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Chiral oxazoline NNP type ligands as well as synthesis method and application thereof

A chiral oxazoline and ligand technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, carbon-based compound preparation, etc., can solve problems such as limiting the effect of catalysts

Active Publication Date: 2017-04-26
SHANGHAI NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Traditional ligands only provide a chiral environment during the catalytic process, and their coordination mode generally does not change, and the ligands rarely participate in the reaction, which limits the role of catalysts to a large extent.

Method used

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  • Chiral oxazoline NNP type ligands as well as synthesis method and application thereof
  • Chiral oxazoline NNP type ligands as well as synthesis method and application thereof
  • Chiral oxazoline NNP type ligands as well as synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0091] A kind of chiral oxazoline class NNP type ligand synthetic method is as follows:

[0092] (1) Synthesis of intermediate S-4a.

[0093]

[0094] Take a 500mL reaction flask, add chiral amino acid S-3a (4.5g, 38.8mmol), dioxane (40mL) and 10% sodium carbonate (100mL) to the reaction flask respectively, and place the reaction flask in an ice bath , stirred mechanically, added 9-fluorenylmethyl chloroformate (10.0 g, 38.8 mmol) and dioxane (100 mL) into the dropping funnel, slowly dropped into the reaction flask, gradually returned to room temperature and stirred overnight. After the reaction was completed, add 100 mL of water, extract three times with 50 mL of ether, take the water phase and put it in an ice bath to cool, and add 1M dilute HCl until the pH is 1. The aqueous solution was extracted three times with 50 mL of ethyl acetate. The oil phases were combined, dried with magnesium sulfate, filtered and spin-dried to obtain intermediate S-4a (12.6 g, 96%).

[00...

Embodiment 2

[0111] Example 2: The intermediate S-8a was prepared by the same method as in Example 1, and then the catalyst 1b was obtained by the following method.

[0112]

[0113] Take a 25mL dry reaction flask and fill it with argon gas to protect it. Add intermediate S-8a crude product (1.9g, 3.8mmol) and anhydrous dichloromethane (20mL) to the reaction flask respectively, cool to -70°C, and slowly add 3M benzene Magnesium bromide (5.1 mL, 15.2 mmol). After the reaction is completed, add saturated ammonium chloride solution to quench, add dichloromethane to extract and separate the liquids, dry the oil phase over magnesium sulfate, filter and spin dry. The catalyst 1b (511mg, 24%) was obtained by using ethyl acetate:petroleum ether=1:20 to pass through the column.

[0114] White solid.IR(KBr)v max 3427,2964,1655,1454,1434,1089,744,697cm -1 ; 1 H NMR (400MHz, CDCl 3 )δ8.01-7.98(m,1H),7.41-7.12(m,18H),7.04-6.92(m,6H),6.10(d,J=8.8Hz,1H),5.24(t,J=9.6Hz ,1H),4.55(t,J=9.2Hz,1H),4....

Embodiment 3

[0115] Example 3: The intermediate S-8a was prepared by the same method as in Example 1, and then the catalyst 1c was obtained by the following method.

[0116]

[0117] Take a 25mL dry reaction bottle and protect it with argon, add the crude intermediate S-8a (1.2g, 2.5mmol) and anhydrous dichloromethane (10mL) to the reaction bottle respectively, cool to -70°C, and slowly add 3M iso Propylmagnesium bromide (3.3 mL, 10 mmol). After the reaction is completed, add saturated ammonium chloride solution to quench, add dichloromethane to extract and separate the liquids, dry the oil phase over magnesium sulfate, filter and spin dry. The catalyst 1c (550mg, 41%) was obtained by using ethyl acetate:petroleum ether=1:20 to pass through the column.

[0118] colorless liquid, 1 H NMR (400MHz, DMSO-d6) δ7.69(s, 1H), 7.40-7.11(m, 17H), 6.97-6.94(m, 1H), 5.15(t, J=9.6Hz, 1H), 4.74( s,1H),4.47(t,J=9.2Hz,1H),3.81(t,J=8.5Hz,1H),2.69(d,J=4.8Hz,1H),1.82-1.73(m,2H), 0.91(d, J=6.4Hz, 3H), ...

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PUM

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Abstract

The invention relates to chiral oxazoline NNP type ligands as well as a synthesis method and an application thereof. The ligands adopt the structure shown in general formula 1 or 2. During preparation, a chiral ligand 1 and a chiral ligand 2 are prepared from Fmoc-Cl and a chiral amino acid compound 3 used as initial raw materials through multi-step reactions. The ligands can be applied to catalytic synthesis of chiral beta ketone ester fluoride and synthesis of propanedione derivatives and chiral malonate derivatives through palladium-catalyzed asymmetric allyl substitution reactions. Compared with the prior art, the reaction condition is mild, operation is easy, repeatability is good, mass preparation can be realized, and the prepared catalyst has higher ee value and yield when applied to beta ketone ester fluoridation and palladium-catalyzed asymmetric allyl substitution reactions.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a synthesis method and application of a chiral oxazoline NNP ligand. Background technique [0002] In recent decades, the research on asymmetric synthesis reactions has achieved vigorous development. Chemists have successfully developed thousands of asymmetric synthetic methods, the vast majority of which rely on the use of chiral ligands. Therefore, the design and synthesis of chiral ligands is a crucial link in asymmetric catalysis. Because there is no universal ligand, and many excellent ligands and catalysts have been patented, its industrial application is greatly limited. Therefore, synthesizing new ligands with independent intellectual property rights, studying the regularity of the influence of their complexes on catalytic reactions, and developing efficient asymmetric catalytic methodology are one of the challenging tasks in the future and are of great signific...

Claims

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Application Information

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IPC IPC(8): C07F9/653B01J31/24C07C67/307C07C69/757C07C45/68C07C49/223C07C49/796C07C67/343C07C69/618C07C69/65C07C201/12C07C205/56
Inventor 邓清海刘炎开吴敦奇
Owner SHANGHAI NORMAL UNIVERSITY
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