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Axial chiral cyclic diphenol compound and its preparation method and application

A compound and axial chiral technology, applied in the field of chiral compounds and their preparation, can solve the problems of limited ligand diversity, unfavorable ligand modification, etc.

Active Publication Date: 2018-04-10
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Unfortunately, the existing bridging chains are all realized through the ether bond formed by the alkyl-oxygen-aryl group, which is not conducive to the further modification of the ligand, so the diversity of such ligands has so far been limited. Very limited, so it is necessary to provide an axial chiral compound with a new structure

Method used

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  • Axial chiral cyclic diphenol compound and its preparation method and application
  • Axial chiral cyclic diphenol compound and its preparation method and application
  • Axial chiral cyclic diphenol compound and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0096] Preparation of compounds shown in embodiment 1, formula I-1 and formula II-1

[0097]

[0098] The reaction equation is as figure 2 shown.

[0099] 13.5g (50mmol) of compound 1 was dissolved in 250ml of tetrahydrofuran, added 5.7g (150mmol) of sodium borohydride, then stirred at room temperature for 12 hours, added 250ml of water, adjusted to pH 1-2 with concentrated hydrochloric acid, then extracted with ethyl acetate, washed once with water, saturated Washed once with brine, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to obtain 13.5 g of Compound A with a yield of 99%.

[0100] 6.12g (90mmol) of imidazole, 19.7g (75mmol) of triphenylphosphine were dissolved in 100ml of dichloromethane, then 12g (75mmol) of liquid bromine was added under ice cooling, stirred for 10 minutes, 8.22g (30mmol) of compound A was added, stirred for 30 minutes, and then directly separated by column chromatography to obtain 11.5 g of compound B with a yield ...

Embodiment 2

[0112] Preparation of compounds shown in embodiment 2, formula I-2 and formula II-2

[0113]

[0114] The reaction equation is as image 3 shown.

[0115] Synthesis of compound shown in formula 2': 1,3-propyl bis (triphenyl bromide ) (17.8mmol, 12.8g) was dissolved in 100mL dry tetrahydrofuran and heated to 70°C. Then add 2.5N n-butyllithium (37mmol, 14.8mL), and then reflux for 0.5 hours, the reaction generates Ph 3 P=CHCH 2 CH=PPh 3 . The compound represented by Formula 1 (14.8 mmol, 4 g) was added to the above solution, and refluxed for 0.5 hours. The reaction solution was cooled to room temperature, and the solution was concentrated by a rotary evaporator, and the residue was separated by column chromatography to obtain the compound shown in Formula 2', yield: 31.6% (1.3g).

[0116] Synthesis of the compound shown in formula 3': the compound shown in formula 2 (4.7mmol, 1.3g) was dissolved in 20mL of dry methylene chloride, boron tribromide (23.5mmol, 5.8g) was ...

Embodiment 3

[0125] Preparation of compounds shown in embodiment 3, formula I-3 and formula II-3

[0126]

[0127] The reaction route is as image 3 In the reaction equation shown, only the number of methylene groups in the compound shown in the raw material formula a is changed to 2, and the rest are the same.

[0128] Synthesis of compound shown in formula 2 ": 1,4-butyl bis (triphenyl bromide ) (17.8mmol, 13.1g) was dissolved in 100mL dry tetrahydrofuran and heated to 70°C. Then add 2.5N n-butyllithium (37mmol, 14.8mL), and then reflux for 0.5 hours, the reaction generates Ph 3 P=CHCH 2 CH 2 CH=PPh 3 (Formula a). The compound represented by Formula 1 (14.8 mmol, 4 g) was added to the above solution, and refluxed for 0.5 hours. The reaction solution was cooled to room temperature, and the solution was concentrated by a rotary evaporator, and the residue was separated by column chromatography to obtain the compound shown in formula 2", yield: 45.0% (1.9g).

[0129] Synthesis o...

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Abstract

The invention discloses an axially chiral cyclo-diphenol compound as well as a preparation method and application thereof. The structural formula of the axially chiral cyclo-diphenol compound is shown in the formula I or formula II, wherein n represents a natural number of 1-5, R1 and R2 represent at least one substituent group on a benzene ring, R3 represents at least one substituent group on a ring A, and R1, R2 and R3 are respectively and independently selected from C1-C5 alkyl, aryl, halogen, nitryl, ether group, sulphonyl, phosphonyl, amino, amide group and ester group; and aryl can be phenyl. The axially chiral cyclo-diphenol compound shown in the formula I or formula II can be used as a chiral ligand in asymmetric reaction. The axially chiral cyclo-diphenol compound shown in the formula I or formula II can be successfully applied to asymmetric reaction of aryl formaldehyde and diethylzinc and has relatively high reaction activity and enantioselectivity.

Description

technical field [0001] The invention relates to a chiral compound and its preparation method and application, in particular to an axial chiral cyclic diphenol compound and its preparation method and application. Background technique [0002] Photoactive organic compounds widely exist in biomolecules, natural products, and pharmaceuticals, and their preparation is mainly through enzymatic organic reactions, organocatalysis, and transition metal asymmetric synthesis. Its catalytic efficiency is highly dependent on chiral induction sources, such as chiral amino acid residues in enzymes, chiral catalysts, and chiral ligands of transition metals. Among the existing asymmetric syntheses, organocatalytic and transition metal catalyzed asymmetric syntheses are most commonly used. Therefore, the development of chiral organocatalysts, especially chiral ligands, is crucial. Over the past few decades, thousands of chiral ligands, many of which are axially chiral, have been developed a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C39/17C07C39/42C07C37/055C07C37/00C07C33/18C07C29/40
CPCC07B2200/07C07C29/40C07C37/00C07C37/055C07C37/0555C07C39/17C07C39/42C07C41/18C07C41/20C07C41/22C07C41/26C07C41/30C07C43/21C07C43/215C07C43/225C07C43/23C07C68/00C07C68/08C07C69/96C07C33/18
Inventor 付华张鹏翔彭飞吴旭东刘灿于吉攀杨海军
Owner TSINGHUA UNIV