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2,2', 6,6'-tetraoxazoline diphenyl ligancy and preparation process thereof

A technology of tetraoxazoline biphenyl and ligand, applied in 2 fields, can solve problems such as waste of resources, and achieve the effects of simple synthesis method, good application prospect, high reactivity and stereoselectivity

Inactive Publication Date: 2006-06-28
SHANGHAI JIAOTONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The purpose of the present invention is to provide a kind of 2,2',6,6'-tetraxazoline biphenyl ligand and its preparation method for the deficiencies in the prior art, so that it avoids the current preparation of single-axis chiral ligands. Problems such as waste of resources that may be caused by the body, and the synthesis method is simple, and the prepared ligand can be used to prepare a catalyst for asymmetric catalytic reactions

Method used

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  • 2,2', 6,6'-tetraoxazoline diphenyl ligancy and preparation process thereof
  • 2,2', 6,6'-tetraoxazoline diphenyl ligancy and preparation process thereof
  • 2,2', 6,6'-tetraoxazoline diphenyl ligancy and preparation process thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] (1) Synthesis of compound I

[0022] Pyrene (3.00g, 14.90mmol) was dissolved in a solution of dichloromethane (60mL), acetonitrile (60mL) and water (100mL), and sodium periodate (29.94g, 140mmol) and trichloride were added to the above solution Ruthenium (120.31 g, 0.58 mmol). The reaction solution was heated to 40°C and stirred for 16h, a yellow precipitate formed. The solid obtained by filtration was dissolved in acetone (200 mL), and the insoluble matter was removed by filtration. The filtrate was concentrated by rotary evaporation to obtain white powder I (2.30 g, 76%).

[0023] 1 H NMR (400MHz, CD 3 COCD 3 ) 6.99 (d, J = 7.6 Hz, 4H, Ar-H), 6.77 (t, J = 7.6 Hz, 2H, Ar-H).

[0024] (2) Synthesis of compound II

[0025] Tetraacid I (1.00 g, 3.03 mmol) was dissolved in dichloromethane (20 mL), placed in an ice bath, and thionyl chloride (1.0 mL, 13.34 mmol) and 16 μLDMF were added to the solution. The temperature of the reaction solution was raised to room temp...

Embodiment 2

[0034] (1) Synthesis of compound I

[0035] The synthesis method refers to (1) in Example 1.

[0036] (2) Synthesis of compound II

[0037] The synthesis method refers to (2) in Example 1.

[0038] (3) Compound III (R 1 =i-Pr,R 2 = R 3 = R 4 =H) Synthesis

[0039] II (1.01 g, 2.49 mmol) was dissolved in dichloromethane (30 mL) and slowly added dropwise to a solution of L-valinol (1.97 g, 14.88 mmol) in dichloromethane (20 mL) under ice bath. After all was added dropwise, triethylamine (2.4 mL, 17.28 mmol) was added rapidly. After stirring at room temperature for 20 hours, wash with water and filter to obtain amido compound III (R 1 =i-Pr, R 2 = R 3 = R 4 =H) (1.44g, 2.14mmol), yield 86%.

[0040] (4) compound IV (R 1 =i-Pr, R 2 = R 3 = R 4 =H) Synthesis

[0041] Methanesulfonyl chloride (1.2 mL, 14.86 mmol) was added dropwise to amido compound III (R 1 =i-Pr,R 2 = R 3 = R 4 =H) (1.0 g, 1.49 mmol), triethylamine (2.5 mL, 17.67 mmol) and dichloromethane (10 mL...

Embodiment 3

[0043] (1) Synthesis of compound I

[0044] The synthesis method refers to (1) in Example 1.

[0045] (2) Synthesis of compound II

[0046] The synthesis method refers to (2) in Example 1.

[0047] (3) Compound III (R 1 =t-Bu, R 2 = R 3 = R 4 =H) Synthesis

[0048] II (1.00 g, 2.46 mmol) was dissolved in dichloromethane (40 mL) and slowly added dropwise to a solution of L-tert-butylleucinol (1.44 g, 12.30 mmol) in dichloromethane (20 mL) under ice bath. After all was added dropwise, triethylamine (1.8 mL, 12.96 mmol) was added rapidly. After stirring at room temperature for 20 hours, wash with water and filter to obtain amido compound III (R 1 =t-Bu, R 2 = R 3 = R 4 =H) (1.51 g, 2.08 mmol), yield 84%.

[0049] 1 H NMR (400MHz, CD 3 OD) 7.46-7.52 (m, 6H, Ar-H), 3.69-3.74 (m, 8H, NCH, OCH), 3.37 (dd, J=10.8, 12.8Hz, 4H, OCH), 0.734 (s, 36H, CH 3 ).

[0050] (4) compound IV (R 1 =t-Bu, R 2 = R 3 = R 4 =H) Synthesis

[0051] Methanesulfonyl chloride (0.5 mL, ...

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Abstract

The invention relates to 2, 2í»,6, 6í»-4-oxazoline biphenyl ligand and the manufacture method that uses pyrene as raw material and oxidizing and opening loop in the oxidizing system of sodium periodate and ruthenium trichloride to gain 2, 2í», 6, 6í»-4-carboxylic acid biphenyl, reacting with thionyl chloride to gain acyl chloride that is dropped into the methylene chloride solution of spasmolytol and alkamine, reacting to gain product that takes reaction with methylsulfonyl chloride and spasmolytol to gain the target product. It has high reacting activity and solid selection and has great prospect. 2, 2í»,6, 6í»-4-oxazoline biphenyl ligand has the structure of R1=hydrogen, phenyl, benzyl group, or alkyl of 1-8 carbon; R2=hydrogen, phenyl, benzyl group, or alkyl of 1-8 carbon; R3=hydrogen, phenyl, benzyl group, or alkyl of 1-8 carbon; and R4=hydrogen, phenyl, benzyl group, or alkyl of 1-8 carbon.

Description

technical field [0001] The present invention relates to a kind of chemical compound and its method in technical field, specifically, relate to a kind of 2,2',6,6'-tetraoxazoline biphenyl ligand and preparation method thereof. Background technique [0002] Oxazoline is a five-membered heterocyclic compound containing N and O atoms. The N atom can be used as an electron-donating atom to coordinate well with metal ions, and oxazoline has been used as a substrate to synthesize various chiral compounds. , and achieved some success, leading chemists to believe that it has great promise as a ligand in asymmetric catalysis. 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, the axial chiral side chain has been widely used in ligands because of its unique rigid structure. In order to obtain axial chiral ligands with a single configuration, they a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D263/12
CPCC07D263/14
Inventor 张万斌张勇健王飞军
Owner SHANGHAI JIAOTONG UNIV
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