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New type spirocyclic diphosphine ligand, and application in asymmetric catalytic hydrogenation

A bisphosphine ligand and spiro ring technology, applied in the field of new spiro ring bisphosphine ligand and its application in asymmetric catalytic hydrogenation, can solve the problems of low conversion number and enantioselectivity

Inactive Publication Date: 2005-01-12
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, the performance in the catalytic hydrogenation of α, β-unsaturated carboxylic acids (such as 2-methyl-2-butenoic acid) and other latent chiral substrates is still not ideal, mainly for the conversion number and enantioselectivity Relatively low (Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R.J.Org.Chem.1987, 52, 3174), and this kind of catalytic hydrogenation products are the best choice for the synthesis of chiral drugs important raw material (Steven, D.; David, N.Deaton Tetrahedron Lett.1991, 32, 4651), so to realize the asymmetric catalytic hydrogenation of the above-mentioned substrates with high efficiency and high enantioselectivity, it is necessary to develop new and efficient Chiral bisphosphine ligands

Method used

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  • New type spirocyclic diphosphine ligand, and application in asymmetric catalytic hydrogenation
  • New type spirocyclic diphosphine ligand, and application in asymmetric catalytic hydrogenation
  • New type spirocyclic diphosphine ligand, and application in asymmetric catalytic hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Example 1: Preparation of 2-bromo-3'-methoxy-1,1'-biphenyl

[0039]

[0040] Under a nitrogen atmosphere, 20 mL THF solution of 3-bromoanisole (16.6 g, 89 mmol) was dropped into 80 mL THF suspension of magnesium chips (2.14 g, 89 mmol), while heating to 55 ° C to initiate the reaction, when the reaction occurred Finally, use a water bath to keep the reaction temperature at about 30°C and add the remaining THF solution of 3-bromoanisole dropwise under temperature control. A reaction flask filled with o-dibromobenzene (20g, 92mmol), tetrakis(triphenylphosphine)palladium (1.5g, 1.3mmol) and 100mL THF. After the dropwise addition, the temperature was controlled at 40° C. for 40 hours. Then, most of the solvent was evaporated under reduced pressure, the reaction liquid was diluted with diethyl ether, washed successively with 3N HCl solution and saturated brine, dried over anhydrous magnesium sulfate, filtered, precipitated under reduced pressure, and dissolved in petrole...

Embodiment 2

[0041] Embodiment 2: Preparation of 2,2'-bis-(3-methoxyphenyl)benzophenone

[0042]

[0043] Under nitrogen atmosphere, n-butyllithium (22mL, 2.0M n-hexane solution, 44mmol) was dropped into the pre-cooled to -78°C and contained 2-bromo-3'-methoxy-1,1'-biphenyl (11.7g, 44mmol) and 100mL THF in a reaction flask. After the dropwise addition, continue to stir at -78°C for 20 minutes, then continue to dropwise add a solution of dimethyl carbonate (1.69g, 18.9mmol) dissolved in 25mL THF, after the dropwise addition, naturally warm to -40°C and hold The temperature was maintained for about 3 hours to obtain a yellow suspension. After naturally rising to room temperature, the solution was removed in vacuo, diluted with dichloromethane, washed with 3N HCl solution, dried over anhydrous magnesium sulfate, filtered, and removed under reduced pressure to obtain a solid, acetic acid Ethyl ester was recrystallized to obtain 5.42 g of white solid. Yield: 70% Melting point: 159-160°C. 1...

Embodiment 3

[0044] Example 3: Preparation of 2,2'-bis-(2-bromo-5-methoxyphenyl)-benzophenone

[0045]

[0046] 2,2'-bis-(3-methoxyphenyl)-benzophenone (10g, 25.4mmol) was dissolved in 100mL of dichloromethane, and kept at low temperature with an ice-water bath, then liquid bromine (8.1 g, 50.8 mmol) in 20 mL of dichloromethane solution and stirred at room temperature for 6 hours, the reaction solution was diluted with dichloromethane, and the organic phase was washed successively with water-saturated sodium bisulfite and saturated aqueous sodium bicarbonate until neutral, sulfuric acid Dried over magnesium, filtered, and precipitated under reduced pressure to obtain 14.2 g of light yellow solid. Yield: 100% Melting point: 158-160°C. 1H NMR (300MHz, CDCl 3 ): 3.69 (s, 3H, Ar-OCH3), 3.37 (s, 3H, Ar-OCH3), 6.63-6.69 (m, 4H, Ar-H), 7.19-7.21 (m, 4H, Ar-H), 7.34-7.50 (m, 5H, Ar-H), 7.59 (d, 1H, J=7.8Hz, Ar-H); 13 C NMR (75 MHz, CDCl 3 ): δ55.4, 113.7, 113.8, 114.4, 115.3, 116.5, 127.2, ...

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Abstract

The invention relates to a new type chirality spiro Hannane and the key midbody spiro diphenol, the composing method and application of ruthenium complex acetate of said chirality spiro Hannane in Alpha, Beta-unsaturated carboxylic acid. The compound can be used as chirality part for asymmetrical catalysis hydrogenating reaction-especialy the Alpha, Beta-unsaturated carboxylic acid has high stereoselectivity, the highest ee value reach 98 percent and has high reaction activity and high transform quantity (S / C=10000).

Description

technical field [0001] The present invention relates to a novel chiral spirocyclic bisphosphine ligand and its intermediate spirocyclic diphenol, its synthesis method and the application of the spirocyclic bisphosphine ligand in the asymmetric catalytic hydrogenation of α,β-unsaturated carboxylic acids . Background technique [0002] Asymmetric catalytic synthesis is a hotspot in the field of organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high enantioselectivity and catalytic activity. The design and synthesis of chiral catalysts is, in a sense, the design and synthesis of chiral ligands, because chiral ligands are the source of asymmetric induction and control of chiral catalysts. In 1966, Wilkinson found that the highly active homogeneous catalyst triphenylphosphine rhodium complex provided a p...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C39/23C07F9/28
Inventor 周其林程旭谢建华王立新张齐侯国华
Owner NANKAI UNIV
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