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Bisoxazoline ligand compound based on tetramethylspiroindane skeleton and its intermediate, preparation method and use

A technology of tetramethylspirodihydroindene and bisoxazoline, which is applied in the field of bisoxazoline ligand compounds, can solve the problems of lengthy reaction steps, high preparation cost, affecting practicability and the like, and achieves easy large-scale application, The effect of a simple synthetic reaction route

Active Publication Date: 2021-02-12
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, starting from the industrially available raw material m-methoxybenzaldehyde, the corresponding SpiroBOX can be obtained through at least 11 steps of synthesis reaction and 1 step of chiral resolution. The reaction steps are lengthy and the preparation cost is high, which affects the practicability.

Method used

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  • Bisoxazoline ligand compound based on tetramethylspiroindane skeleton and its intermediate, preparation method and use
  • Bisoxazoline ligand compound based on tetramethylspiroindane skeleton and its intermediate, preparation method and use
  • Bisoxazoline ligand compound based on tetramethylspiroindane skeleton and its intermediate, preparation method and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] 3,3,5,3',3',5'-hexamethyl-1,1'-spiroindane-7,7'-dicarbaldehyde (II-b) and 3,3,5,3' ,Synthesis of 3',5'-hexamethyl-1,1'-spiroindane-7,7'-dicarboxylic acid (III-b)

[0037]

[0038] The first step: In a 500mL three-necked flask, add 3,3,5,3',3',5'-hexamethyl-1,1'-spirodihydroindane-6,6'-diol (HMSPINOL, 10mmol, 3.4g), hexamethylenetetramine (HMTA, 80mmol, 11.2g), N 2 Protect. Then 120 mL of trifluoroacetic acid was added, and the reaction was refluxed overnight. The next day, 120 mL of glacial acetic acid was added, and the reflux reaction was continued for 3 days. Then the temperature was lowered to 95° C., 120 mL of hydrochloric acid (4 mol / L) was added, stirred for 5 hours, the reaction was stopped, and the temperature was lowered to room temperature. The reaction solution was poured into water, a large amount of precipitates were precipitated, and the yellow solid product II-b1 (3.2 g, yield: 82%) was obtained by suction filtration. m.p.283.7-285.6°C; 1 H NMR ...

Embodiment 2

[0043] (S)-3,3,5,3',3',5'-hexamethyl-1,1'-spiroindane-7,7'-dicarbaldehyde ((S)-II-b) and (S)-3,3,5,3',3',5'-Hexamethyl-1,1'-spiroindane-7,7'-dicarboxylic acid ((S)-III-b) synthesis

[0044]According to the process of Example 1, chiral (S)-3,3,5,3',3',5'-hexamethyl-1,1'-spirodihydroindene-6,6'-bis alcohol ((S)-HMSPINOL) instead of 3,3,5,3',3',5'-hexamethyl-1,1'-spiroindane-6,6'-diol (HMSPINOL), i.e. The corresponding (S)-3,3,5,3',3',5'-hexamethyl-1,1'-spirodihydroindene-7,7'-dicarbaldehyde ((S)- II-b, total yield 65%) and (S)-3,3,5,3',3',5'-hexamethyl-1,1'-spiroindane-7,7'-bis Formic acid ((S)-III-b, 60% overall yield).

Embodiment 3

[0046] Synthesis of 3,3,3',3'-tetramethyl-1,1'-spiroindane-6,6'-dihydroxy-7,7'-dicarbaldehyde (II-c)

[0047]

[0048] Add 5.2g compound (BMSPINOL, 12.4mmol), 10.8g hexamethylenetetramine (HMTA, 77mmol) in the reaction bottle, nitrogen protection, add 150mL trifluoroacetic acid (TFA), heat and reflux overnight, then add 150mL acetic acid , continue the reflux reaction for 72 hours, add 200 mL of 6 mol / L hydrochloric acid, stir and reflux for 28 hours for hydrolysis, add 100 mL of water, continue stirring and reacting for 24 hours, then cool the reaction solution, suction filter and fully wash the filter cake with water, and dry the filter cake to obtain 4.6g yellow powdery solid product II-aa, yield 80%. The melting point is 226-227°C. 1 H NMR (400MHz, CDCl 3 )δ12.55(s, 2H), 9.60(s, 2H), 7.30(s, 2H), 2.56(d, J=13.5Hz, 2H), 2.39(d, J=13.5Hz, 2H), 1.42( s,18H),1.37(s,6H),1.35(s,6H).

[0049] Add 2g of compound II-aa (4.2mmol) and 10g of anhydrous aluminum chloride (75mmol...

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Abstract

The invention discloses a bisoxazoline ligand compound based on a tetramethylspiroindane skeleton, an intermediate, a preparation method and an application thereof. The bisoxazoline ligand compound is a compound having a structure represented by general formula I or an enantiomer, a racemate or a diastereomer of the compound. The bisoxazoline ligand is prepared from cheap and easy-to-obtain tetramethylspiroindanediol as a starting material through a series of reaction steps, and the key intermediate is a compound having the structure shown in the general formula II. The invention develops a novel oxazoline ligand, which can be used to catalyze organic reactions, especially can be widely used as a chiral oxazoline ligand in metal-catalyzed asymmetric reactions, and has economical practicability and industrial application prospects.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, and relates to a novel bisoxazoline ligand compound based on a tetramethylspiroindane skeleton, an intermediate, a preparation method and an application thereof. Such ligands can be used in coupling reactions or asymmetric catalytic reactions. Background technique [0002] Asymmetric catalysis is one of the most active research fields in synthetic chemistry today, and this technology is the most direct and effective chemical method to obtain chiral compounds. It has the advantages of chiral multiplication, high enantioselectivity, economy and easy industrialization. Realizing highly efficient and selective asymmetric catalytic reactions is a challenging topic in the field of synthetic chemistry. One of the core scientific issues is the development and discovery of new and efficient chiral ligands and their catalysts. Although the design and synthesis of chiral ligands has achieved rap...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D263/12C07D263/14C07D263/64B01J31/22C07D307/93C07F7/08
CPCC07D263/12C07D263/14C07D263/64C07D307/93C07F7/0805B01J31/22C07B2200/07C07B2200/13B01J2531/0266B01J2231/42B01J2531/842C07D413/10
Inventor 林旭锋顾昊睿孙伟晔
Owner ZHEJIANG UNIV
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