Chirality phosphine nitrogen compound containing N-aryl as well as synthetic method and application thereof

A synthesis method and compound technology, which can be applied to organic compounds/hydrides/coordination complex catalysts, compounds of Group 5/15 elements of the periodic table, chemical instruments and methods, etc., which can solve the problem of expensive, diastereomeric selection It can solve the problems of poor control of properties and poor control of enantioselectivity, so as to achieve the effect of expanding the scope of use, high enantioselectivity and excellent yield.

Active Publication Date: 2013-05-08
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The synthesis of this kind of ligand is relatively complicated. Although it has been commercialized, the price is very expensive. More importantly, it has great limitations and the universality of the substrate is not very good.
Such as poor enantioselectivity control for ortho-substituted cinnamon carbonate substrates [(a) López, F.; Ohmura, T.; Hartwig, J.F.J. Am. Chem. Soc. 2003, 125, 3426. (b ) Polet, D.; Alexakis, A.; Tissot-Croset, K.; Corminboeuf, C.; .;Hartwig, J.F.J.Am.C

Method used

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  • Chirality phosphine nitrogen compound containing N-aryl as well as synthetic method and application thereof
  • Chirality phosphine nitrogen compound containing N-aryl as well as synthetic method and application thereof
  • Chirality phosphine nitrogen compound containing N-aryl as well as synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Embodiment 1: Synthesis based on axial chiral N-arylphosphine nitrogen compounds:

[0044]

[0045] Under argon protection, add toluene (50mL) and triphenylphosphine (0.67mL, 7.7mmol) into a dry 250ml three-necked flask, cool to 0°C; in another dry 25ml flask In , add aromatic secondary amine (7.7mmol), toluene (8mL), and triethylamine (1.8mL, 12.9mmol) to make a mixed solution, and then gradually drop the mixed solution into the above 250ml flask. After the dropwise addition, the temperature was raised to 80°C for 6 hours, and then gradually cooled to 0°C. A solution of binaphthyl diol (BINOL) (7.0 mmol) and triethylamine (3.5 mL, 25.2 mmol) in toluene (30 mL) and tetrahydrofuran (6 mL) was slowly added to the system. The system was stirred overnight at room temperature (25°C), filtered through celite, and the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (petroleum ether / ethyl acetate / triethylamine: ...

Embodiment 2

[0154] Embodiment 2: Synthesis based on axial chiral N-arylphosphine nitrogen compounds:

[0155]

[0156] Under argon protection, add toluene (50mL) and triphenylphosphine (0.67mL, 7.7mmol) into a dry 250ml three-necked flask, cool to 0°C; in another dry 25ml flask In , add aromatic secondary amine (7.7mmol), toluene (8mL), and triethylamine (1.8mL, 12.9mmol) to make a mixed solution, and then gradually drop the mixed solution into the above 250ml flask. After the dropwise addition, the temperature was raised to 80°C for 6 hours, and then gradually cooled to 0°C. A solution of diphenol 2 (7.0 mmol) and triethylamine (3.5 mL, 25.2 mmol) in toluene (30 mL) and tetrahydrofuran (6 mL) was slowly added to the system. The system was stirred overnight at room temperature (25°C), filtered through celite, and the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (petroleum ether / ethyl acetate / triethylamine: 20 / 1 / 0.01). ...

Embodiment 3

[0171] Embodiment 3: Synthesis based on axial chiral N-arylphosphine nitrogen compounds:

[0172]

[0173] Under argon protection, in a dry 250 ml three-necked flask, add toluene (50 mL) and triphenylphosphine (0.67 mL, 7.7 mmol), cool to 0 °C; in another dry 25 ml flask , Add aromatic secondary amine (7.7mmol), toluene (8mL), and triethylamine (1.8mL, 12.9mmol) to prepare a mixed solution, and then gradually drop the mixed solution into the above-mentioned 250ml flask. After the dropwise addition was completed, the temperature was raised to 80° C. for 6 hours, and then gradually cooled to 0° C. A solution of diphenol 3 (7.0 mmol) and triethylamine (3.5 mL, 25.2 mmol) in toluene (30 mL) and tetrahydrofuran (6 mL) was slowly added to the system. The system was stirred overnight at room temperature (25°C), filtered through celite, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (petroleum ether / ethyl acetate / ...

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Abstract

The invention provides a chirality phosphine nitrogen compound containing N-aryl as well as a synthetic method and application thereof. The phosphine nitrogen compound is based on axial chirality or comprises a helical chirality skeleton, and is synthetized by taking optically pure axial chirality or helical chirality glycols compound, phosphorus trichloride and aromatic secondary amine as raw material for reaction. The raw material used in the method is easy to obtain, the reaction condition is mild, and the products are easy to separate and purify. The N-aryl phosphine nitrogen compound base on the axial chirality or the helical chirality skeleton synthetized by the method can be effectively applied in substitution reaction of allyl catalyzed by metal iridium, so that the product can be obtained with high enantioselectivity and regioselectivity, and the substrate scope of the product is greatly widened.

Description

technical field [0001] The present invention relates to N-aryl phosphine nitrogen compounds based on axial chiral or helical chiral skeleton, a synthesis method and application thereof. The method can synthesize the ligand with a high yield and successfully apply the ligand to a In a series of metal iridium-catalyzed asymmetric allyl substitution reactions. Background technique [0002] Metal iridium-catalyzed asymmetric allyl substitution reactions can construct carbon-carbon bonds and carbon-heterobonds with high enantioselectivity and regioselectivity, and have been widely used in synthesis. At present, the ligands for such reactions are mainly Ferringa ligands and their derivatives [(a) Feringa, B.L.Acc.Chem.Res. 2000, 33, 346. (b) Alexakis, A.; Rosset, S.; Allamand, J. ; March, S.; Guillen, F.; Benhaim, C. Synlett 2001, 1375-1378. (c) Naasz, R.; Arnold, L.A.; Minnaard, A.J.; Feringa, B.L. Angew. Chem. 40, 927-930. (d) Polet, D.; Alexakis, A. Synthesis 2004, 2586-2590....

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/22C07D471/04
Inventor 游书力卓春祥刘文博
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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