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Chiral nitrogen-sulfur bidentate ligand and synthesis method and application thereof

A synthetic method and a chiral technology, applied in the field of chiral compound synthesis, can solve the problem of not finding a ligand and the like, and achieve the effects of simple operation, high enantioselectivity and mild reaction conditions

Inactive Publication Date: 2015-09-23
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Nevertheless, given the complexity of organic reactions, a ligand with general applicability has not yet been found, which means that the exploration of unreported chiral ligands will continue

Method used

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  • Chiral nitrogen-sulfur bidentate ligand and synthesis method and application thereof
  • Chiral nitrogen-sulfur bidentate ligand and synthesis method and application thereof
  • Chiral nitrogen-sulfur bidentate ligand and synthesis method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0039] Synthesis of Chiral Nitrogen-Sulfur Bidentate Ligands

[0040] Add compound 1 (pyridine-2,6-dicarboxylic acid, 5.0 g, 30.0 mmol) and 10 mL of methanol into a 100 mL egg-shaped flask, drop into 10 mL of concentrated sulfuric acid, and heat to reflux. After stopping the reaction, add sodium carbonate and sulfuric acid to react. When the solution is neutral, extract with DCM three times, wash with saturated brine once, and add anhydrous sodium sulfate to dry. Suction filtration, spin-dried organic solvent to obtain compound 1a.

[0041] Add compound 1a (4.0g, 20.5mmol), 30mL methanol and 20mL dichloromethane into a 250mL three-necked flask, add NaBH 4 (0.86g, 22.4mmol), the reaction was stirred. After stopping the reaction, the solvent was spin-dried and separated by column to obtain compound 2a.

[0042] Add NaH (0.36g, 15.0mmol) and 20mL tetrahydrofuran into the reaction tube, stir to form a suspension, add compound 2a (2.0g, 12.0mmol) into the reaction tube, stir for...

Embodiment 2～19

[0046] Study on Additives, Solvents and Ligands of Palladium-Catalyzed Asymmetric Allyl Reaction

[0047]

[0048] Wherein mol refers to mole, Base refers to base, Solvent refers to solvent, Ligand refers to ligand, Time refers to time, equiv. refers to equivalent, ee refers to enantiomeric excess percentage.

[0049] In a dry reaction tube protected by argon, add 4.0mol% [Pd(C 3 h 5 )Cl] 2 , 8.0mol% ligand, stirred at room temperature for 30 minutes, then added 1.0equiv.5a (0.2mmol), and continued to stir for 10 minutes, while adding 3.0equiv.6a (1.5mmol) and 3.0equiv. of Base to another reaction tube In 1.5 Solvent solvent, stir the reaction to pre-prepare the nucleophile, add the nucleophile to the catalyst, and stir the reaction. After the reaction was completed, the residue was removed by thin-layer chromatography under reduced pressure to obtain the target product (petroleum ether / dichloromethane=1 / 1, or petroleum ether / ethyl acetate=10 / 1, v / v).

[0050] The diffe...

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Abstract

The invention relates to a chiral nitrogen-sulfur bidentate ligand and a synthesis method and an application thereof. The chiral nitrogen-sulfur bidentate ligand is obtained by esterifying carboxylic acid firstly and then carrying out a reaction with chiral sulfinyl amine; the ligand is combined with a transition metal palladium, symmetrical allyl acetate is used as a substrate, dimethyl malonate and dimethyl fluoromalonate are used as nucleophilic reagents, and a chiral carbon-carbon bond is successfully constructed. Compared with the prior art, the chiral nitrogen-sulfur bidentate ligand has easily obtained synthetic raw materials, and the synthetic method is simple; the prepared chiral nitrogen-sulfur bidentate ligand is N-(sulphinyl)picolinamide with optical activity is applied in construction of the chiral carbon-carbon bond catalyzed by the transition metal palladium, the reaction conditions are mild, the operation is simple, in addition, the reaction yield is also better and is generally 78%-99%, and the enantioselectivity is high and has the highest value of 93%.

Description

technical field [0001] The invention relates to a chiral nitrogen-sulfur bidentate ligand and its synthesis method and application, belonging to the field of chiral compound synthesis. Background technique [0002] Chirality is a common natural phenomenon, ranging from the spiral direction of galaxies in the universe to the arrangement of different functional groups in molecules, all related to chirality. Chiral substances are involved in many physiological activities in organisms. Similar substances with the same chemical composition but different chirality may have completely different effects when entering the organism. Taking the "Thalidomide" incident as an example, the Federal German pharmaceutical company put the compound Thalidomide (Thalidomide) into the European market as an anti-pregnancy drug, and later found that the drug has a strong teratogenic effect on newborn babies. Studies have shown that Thalidomide The molecule contains a chiral C-N bond, and the drug ...

Claims

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Application Information

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IPC IPC(8): C07D213/81B01J31/22C07B53/00C07C67/343C07C69/65
Inventor 赵晓明高宁蔡成思蔡爵旺
Owner TONGJI UNIV
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