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Chiral ferrocene diphosphine ligands, preparation method and application thereof

A technology for chiral ferrocene and bisphosphine ligands is applied in chemical instruments and methods, preparation of organic compounds, preparation of aminohydroxy compounds, etc. The effect of stable moisture and easy availability of raw materials

Active Publication Date: 2018-12-04
FOURTH MILITARY MEDICAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although tens of thousands of chiral ligands have been reported, many of which also exhibit high stereoselectivity, there are not many examples that are actually used in industrial production due to catalytic activity or cumbersome preparation.

Method used

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  • Chiral ferrocene diphosphine ligands, preparation method and application thereof
  • Chiral ferrocene diphosphine ligands, preparation method and application thereof
  • Chiral ferrocene diphosphine ligands, preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Add dropwise ( S )-8 (21 g, 74.5 mmol) in ether, after the dropwise addition, slowly add the dried TMEDA (28.6 mL, 192 mmol), after the addition, the reaction solution was raised to room temperature for 24 h. Stand still, extract the supernatant with a syringe to obtain a large amount of deep purple solid, wash twice with dry ether, extract the supernatant in the same way, and remove the remaining solvent with an oil pump to obtain 13.1 g of dilithium salt, which can be obtained without purification. used directly in the next reaction. Weigh the lithium salt (2.94 g, 10 mmol) obtained in the previous step in the glove box and add it to a one-necked bottle, inject 60 mL of dry n-hexane under a nitrogen atmosphere, and then slowly inject phosphorus trichloride (0.87 mL, 10 mmol), at room temperature Stir for 12 h. The insoluble matter was removed by suction filtration, and the solvent was evaporated to dryness to obtain a brown solid crude product, which was recrystalli...

Embodiment 2

[0043]

[0044] by( R )-8 is that raw material obtains phosphine chloride ( R )-5. Phosphine chloride ( R )-5 is that the raw material obtains the orange-yellow bubbly product ( R , S , R )-2 3.74 g, yield 66% (ethyl acetate: petroleum ether: triethylamine=1:5:0.5%). 1 H NMR (400Hz, CDCl 3 ) δ 7.97-7.81 (m, 3H), 7.69 (t, J = 8.4 Hz, 2H),7.45-7.37 (m, 2H), 7.33-7.28 (m, 1H), 7.28-7.12 (m,3H), 6.74 ( d, J = 8.3 Hz, 1H), 4.39-4.22 (m, 1H), 4.11 (dd, J = 6.9, 2.7 Hz, 1H), 4.07-4.04 (m, 1H), 4.02 (s, 5H), 3.43 -3.30 (m, 1H), 2.98- 2.79 (m, 1H), 2.80-2.66 (m, 2H), 2.54(t, J = 13.0 Hz, 1H), 2.14 (s, 6H), 1.25 (d, J = 6.8 Hz, 3H); 13 C NMR (101 Hz, CDCl 3 ) δ 135.48, 135.17, 133.83, 132.70, 132.33, 132.23, 132.07, 131.83,128.93, 128.20, 128.13, 127.57, 126.95, 126.72, 126.54, 125.79, 125.63,124.84, 124.46, 96.83, 73.63, 70.30, 69.47, 69.26, 67.48, 56.79, 39.17, 32.80, 29.50, 7.89; 31 P NMR (162 Hz, CDCl 3 ) δ -6.58; HRMS (ESI) calcd for C 36 h 35 FeNP[M+H] + : ...

Embodiment 3

[0046]

[0047] To the monophosphine intermediate ( R , S , R )-2 (284 mg, 0.5 mmol) in glacial acetic acid solution was added bis(3,5-dimethylphenyl) phosphine 3a (133 mg, 0.55 mmol), the reaction temperature rose to 82 ~ 107 ° C, nuclear magnetic monitoring to the reaction End. Cooled to room temperature, dichloromethane diluted the reaction solution, washed with water, saturated sodium bicarbonate solution and saturated brine successively, dried, spin-dried, and column chromatography (ethyl acetate:petroleum ether=1:30) gave orange bisphosphine Ligand( R , S , R )-Ia275 mg, yield 72%. 1 H NMR (400Hz, CDCl 3 ) δ 8.03 (d, J = 8.3 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.85 (dd, J = 16.0, 8.2 Hz, 2H), 7.77 (d, J = 8.3 Hz, 1H), 7.54-7.40 (m, 2H), 7.37 (t, J= 7.5 Hz, 1H), 7.24-7.14 (m, 3H), 7.11 (d, J = 8.5 Hz, 1H), 6.96 (d, J = 7.1Hz , 3H), 6.89-6.75 (m, 3H), 4.27 (s, 5H), 4.14 (s, 1H), 4.11 (s, 1H), 3.81(t, J = 5.7 Hz, 1H), 3.75 (s, 1H), 3.25 (d, J = 14.4 Hz, 1H), 3....

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Abstract

The invention discloses chiral ferrocene diphosphine ligands. The ligands take chiral ferrocene amine as the raw material, after ortho-lithiation, the lithiated raw material reacts with a phosphine chloride to obtain a monophosphine intermediate, and the intermediate reacts with different secondary phosphines, thus obtaining chiral ferrocene diphosphine ligands with different chiral centers. The diphosphine ligands provided by the invention have the characteristics of novel structure, stability in air and simple synthesis, the complex catalysts formed by the diphosphine ligands and metals havestrong substrate universality, and show high catalytic activity and stereoselectivity in asymmetric hydrogenation reaction of latent chiral olefins, latent chiral ketones, latent chiral imines and the like.

Description

technical field [0001] The invention relates to a class of chiral ferrocene bisphosphine ligand and its preparation method and application. Background technique [0002] The methods for synthesizing optically active compounds mainly include: racemate resolution, chiral source synthesis, asymmetric induction, chiral amplification, and catalytic asymmetric synthesis, etc., and the asymmetric catalytic hydrogenation in catalytic asymmetric synthesis is due to its atomic The advantages of economy and simple post-treatment have become the most ideal method for the synthesis of chiral compounds. The key to asymmetric catalytic hydrogenation is the metal complex catalyst with high activity and high stereoselectivity, and the ligand is its core and key. Therefore, designing and synthesizing ligands with novel structures has always been a hot spot in the research of asymmetric catalytic hydrogenation reactions, and it is also the most active field in the research of asymmetric synth...

Claims

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Application Information

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IPC IPC(8): C07F17/02B01J31/24C07C217/08C07C213/02
CPCB01J31/2495B01J2231/643B01J2531/0225B01J2531/0241B01J2531/827B01J2531/842C07C213/02C07C217/08C07F17/02
Inventor 张生勇聂慧芳王巧峰姚琳魏朝李穆琼
Owner FOURTH MILITARY MEDICAL UNIVERSITY
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