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Process for synthesizing 5,5' bit connected 1,1'-diphenyl kind axle chirality ligand

A synthesis method and axial chirality technology, which can be applied in the direction of organic chemistry, etc., can solve the problems of restricting and restricting the rotation angle of biphenyl, and achieve the effect of good application prospect, high reactivity and stereoselectivity.

Inactive Publication Date: 2007-11-14
SHANGHAI JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Its disadvantage is that these two larger groups also limit the angle at which biphenyl can rotate, that is, limit the dihedral angle

Method used

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  • Process for synthesizing 5,5' bit connected 1,1'-diphenyl kind axle chirality ligand
  • Process for synthesizing 5,5' bit connected 1,1'-diphenyl kind axle chirality ligand
  • Process for synthesizing 5,5' bit connected 1,1'-diphenyl kind axle chirality ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] (1) Preparation of compound IV from 2-bromo-4-methoxybenzophenone

[0040] Under ice bath, slowly drop bromine (2.8mL, 35.1mmol) into NaOH (4.5g, 111.4mmol) aqueous solution (10mL), stir for 10min, then add 2-bromo-4-methoxybenzophenone (2.1 g, 9.2mmol) was dropped into the above reaction solution and stirred at room temperature for 15h. After the reaction finishes, add aqueous sodium sulfite to eliminate unreacted sodium hypobromite. The neutral compound was separated by extraction with ethyl acetate, and the aqueous phase was acidified with 6N hydrochloric acid in an ice bath, and a large amount of white solid appeared. Filtration afforded IV as a white solid (2.0 g, 95%).

[0041] 1 H NMR (CDCl 3 , 300MHz) 8.05 (d, J = 8.7Hz, 1H, Ar-H), 7.23 (d, J = 2.7Hz, 1H, Ar-H), 6.91 (dd, J = 8.7, 2.7Hz, 1H, Ar- H), 3.87(s, 3H, OCH 3 ).

[0042] (2) Preparation of Compound V from Compound IV

[0043]Under ice-cooling, thionyl chloride (2.9mL, 38.7mmol) was slowly added d...

Embodiment 2

[0061] (1) Preparation of compound IV from 2-bromo-4-methoxybenzophenone

[0062] Under ice bath, bromine (2.7mL, 34.2mmol) was slowly dropped into NaOH (4.5g, 111.4mmol) aqueous solution (20mL), stirred for 10min, and then 2-bromo-4-methoxybenzophenone (1.3 g, 5.7 mmol) was dropped into the above reaction solution and stirred at 50°C for 15h. After the reaction finishes, add aqueous sodium sulfite to eliminate unreacted sodium hypobromite. The neutral compound was separated by extraction with ethyl acetate, and the aqueous phase was acidified with 6N hydrochloric acid in an ice bath, and a large amount of white solid appeared. Filtration afforded IV as a white solid (1.2 g, 92%).

[0063] (2) Preparation of Compound V from Compound IV

[0064] Under ice-cooling, thionyl chloride (3.2mL, 42.8mmol) was slowly added dropwise to a solution of 2-bromo-4-methoxybenzoic acid IV (1.0g, 4.3mmol) in methanol (10mL), raised to It was heated to reflux at room temperature, and the rea...

Embodiment 3

[0076] (1) Preparation of compound IV from 2-bromo-4-methoxybenzophenone

[0077] Under ice bath, slowly drop bromine (1.6mL, 20.3mmol) into NaOH (3.5g, 86.6mmol) aqueous solution (40mL), stir for 10min, then add 2-bromo-4-methoxybenzophenone (1.5 g, 6.6 mmol) was dropped into the above reaction solution and stirred at 70°C for 15h. After the reaction finishes, add aqueous sodium sulfite to eliminate unreacted sodium hypobromite. The neutral compound was separated by extraction with ethyl acetate, and the aqueous phase was acidified with 6N hydrochloric acid in an ice bath, and a large amount of white solid appeared. Filtration afforded IV as a white solid (0.9 g, 61%).

[0078] (2) Preparation of Compound V from Compound IV

[0079] Under ice-cooling, thionyl chloride (1.6mL, 21.4mmol) was slowly added dropwise to a solution of 2-bromo-4-methoxybenzoic acid IV (1.0g, 4.3mmol) in methanol (10mL), raised to It was heated to reflux at room temperature, and the reaction was m...

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Abstract

The invention relates to 5, 5' connecting 1, 1'-biphenyl class axis chirality ligand. It uses 2-bromine-4-anisole ketone as raw material to take oxidation and esterification to gain compounding V, which would gain 5, 5'-dihydroxy-1, 1'-biphenyl -2, 2'-bimethyl formate that would react with saturated dihalide to gain 5,5'-connecting-(R) and (S)configuration compounding that would take reaction with chirality alkamine to gain (R) and (S) type amide class compounding, finally using methylsulfonyl chloride to gain the target compound under the condition of spasmolytol existing. It could be used in kinds of asymmetry reaction, has high reacting activity and solid selection, and bright application prospect.

Description

technical field [0001] The invention relates to a method in the technical field of chemical engineering, in particular to a method for synthesizing 1,1'-biphenyl-like axial chiral ligands connected at the 5,5' position. Background technique [0002] The key to asymmetric catalytic synthesis is how to design and synthesize chiral catalysts with high selectivity and catalytic activity, in which chiral ligands are the source of asymmetric induction and control of catalysts. C2-type chiral bisoxazoline ligands are widely used in metal-catalyzed asymmetric reactions due to their special structure, such as asymmetric cyclopropanation, intramolecular Wacker-Type cyclization, and asymmetric reactions of alkenes. Symmetric oxidation reactions and intramolecular [2+1] cycloaddition reactions, etc. After 30 years of development, a large number of chiral oxazoline ligands have emerged, especially chiral oxazoline ligands with various chiral side chains have been developed. Among them,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D413/14
Inventor 张万斌张勇健王飞军
Owner SHANGHAI JIAOTONG UNIV