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C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands as well as synthetic method and application thereof

A diphenylamine-type and bisoxazoline technology, which is applied in the field of de-C2-symmetrical diphenylamine-type chiral bisoxazoline ligands and its synthesis and application, can solve the problem of single electronic effect, and achieve a simple synthesis method , improve enantioselectivity, mild condition effect

Active Publication Date: 2019-09-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the existing chiral ligand skeleton has a single electronic effect. When applied to asymmetric catalytic reactions, there is still room for further improvement of the enantioselectivity of the reaction, and the types of catalytic reactions need to be further expanded.

Method used

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  • C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands as well as synthetic method and application thereof
  • C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands as well as synthetic method and application thereof
  • C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands as well as synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041]

[0042] 5.48g anthranilic acid, 7.44g 2-chloro-5-methoxybenzoic acid, 5.52g K 2 CO 3 , 0.378g copper powder and 1.14g CuI were added to the round bottom flask and mixed, then DMF was added, and placed at reflux temperature to react for 3 hours. After cooling, filter, add dilute hydrochloric acid to the filtrate until the solution is weakly acidic, stir and filter with suction to obtain the solid product 2-((2-carboxyphenyl)amino)-5-methoxybenzoic acid.

[0043] 1.35g (R)-(-)-2-phenylglycinol, 2.20g 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1.55g 1-hydroxy Benzotriazole was dissolved in THF, and 1.44 g of 2-((2-carboxyphenyl)amino)-5-methoxybenzoic acid was added. React at room temperature for 12 hours. Quench the reaction with ammonium chloride solution, remove the solvent under reduced pressure, add ethyl acetate to dissolve, wash with water, and extract three times. The organic phase is dried with sodium sulfate, the solvent is removed, and i...

Embodiment 2

[0047]

[0048] 5.48g anthranilic acid, 6.98g 2-chloro-5-fluorobenzoic acid, 5.52g K 2 CO 3 , 0.378g copper powder and 1.14g CuI were added to the round bottom flask and mixed, then DMF was added, and placed at reflux temperature to react for 3 hours. After cooling, filter, add dilute hydrochloric acid to the filtrate until the solution is weakly acidic, stir and filter with suction to obtain the solid product 2-((2-carboxyphenyl)amino)-5-fluorobenzoic acid.

[0049] 1.35g (R)-(-)-2-phenylglycinol, 2.20g 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1.55g 1-hydroxy Benzotriazole was dissolved in THF, and 1.10 g of 2-((2-carboxyphenyl)amino)-5-fluorobenzoic acid was added. React at room temperature for 12 hours. Quench the reaction with ammonium chloride solution, remove the solvent under reduced pressure, add ethyl acetate to dissolve, wash with water, and extract three times. The organic phase is dried with sodium sulfate, the solvent is removed, and it i...

Embodiment 3

[0053]

[0054] 5.48g anthranilic acid, 9.42g 2-chloro-5-bromobenzoic acid, 5.52g K 2 CO 3 , 0.378g copper powder and 1.14g CuI were added to the round bottom flask and mixed, then DMF was added, and placed at reflux temperature to react for 3 hours. After cooling, filter, add dilute hydrochloric acid to the filtrate until the solution is weakly acidic, stir and filter with suction to obtain the solid product 2-((2-carboxyphenyl)amino)-5-bromobenzoic acid.

[0055] 1.68g 2-((2-carboxyphenyl)amino)-5-bromobenzoic acid and 10mL SOCl 2 Add it to a round-bottomed flask, heat to reflux for 4 hours, and remove excess SOCl by rotary evaporation 2 , Add the diacid chloride obtained from the precipitation into dichloromethane. Under the condition of ice bath, the dichloromethane solution of diacid chloride was added dropwise to the dichloromethane solution containing 1.35g (R)-(-)-2-phenylglycinol and 3.8mL triethylamine. After the dropwise addition was completed, it was stirred...

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Abstract

The invention discloses C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands represented by a formula 3 shown in the description, a synthetic method of the ligands and an application ofthe ligands in an asymmetric catalytic reaction. According to the ligands provided by the invention, different groups are introduced to a diphenylamine skeleton to remove C2-symmetry to realize precise regulation and control of an ''electron effect'' of the ligand skeleton; and the ligands are prepared by the steps of preparing a compound represented by a formula 1 shown in the description by using an anthranilic acid derivative and an o-chlorobenzoic acid derivative as starting materials, performing a reaction on the compound represented by the formula 1 and a chiral amino alcohol compound represented by a formula 4 shown in the description to obtain beta-bishydroxyamide represented by a formula 2 shown in the description, and performing condensation on the beta-bishydroxyamide to obtainthe C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands represented by the formula 3. The invention also provides the application of a catalyst formed by performing coordination on the C2-symmetry-removing diphenylamine-type chiral bisoxazoline ligands, a copper salt, a zinc salt, a nickel salt, an iron salt or a rhodium salt in the asymmetric catalytic reaction.

Description

technical field [0001] The present invention relates to a kind of de-C 2 -Symmetrical diphenylamine-type chiral bisoxazoline ligand and its synthesis method and application. Background technique [0002] Metal complexes, as the most common chemical catalysts, have attracted extensive attention due to their high catalytic performance and excellent chiral induction ability, in which chiral ligands play a vital role as chiral sources. In the early 1990s, Nishiyama et al first reported the first chiral bisoxazoline ligand Pybox and applied it to the asymmetric hydrosilylation reaction of simple ketones, and obtained excellent results (Organometallics, 1991, 10:2706 -2708). So far, chiral bisoxazoline ligands with different skeleton structures have been developed successively. Since Guiry's research group introduced the diphenylamine skeleton into the bisoxazoline ligand for the first time in 2002 (Tetrahedron Letters, 1995, 36:8745-8748), this type of ligand has also been wid...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D263/14C07D263/10B01J31/22C07C67/313C07C69/76C07C67/307C07C69/757C07B53/00C07D307/85C07D209/10C07C331/14
CPCC07D263/14C07D263/10B01J31/2217C07C67/313C07C67/307C07B53/00C07D307/85C07D209/10C07C331/14C07C2602/10C07B2200/07C07C2602/08B01J2531/16C07C69/76C07C69/757B01J31/182B01J2231/348B01J2231/4294B01J2231/4277B01J2540/20B01J2540/225B01J2540/40B01J2540/10B01J2531/0266B01J2531/26B01J2531/822B01J2531/847B01J2531/842C07F1/08B01J31/1815B01J2231/32B01J2231/324B01J2231/44
Inventor 许丹倩王益锋王彪徐振元
Owner ZHEJIANG UNIV OF TECH
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