1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand as well as preparation method and application thereof

A perfluoroalkylphosphine and ferrocene technology, which is applied in the preparation of carboxylic acid esters, chemical instruments and methods, and the preparation of organic compounds, can solve problems such as poor results, complicated synthesis methods, and no regioselectivity.

Active Publication Date: 2014-05-07
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
View PDF2 Cites 12 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Moderate to excellent regioselectivity and enantioselectivity can be obtained for linear and branched allyl substrates, especially when the allyl substrate is 1-naphthyl, high regioselectivity and enantioselectivity, but unsatisfactory results for aryl substituents in general, especially those containing electron-withdrawing groups, and poor results for alkyl-substituted allylic substrates, with almost no Regional selectivity [(a) R.;Pfaltz,A.Angew.Chem.,Int.Ed.1998,37,323.(b)Hilgraf,R.;Pfaltz,A.Synlett.1999,1814.(c)Hilgraf,R.;Pfaltz,A. Adv. Synth. Catal. 2005, 347, 61.]
In 2001, Hou Xuelong and Dai Lixin's group designed and synthesized 1,1'-ferrocene phosphine nitrogen ligand SIOC-PHOX. In the reaction of malonate and b

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • 1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand as well as preparation method and application thereof
  • 1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand as well as preparation method and application thereof
  • 1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] In Example 1, the preparation method and conditions of the compound without specific experimental steps are the same as the preparation P1: (S)-1-(4,5-dihydro-4-isopropyl-oxazoline)-1'- The method and conditions of bistrifluoromethylphosphinoferrocene differ only in that different reaction substrates are used to prepare corresponding products.

[0079] P1: Synthesis of (S)-1-(4,5-dihydro-4-isopropyl-oxazoline)-1’-bistrifluoromethylphosphinoferrocene

[0080]

[0081] where rt means room temperature.

[0082] Under nitrogen protection, oxazoline bromide ferrocene (3.38g, 9mmol) was added to the dry reaction flask, dissolved in 55mL ether, TMEDA (1.6mL, 10.8mmol) was added at -78°C, n-butyllithium ( 4.5mL, 2.4M, 10.8mmol) After stirring at this temperature for 2 hours, 3mL of P(OPh) 3 After being dissolved in 5 mL of ether, it was slowly added to the reaction, and the reaction was naturally raised to room temperature, and stirred overnight. The reaction solvent was ...

Embodiment 2

[0131]

[0132] Under nitrogen protection at room temperature, Pd 2 (dba) 3 (9.2mg, 0.01mmol) and ligand (9.6mg, 0.02mmol) were dissolved in 5mL DCE and stirred at room temperature for 30 minutes. Add allyl carbonate (96mg, 0.5mmol), dimethyl malonate (0.17mL, 1.5mmol), BSA (0.37mL, 1.5mmol) and NaOAc (1.0mg, 0.015mmol), react at room temperature, TLC tracking After the reaction is complete, dilute with DCM, quench by adding saturated ammonium chloride solution at 0°C, extract with DCM, combine the organic phases, dry over anhydrous sodium sulfate, and remove the solvent under reduced pressure to obtain a crude product. Purified by column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain 88.2 mg of product, yield 71%, b / l = 10 / 90, 70% ee.

Embodiment 3 2

[0133] Example 3 Application of perfluoroalkyl P-N ligands of ferrocene skeleton in allylation reaction

[0134]

[0135] General experimental operation: under nitrogen protection at room temperature, Pd 2 (dba) 3 (9.2mg, 0.01mmol) and ligand (9.6mg, 0.02mmol) were dissolved in 5mL DCE and stirred at room temperature for 30 minutes. Add allyl carbonate (96mg, 0.5mmol), dimethyl malonate (0.17mL, 1.5mmol), BSA (0.37mL, 1.5mmol) and NaOAc (1.0mg, 0.015mmol), react at room temperature, TLC tracking After the reaction is complete, dilute with DCM, quench by adding saturated ammonium chloride solution at 0°C, extract with DCM, combine the organic phases, dry over anhydrous sodium sulfate, and remove the solvent under reduced pressure to obtain a crude product. The ratio of the product was purified by column chromatography (petroleum ether: ethyl acetate = 10:1), and the ee value was determined by chiral HPLC.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention relates to a 1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand as well as a preparation method and an application thereof. The preparation method of the 1, 1'-ferrocene perfluoroalkyl phosphine nitrogen ligand comprises the following steps: (1) reacting oxazoline bromoferrocene with a butyl lithium compound in an organic solvent under the condition of existence of an additive; (2) mixing reaction liquid obtained in the step (1) with triphenyl phosphite; and (3) in the solvent, reacting an isodecyl diphenyl phosphite derivative obtained in the step (2) and cesium fluoride with TMSCnF2n+1. The invention also relates to the application of the ligand in an asymmetric allyl displacement reaction catalyzed by metallic palladium. The ligand provided by the invention can be used for catalyzing the allyl displacement reaction of single substituted allyl carbonic ester in a high domain selectivity and high enantioselectivity manner. The synthetic method is simple, mild in conditions, high in yield, convenient in purification and suitable for industrial production; starting materials are low in cost and easy to obtain.

Description

technical field [0001] The invention relates to a 1,1'-ferrocene perfluoroalkylphosphine nitrogen ligand, its preparation method and application. Background technique [0002] Transition metal-catalyzed asymmetric allyl substitution reactions are one of the important reactions for the formation of carbon-carbon bonds and carbon-heteroatom bonds, and are widely used in total synthesis. Metals such as palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), molybdenum (Mo), tungsten (W), nickel (Ni) and copper (Cu) can all catalyze this reaction. The most, and the most detailed study is the metal palladium. Chemists represented by Trost have done a lot of research work on this reaction, which has greatly developed and applied this reaction. Nevertheless, there are still some challenges in the application of allylation reactions and have not been well resolved. One of the difficulties is regioselectivity. In palladium-catalyzed allyl substitution reactions, for monosubsti...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): C07F19/00B01J31/24C07C67/343C07C69/618C07C69/734C07C69/65C07D333/24C07D307/54
Inventor 游书力赖增伟叶克印
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap