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Axial chirality monophosphine ligand in chiral bridging and preparation method thereof

An axial chirality and chirality technology, which is applied in the field of chiral monophosphine ligands and their preparation, which can solve the problems of lack of ligands and catalytic systems, asymmetry, and limited catalytic examples.

Active Publication Date: 2017-06-13
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the asymmetric Suzuki coupling reaction substrates have very strict requirements on ligands, and there are very limited examples of successful catalytic applications of existing ligands. There is still a lack of asymmetric coupling of heterocyclic compounds and large hindered biaryls. Effective ligands and catalytic systems, there is an urgent need to develop new chiral ligands and catalytic systems to solve the hot problem of asymmetric catalytic synthesis of chiral biaryl compounds

Method used

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  • Axial chirality monophosphine ligand in chiral bridging and preparation method thereof
  • Axial chirality monophosphine ligand in chiral bridging and preparation method thereof
  • Axial chirality monophosphine ligand in chiral bridging and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Taking the preparation of (R)-[6,6'-((S,S)-2,3-butanedioloxy)]-2-diphenylphosphinebiphenyl as an example

[0031]

[0032] Preparation of 6,6'-dimethoxy-2-hydroxybiphenyl:

[0033] Under nitrogen protection, 15g (60mmol) 2-iodo-3-methoxyphenol 1, 13.68g (90mmol) 2-methoxyphenylboronic acid, 24.84g (180mmol) potassium carbonate, 538mg (2.4mmol) palladium acetate Suspend in 150mL N,N-dimethylformamide (DMF) and 150mL water, heat up to 50°C, stir for 24 hours, distill off DMF and water under reduced pressure, pour the reaction residue into 1mol / L hydrochloric acid, wash with acetic acid Ethyl ester was extracted 3 times, and the organic phases were combined. The organic phase was dried with anhydrous magnesium sulfate, and the crude product was purified by column chromatography to obtain 10.2 g of product 6,6'-dimethoxy-2-hydroxybiphenyl with a yield of 74%.

[0034] Product Analysis Results: 1 H NMR (400MHz, CDCl 3 ): δ7.41-7.45(m,1H),7.27-7.33(m,2H),7.0...

Embodiment 2

[0050] Example 2: Taking the preparation of (S)-[6,6'-((2R,4R)-2,4-pentanedioloxy)]-2-diphenylphosphinebiphenyl as an example

[0051]

[0052] Under nitrogen protection, 1.2g (3.24mmol) of 6,6'-dihydroxy-2-diphenylphosphinebiphenyl, 2.43g (7.45mmol) of cesium carbonate were suspended in 80mL of dry N,N-dimethylformaldehyde Amide (DMF), stirred at 80°C for 1 hour. Then, 2.67 g (6.48 mmol) of p-toluenesulfonate of (2S,4S)-2,4-pentanediol was dissolved in 40 mL of dry DMF, and slowly added dropwise to the reaction liquid over 4 hours. The reaction solution was continuously stirred at 80° C. for 30 hours, and DMF was distilled off under reduced pressure. The reaction residue was poured into 1mol / L hydrochloric acid, extracted three times with ethyl acetate, and the organic phases were combined. The organic phase was dried with anhydrous magnesium sulfate, and the crude product was purified by column chromatography to obtain 0.31 g of product (S)-[6,6'-((2R,4R)-2,4-pentanedio...

Embodiment 3

[0054] Example 3: Taking the preparation of (S)-[6,6'-((2R,5R)-2,5-hexanedioloxy)]-2-diphenylphosphine biphenyl as an example

[0055]

[0056]Under nitrogen protection, 1.2g (3.24mmol) of 6,6'-dihydroxy-2-diphenylphosphinebiphenyl, 2.43g (7.45mmol) of cesium carbonate were suspended in 80mL of dry N,N-dimethylformaldehyde Amide (DMF), stirred at 80°C for 1 hour. Then, 2.76 g (6.48 mmol) of p-toluenesulfonate of (2S,5S)-2,4-hexanediol was dissolved in 40 mL of dry DMF, and slowly added dropwise to the reaction liquid over 4 hours. The reaction solution was continuously stirred at 80° C. for 30 hours, and DMF was distilled off under reduced pressure. The reaction residue was poured into 1mol / L hydrochloric acid, extracted three times with ethyl acetate, and the organic phases were combined. The organic phase was dried with anhydrous magnesium sulfate, and the crude product was purified by column chromatography to obtain 0.61 g of the product (S)-[6,6'-((2R,5R)-2,5-hexanedi...

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Abstract

The invention discloses an axial chirality monophosphine ligand in chiral bridging and a preparation method thereof. An optical pure ligand which has both chiral chains in bridging and axial chirality is obtained by using biphenyl as a framework through accurate chiral recognition and control, a synthesis method is simple and economic, separation and purification can be realized through a silica-gel column chromatography separation method, a complicated chiral resolution process is avoided, and the obtained chiral ligand has the advantages of high reaction activity, good enantioselectivity and the like in an investigative model reaction; particularly, the effect in an asymmetric Suzuki reaction of palladium-catalyzed bromo-heterocyclic aromatic and arylboronic acid is excellent.

Description

technical field [0001] The invention belongs to the field of chemical catalysis, and in particular relates to a class of chiral monophosphine ligands and a preparation method thereof. Background technique [0002] In asymmetric catalytic reactions, the influence of ligands is extremely critical. Since ligands are not versatile, changes in substrate structure often lead to significant changes in catalyst activity and enantioselectivity, which requires suitable ligands and substrates. objects match each other. Therefore, the design and synthesis of chiral ligands and new catalytic reactions are undoubtedly hot spots in the development of asymmetric catalysis (Noyori, R; Ohkuma, T. Angew. Chem. Int. Ed. 2002, 41, 2008–2022.), The former focuses on the design and synthesis of new ligands, while the latter explores new reactions. Chiral phosphine ligands are one of the most widely used and successful types of ligands in asymmetric catalysis, and play a crucial role in the devel...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/60C07F9/655B01J31/24
CPCC07F9/60C07F9/65527B01J31/2447B01J2531/0266B01J2531/824B01J2231/4211
Inventor 邱立勤夏旺周贤太
Owner SUN YAT SEN UNIV
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