Ph 2 PC H ), 2.96 (td, J =13.4Hz, J= 3.3Hz, 1H, Ph 2 PC H H), 2.23-2.28 (overlapped m, 2H, Ph 2 PCH H and Ph 2 PCHC H H), 1.87 (m, 1H, Ph 2 PCHCH H ); 13 C NMR (125.7MHz, CD 3 CN): Δ = 164.21, 140.14, 138.52, 138.07, 138.02, 137.51, 134.30, 133.71, 133.54, 130.24, 129.71, 129.52, 123.94, 57.97, 51.07, 37.8.8, 36.8, 36.8, 36.8, 35.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8, 36.8...

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Abstract

The invention relates to imidazole ionic liquid supported chiral phosphine ligands and a preparation method thereof, and application of rhodium complex of the chiral phosphine ligand in asymmetric catalytic hydrogenation of alpha-dehydroamino acid and derivatives thereof. The imidazole ionic liquid supported chiral phosphine ligands are synthesized by introducing cations of an imidazole ionic liquid into proline-derived chiral diphosphine ligand molecules, thereby effectively enhancing the activity, stereoselectivity and affinity with the imidazole ionic liquid of the catalyst. When being used for asymmetric catalytic hydrogenation of alpha-dehydroamino acid and derivatives thereof, the rhodium complex of the phosphine ligands has high enantioselectivity (ee=95.2%) and high conversion frequency (TOF=24000h<-1>), and can effectively inhibit rhodium loss; and after several cycles, the activity and stereoselectivity of the catalyst are not obviously lowered, and the rhodium loss is only 0.1-0.2%.

Description

[0001] technical field [0002] The present invention relates to an organic compound in the technical field of chemistry and chemical engineering and a preparation method thereof, in particular to a synthesis method of a chiral bisphosphine ligand supported by an ionic liquid and a rhodium complex thereof in alpha-dehydroamino acid and its derivatives applications in asymmetric catalytic hydrogenation. Background technique [0003] At present, the research on asymmetric hydrogenation has become one of the research hotspots in the frontier field of chemistry. It has the most literature reports and the most in-depth research, and has gradually become the core technology of chiral synthesis. The homogeneous asymmetric hydrogenation reaction has the advantages of high catalytic activity, good stereoselectivity, and mild reaction conditions. However, its disadvantage is that the separation and recycling of chiral noble metal catalysts are difficult to solve. Therefore, the conc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6558B01J31/24C07C233/47C07C231/12C07B53/00
CPCY02P20/54
Inventor 金欣徐新福
Owner 山东格新精工有限公司
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