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Imine ligand containing camphor

An imide phosphine and camphor technology, applied in the field of imid phosphine ligands, can solve the problems of poor enantioselectivity and yield, affecting industrial application, complex ligand synthesis, etc., achieving simple operation, easy structure modification, The effect of a simple synthesis route

Active Publication Date: 2016-07-20
杭州晶苯科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, some existing chiral phosphine nitrogen ligands have some defects in the asymmetric synthesis: 1. The ligand synthesis is complicated and difficult to prepare; 2. The substrate universality is poor; 3. The enantioselectivity and yield are poor. Influencing industrial applications

Method used

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  • Imine ligand containing camphor
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  • Imine ligand containing camphor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] (S)-1-(2-(diphenylphosphine)phenyl)ethyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine Synthesis.

[0029] Add p-methylbenzene to a solution of (S)-1-[2-(diphenylphosphine)phenyl]ethylamine (2.135g, 7.0mmol) and natural camphor (1.064g, 7.0mmol) in toluene (35mL) Sulphonic acid (5mg), heated under reflux for twelve hours, evaporated toluene in vacuo. The residue was extracted with ethyl acetate (3×10 mL), the organic phases were combined, and the organic phases were washed with water and saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product that was further separated and purified by column chromatography to obtain a pure product (S)-1-(2-(diphenylphosphine)phenyl) as a colorless oil Ethyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine 2.551 g, yield 83%. 1HNMR (400MHz, CDCl 3 )δ7.77(dd, J=7.1,4.2Hz,1H),7.27–7.11(m,11H),6.98(td,J=7.6,1.0Hz,1H),6.72(ddd,J=...

Embodiment 2

[0031] (R)-1-(2-(diphenylphosphine)phenyl)ethyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine Synthesis.

[0032] Add benzenesulfonic acid (5mg) to (R)-1-[2-(diphenylphosphine)phenyl]ethylamine (1.525g, 5.0mmol) and natural camphor (0.760g, 5.0mmol) in toluene (25mL ) solution, heated to reflux for twelve hours, and evaporated the toluene under reduced pressure. The residue was extracted with ethyl acetate (3×10 mL), the organic phases were combined, and the organic phases were washed with water and saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain the crude product, which was further separated and purified by column chromatography to obtain the pure product (R)-1-(2-(diphenylphosphine)phenyl) Ethyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine 1.823g, yield 83%. 1 HNMR (400MHz, CDCl 3 )δ7.74(dd, J=7.1,4.3Hz,1H),7.26–7.12(m,11H),7.00(td,J=7.6,1.1Hz,1H),6.76–6.73(m,1H),5.1...

Embodiment 3

[0034] (S)-1-(2-(diphenylphosphine)phenyl)propyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine Synthesis.

[0035] To a solution of (S)-1-[2-(diphenylphosphine)phenyl]propylamine (1.596 g, 5.0 mmol) and natural camphor (0.836 g, 5.5 mmol) in THF (15 mL) was added tetraethyl titanate (1.140g, 5.0mmol), heated to reflux for ten hours, and evaporated THF under reduced pressure. The residue was extracted with ethyl acetate (3×10 mL), the organic phases were combined, and the organic phases were washed with water and saturated sodium chloride solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product that was further separated and purified by column chromatography to obtain a pure product (S)-1-(2-(diphenylphosphine)phenyl) as a colorless oil Propyl-N-(1,7,7-trimethyl-bicyclo[2,2,1]heptane)-2-imine 1.813g, yield 80%. 1 HNMR (400MHz, CDCl 3 )δ7.66-7.64(m,1H),7.21-7.11(m,11H),6.97(t,J=7.56Hz,1H),6.77-...

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Abstract

The invention relates to the field of phosphinamine ligands, and discloses an imine ligand containing camphor having six chemical structural formulas.Natural camphor and chiral amine containing phosphine serve as raw materials and are subjected to dehydration condensation in the presence of a condensating agent to synthesize the imine ligand containing camphor.The imine ligand containing camphor has the advantages that the raw materials are easy to obtain, a synthesis route is simple, operation is easy, and the imine ligand is easy to purify and high in asymmetric catalysis efficiency.

Description

technical field [0001] The invention relates to the field of phosphine nitrogen ligands, in particular to a camphor-containing imidophosphine ligand. Background technique [0002] Chiral phosphine nitrogen ligands have been widely used in the synthesis of biologically active natural products and pharmaceutical intermediates (Trost BM., Crawley ML. Chem. Rev. 2003, 103, 2921-2943). Although the reported ligand types that can catalyze the allylic alkylation reaction also include phosphine ligands and nitrogen ligands, chiral phosphine nitrogen ligands occupy an absolute dominant position, and their palladium complexes have a breakthrough in this reaction. The catalytic effect of (McmanusHA, GuiryP.J.Chem.Rev.2004,104,4151~4202). However, some existing chiral phosphine nitrogen ligands have some defects in the asymmetric synthesis: 1. The ligand synthesis is complicated and difficult to prepare; 2. The substrate universality is poor; 3. The enantioselectivity and yield are poo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50C07F17/02
CPCC07F9/5022C07F9/5054C07F17/02
Inventor 陈巍峰刘巧灵李志芳徐利文郑战江
Owner 杭州晶苯科技有限公司
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