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Electron-deficient axially-chiral diphosphine ligands, and preparation method thereof

A bisphosphine ligand and electron-deficient technology, which is applied in the field of design and synthesis of electron-deficient bisphosphine ligands, can solve the problems of less and less research on electronic effects, and achieve fewer reaction steps, high yield, and high yield. high rate effect

Inactive Publication Date: 2013-07-17
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, compared with the steric effects of bisphosphine ligands, there are relatively few studies on their electronic effects.
Most of the reported bisphosphine ligands are electron-rich bisphosphine ligands (relative to triphenylphosphine), and less research has been done on electron-deficient bisphosphine ligands, especially fluorine-containing bisphosphine ligands. body

Method used

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  • Electron-deficient axially-chiral diphosphine ligands, and preparation method thereof
  • Electron-deficient axially-chiral diphosphine ligands, and preparation method thereof
  • Electron-deficient axially-chiral diphosphine ligands, and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1: Synthesis of 3-trifluoromethoxyphenyldiphenylphosphine oxide (2a)

[0056]

[0057] Under nitrogen protection, magnesium chips (0.528g, 22.0mmol) and freshly distilled tetrahydrofuran (20mL) were added to a 250mL three-neck flask (fired in vacuum), and then iodine crystals (0.040g, 0.16mmol) were added. Stir, and slowly add a small amount of 3-trifluoromethoxybromobenzene 1a (3.0 mL, 20.0 mmol) in tetrahydrofuran (20 mL) dropwise at room temperature to initiate the reaction. boiling state. After the dropwise addition, the temperature was raised to 70° C. for reflux reaction for 2 h. Then, the reaction system was lowered to 0°C, and a solution of diphenylphosphorous chloride (4.1 mL, 22.0 mol) in tetrahydrofuran (15 mL) was slowly added dropwise. After the dropwise addition, the system was slowly raised to room temperature, and the reaction was continued for 3 h. The reaction system was lowered to 0°C, anhydrous methanol (10 mL) was slowly added, and sti...

Embodiment 2

[0058] Example 2: Synthesis of (±)-(6,6'-bistrifluoromethoxyphenyl)-2,2'-bis(diphenylphosphine oxide) (rac-3a)

[0059]

[0060] Under the protection of nitrogen, diisopropylamine (14.1 mL, 100.3 mmol) and freshly distilled tetrahydrofuran (100 mL) were added into a 500 mL three-necked flask (fired in vacuum). Cool the system to -78°C, add n-butyllithium (concentration in n-hexane: 2.5mol / L, 36.2mL, 90.5mmol) drop by drop under stirring, after the addition is complete, control the system temperature at -78°C to continue the reaction After 1h, a lithium diisopropylamide solution was obtained. Compound 3-trifluoromethoxyphenyldiphenylphosphine oxide 2a (27.323g, 75.4mmol) was dissolved in freshly distilled tetrahydrofuran (60mL), and added dropwise to the prepared diisopropylamino In the lithium solution, it took 20 minutes to complete the addition. After the addition was complete, the temperature of the system was controlled at -78°C to continue the reaction for 1 h. Then...

Embodiment 3

[0061] Example 3: Resolution of (±)-(6,6'-ditrifluoromethoxyphenyl)-2,2'-bis(diphenylphosphine oxide) (rac-3a)

[0062]

[0063] In a 250 mL round bottom flask was added (±)-(6,6'-ditrifluoromethoxyphenyl)-2,2'-bis(diphenylphosphine oxide)rac-3a (6.857 g, 9.5 mmol) and chloroform (27mL), the system was heated to 40°C, stirred to dissolve rac-3a, and the resolving agent D-di-p-methoxybenzoyl tartaric acid (D)-DMTA (4.568g, 9.5mmol) was dissolved A solution of ethyl acetate (41 mL) was added to the system, a large amount of white precipitates formed in the stirred solution, and the reaction was continued at 40°C for 0.5h, and then at room temperature for 1h. After filtering (recovering the filtrate), the solid was washed 3 times with a mixed solvent of chloroform and ethyl acetate (1 / 3). The solid was transferred to a round-bottomed flask, and the remaining chloroform and ethyl acetate were pumped off with an oil pump to obtain 4.447 g of the salt formed by (S)-3a and (D)-DM...

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Abstract

The invention relates to a design and synthesis method of electron-deficient axially-chiral diphosphine ligands. The method comprises the following steps: processing a compound 3-trifluoromethoxyphenyl halide to prepare a Grignard reagent, carrying out a Grignard reaction, oxidizing to obtain 3-trifluoromethoxyphenylphosphine oxide, carrying out oxidation coupling under the action of an oxidant to obtain a diphenylphosphine compound, slitting by using a chiral acid to obtain a chiral acid salt of the diphenylphosphine compound, resolving through using an alkali to obtain an optically pure diphenylphosphine compound, and reducing through using trichlorosilane to obtain an axially chiral diphosphine ligand. The electron-deficient axially-chiral diphosphine ligands can be effectively used for the asymmetric hydrogenation of quinoline derivatives after the electron-deficient diphosphine ligands are coordinated with a metal precursor. The method has the advantages of simple operation and high yield, and the electron-deficient axially-chiral diphosphine ligands synthesized through the method have a special electron deficiency effect.

Description

technical field [0001] The invention relates to the design and synthesis of a class of electron-deficient bisphosphine ligands with axial chirality. Background technique [0002] Chiral bisphosphine ligands are an important class of ligands in asymmetric catalytic reactions, especially in reactions catalyzed by transition metals. Therefore, the design and synthesis of chiral bisphosphine ligands is still an ongoing scientific research important content. (Document 1: Tang, W.-J; Zhang, X. Chem. Rev. 2003, 103, 3029.) [0003] At present, compared with the steric effects of bisphosphine ligands, there are relatively few studies on their electronic effects. Most of the reported bisphosphine ligands are electron-rich bisphosphine ligands (relative to triphenylphosphine), and less research has been done on electron-deficient bisphosphine ligands, especially fluorine-containing bisphosphine ligands. body. (Document 2: Pollock, C.L.; Saunders, G.C.; Smyth, E.C.M.S.; Sorokin, V....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50
Inventor 周永贵张德旸
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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