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Novel pyridyl crown ether-containing chiral diphosphine ligand and application thereof in asymmetric catalytic reaction

A technology of pyridyl crown ether and pyridyl bisphosphorus, which is applied in the field of novel chiral bisphosphorus ligands containing pyridyl crown ether and its application in asymmetric catalytic reactions, and can solve the problems of inability to adjust the ligand structure

Inactive Publication Date: 2016-05-18
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these ligands give good catalytic results in some asymmetric catalytic reactions, these ligands need to be synthesized by different methods, so the structure of the ligands cannot be adjusted by simply changing the catalytic reaction conditions.

Method used

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  • Novel pyridyl crown ether-containing chiral diphosphine ligand and application thereof in asymmetric catalytic reaction
  • Novel pyridyl crown ether-containing chiral diphosphine ligand and application thereof in asymmetric catalytic reaction
  • Novel pyridyl crown ether-containing chiral diphosphine ligand and application thereof in asymmetric catalytic reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0077] Example 1: Preparation of pyridyl crown ether compound II by 2,6-dichloropyridine

[0078]

[0079] Add NaH (1.92g, 80.0mmol) and KPF to a dry 500mL three-necked flask 6 (3.86g, 21mmol), N 2 Add THF (200mL) under protection, heat to reflux, slowly drop a THF solution (100mL) of 2,6-dichloropyridine (2.96g, 20.0mmol) and tetraethylene glycol (3.88g, 20.0mmol) into the reaction solution . After the addition was completed, the reaction was continued under reflux for three days. After cooling to room temperature, the excess NaH was quenched with methanol and water, the solvent was evaporated under reduced pressure, and the 2 Cl 2 (100mL) and water (70mL) to dissolve the reactant, extract and separate, and use CH 2 Cl 2 (20 mL×3) extraction. The combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by column chromatography (SiO 2 :acetone / CH 2 Cl 2 =1:10) to obtain pyridyl crown ether compoun...

Embodiment 2

[0080] Embodiment 2: Preparation of monobrominated pyridyl crown ether compound III by pyridyl crown ether compound II

[0081]

[0082] Add compound II (2.45 g, 9.12 mmol) and CH in a 100 mL single-necked round bottom flask 2 Cl 2 (50mL), after the reaction solution was cooled to -70°C, CH 2 Cl 2 The solution (50 mL) was slowly added dropwise into the single-necked flask. Monitor the reaction by TLC until the raw material disappears, and add saturated Na 2 CO 3 solution to quench the reaction with CH 2 Cl 2 The aqueous phase was extracted (30 mL×3), and the organic phases were combined and dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by column chromatography (SiO 2 :acetone / CH 2 Cl 2 =1:100) to obtain the dibrominated by-product and the target product monobromopyridyl crown ether compound III (white solid, 2.71g, 85% yield). 1 HNMR (500MHz, CDCl 3 ): δ7.62(d, J=8.0Hz, 1H), 6.24(d, J=8.0Hz, 1H), 4.68(t, J=5.7Hz,...

Embodiment 3

[0083] Example 3: Preparation of monophosphine ligand IV containing pyridyl crown ether from monobromopyridyl crown ether compound III

[0084]

[0085] Add i-Pr to a 500 mL dry two-neck round bottom flask 2 NH (30.1mL, 214mmol) and THF (100mL), the reaction flask was placed in a low-temperature cooling liquid at -78°C, and the n-BuLi (84.5mL, 186mmol, 2.2Minhexane) solution was slowly added dropwise to the round bottom flask. Maintain the reaction mixture at -78°C and stir for 10 minutes, warm up to -10°C and stir for 30 minutes, then put it into a low-temperature cooling liquid at -78°C, and add monobromopyridyl crown ether compound III (49.6g, 142mmol) in THF The solution (100 mL) was slowly added dropwise to the LDA solution just prepared. After the addition was complete, the reaction mixture was stirred for 30 minutes, and then (3,5-Me 2 C 6 h 3 ) 2 PCl (43.5 g, 157 mmol) was dissolved in THF (30 mL). After the dropwise addition, the reaction mixture was slowly wa...

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Abstract

The invention discloses a novel pyridyl crown ether-containing chiral diphosphine ligand and an application thereof in an asymmetric catalytic reaction. The structural formulas of the chiral diphosphine ligand and an intermediate thereof, namely a pyridyl crown ether-containing monophosphorous ligand are shown by (I) and (I') respectively. The transition metal compounds of the chiral diphosphine ligands can serve as a catalyst of an asymmetric reaction; the pyridyl crown ether-containing chiral diphosphine ligand is a kind of novel adjustable chiral ligand; and through the complexing of different objects such as alkali metal ions, alkaline-earth metal ions, rare-earth metal ions, ammonium salt and organic amine salt with a ligand, the control on the space structure and electronic properties of the catalyst can be realized. The transition metal (Rh and Ir) complex of the pyridyl crown ether-containing chiral diphosphine ligand in complexing assembly with alkali metal ions shows excellent catalytic activity and good stereoselectivity.

Description

technical field [0001] The present invention relates to the synthesis of a novel pyridyl crown ether-containing chiral bisphosphorus ligand and its transition metal complexes with adjustable spatial structure and electronic properties. These transition metal complexes can be used as catalysts for asymmetric reactions, such as: Hydrogenation, Hydrotransfer, Allyl Alkylation, Hydrosilylation, Hydroboration, Hydroformylation, Olefin Metathesis, Hydrocarboxylation, Hydrovinylation, Isomerization, Cyclopropane Reaction, Diels-Alder reaction, Heck reaction, Aldol reaction, Michael addition reaction, epoxidation reaction, kinetic resolution and [m+n] cycloaddition reaction, especially ligand capping of transition metal complexes Ethers can be complexed with different alkali metal ions, alkaline earth metal ions, rare earth metal ions, ammonium salts or organic amine salts to form supramolecular catalysts with a host-guest assembly structure, and realize the regulation of the spatial ...

Claims

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Application Information

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IPC IPC(8): C07F9/6561C07F15/00C07F19/00C07D498/08B01J31/24C07B53/00C07C233/47C07C231/12C07D307/54C07D333/24C07D215/06
CPCC07F9/6561B01J31/2452B01J2231/645B01J2231/646B01J2531/0241B01J2531/822B01J2531/827C07B53/00C07C231/12C07D215/06C07D307/54C07D333/24C07D498/08C07F15/0033C07F15/0073C07C233/47
Inventor 吴静章喜昌李世军
Owner HANGZHOU NORMAL UNIVERSITY
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