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Synthetic method of axis-unsymmetric chiral diphosphine ligand
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A technology of a chiral bisphosphine ligand and a synthesis method, which is applied in the field of synthesis of asymmetric axis chiral bisphosphine ligands, can solve the problems of high enantioselectivity and the like, and achieves few reaction steps, high yield and easy raw materials. the effect
Inactive Publication Date: 2011-10-26
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Since there is no universal chiral ligand, and the substrates of the reaction are diverse, no chiral ligand exhibits high enantioselectivity for all substrates
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Embodiment 1
[0039] Embodiment 1: the synthesis of compound (2)
[0040] In the reaction flask of nitrogen protection, add compound (1) (0.217 mmol), and CH 3 (CH 2 ) 7 Add deoxygenated acetone after Br (0.326 mmol), and then add potassium carbonate (1.08 mmol), and heat to reflux. Follow the reaction, after 8 hours, stop the reaction, drop to room temperature, filter off potassium carbonate, silica gel column chromatography, the eluent is petroleum ether / ethyl acetate (v / v, 4:1); obtain product (2) , the yield was 81%.
Embodiment 2
[0041] Embodiment 2: the synthesis of compound (3)
[0042] In the nitrogen-protected reaction flask, add compound (2) (0.177 mmol), and polyethylene glycol monomethyl ether methanesulfonate (MeO-PEG-OMs, its molecular weight is 1978) (0.177 mmol), after Add deoxygenated N,N-dimethylformamide, then cesium carbonate (0.708 mmol), and heat to 65°C for 16 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was dissolved in 10 ml of dichloromethane as a solvent, then the cesium carbonate was filtered off, most of the dichloromethane was spun off, cooled to 0°C, and n-hexane was added, and a solid precipitated out. The precipitated solid was suction filtered to obtain the product with a yield of 70%.
Embodiment 3
[0043] Embodiment 3: application in quinoline hydrogenation reaction
[0044] Put [Ir(COD)Cl] into the reaction flask 2 (0.0025 mmol) and this kind of axial chiral bisphosphine ligand (0.0055 mmol), stirred at room temperature in 1 ml of toluene for 10 minutes, after dissolving iodine (0.025 mmol) in 1 ml of toluene, adding quinoline substrate (0.5 mmol) of the reaction flask, the stirred catalyst was added to the vial containing iodine and the substrate. Put the reaction bottle into a stainless steel autoclave, replace it with hydrogen three times, and finally fill it with 40 atmospheres of hydrogen pressure, react at room temperature for 12 hours, remove the solvent, and obtain the product by direct column chromatography. The reaction formula and the structure of the ligand are as follows:
[0045]
[0046] The conversion of the reaction is complete, and the enantiomeric excess of the product can reach 92% as determined by chiral liquid chromatography.
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Abstract
Disclosed is a method to synthesize asymmetric chiral diphosphine ligand. MeO-Biphep is demethylated to produce di-hydroxyl Biphep which then reacts with halogen compound or sulphonic acid ester compound in acetone under the action of inorganic base, producing monocarboxyl protected Biphep; the monocarboxyl protected Biphep is dissolved in N,N-dimethylformamide and then reacts with halogen compound, sulphonic acid ester compound, polyethylene glycol mono-methyl ether sulfonic ester or dendritic macromolecular brominated polyether compound to produce asymmetric chiral diphosphine whose stereome and electronic effect can be finely adjusted. After being coordinated with metal precursor, the asymmetric chiral diphosphine ligand can be effectively applied to the asymmetric hydrogenation of keto ester, imine, alkene and aromatic compounds. The method is simple and convenient to operate, and the asymmetric chiral diphosphine ligand is easy to produce derivatives to realize the diversification of the ligand, thus effectively regulating enantio-selectivity of the reaction.
Description
technical field [0001] The invention relates to a synthesis method of an asymmetric axial chiral bisphosphine ligand, in particular to a synthesis method of an asymmetric axial chiral bisphosphine ligand whose stereoscopic and electronic effects can be finely adjusted. technical background [0002] Axichiral bisphosphine ligands have been widely used in asymmetric synthesis. The axial chiral bisphosphine ligand molecule does not have a chiral center, but relies on the rotation of the C-C single bond connecting the two aromatic rings to be hindered by the chiral axis, so that the entire molecule has optical activity. Noyor first successfully synthesized the famous BINAP bisphosphine ligand, and after coordinating with various metal precursors, it has been well applied in asymmetric hydrogenation reactions. =N, C=O) catalytic hydrogenation is highly reactive and enantioselective. Biphenyl bisphosphine ligands similar in structure to BINAP have also been synthesized successiv...
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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50
Inventor 周永贵王小兵
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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