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Chiral PCN pincerlike metal compound derived from diphenyl prolinol and synthesis method thereof

A technology for diphenylprolinol and metal compounds, which is applied in the field of chiral PCN pincer metal compounds and synthesis, can solve the problems of unreported literature on asymmetric pincer shape metal compounds, complicated purification and separation of ligands, and the like, and achieves the The effect of high product yield, simple operation and high catalytic activity

Inactive Publication Date: 2010-08-11
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, the research work on the synthesis and application of asymmetric pincer metal compounds containing phosphine chirality has not been reported in the literature.
At the same time, for the reported phosphine ligand pincer metal compounds, tedious purification and separation of ligands are often required, which is a very annoying work for organic synthesis

Method used

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  • Chiral PCN pincerlike metal compound derived from diphenyl prolinol and synthesis method thereof
  • Chiral PCN pincerlike metal compound derived from diphenyl prolinol and synthesis method thereof
  • Chiral PCN pincerlike metal compound derived from diphenyl prolinol and synthesis method thereof

Examples

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example 1

[0026] Example 1: 2-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-6-((S)-3, Synthesis of 3-diphenylpyrrolemethanol phosphite) phenylpalladium chloride (II):

[0027] Under nitrogen protection, the Et 3 After cooling 3mL of N (1mmol, 138.5μL) toluene solution to -35°C, add PCl in sequence 3 (0.275mmol, 24.3μL), diphenylprolinol (0.25mmol, 63.25mg) in toluene solution 1mL; after the dropwise addition, continue to stir for 30 minutes, then rise to room temperature and stir for 3.5 hours; re-cool to -35°C, add Et 3 N (0.5mmol, 69.5μL), 1-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-3-hydroxy Benzene (0.25mmol, 77.6mg), continued to stir for 10 minutes, then rose to room temperature and stirred for 20 hours, added Et 3 N (0.5mmol, 69.5μL), PdCl 2 (0.25mmol, 44.3mg), heated to reflux for 24 hours; wherein the molar ratio of each reactant is Et 3 N: chiral diphenylprolinol: phosphine trichloride: 1-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyp...

example 2

[0029] Example 2: 2-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-6-((S)-3, Synthesis of 3-diphenylpyrrolemethanol phosphite) phenylpalladium chloride (II):

[0030] Under nitrogen protection, after cooling 4 mL of diisopropylethylamine (2 mmol, 346.1 μL) in dichloroethane to -20 °C, add PCl in sequence 3 (0.275mmol, 24.3μL), 1mL of dichloroethane solution of diphenylprolinol (0.25mmol, 63.25mg); after the dropwise addition, continue to stir for 1 hour, then rise to room temperature and stir for 5 hours; re-cool to -20 ℃, add 1-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-3-hydroxybenzene (0.25mmol, 77.6 mg), continue to stir for 40 minutes, then rise to room temperature and stir for 28 hours, add PdCl 2 (0.25mmol, 44.3mg), heated to reflux for 24 hours. Wherein the molar ratio of each reactant is diisopropylethylamine: chiral diphenylprolinol: phosphine trichloride: 1-((S)-4-isopropyl-4,5-dihydro -1-p-methoxyphenyl-1H-imidazol-2-yl)-...

example 3

[0032] Example 3: 2-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-6-((S)-3, Synthesis of 3-diphenylpyrrolemethanol phosphite) phenyl nickel(II) chloride: under nitrogen protection, Et 3 After cooling 3mL of N (1mmol, 138.5μL) toluene solution to -35°C, add PCl in sequence 3 (0.275mmol, 24.3μL), diphenylprolinol (0.25mmol, 63.25mg) in toluene solution 1mL. Stirring was continued for 30 minutes after the dropwise addition was completed, and then raised to room temperature and stirred for 3.5 hours. Recool to -35°C, add Et 3 N (0.5mmol, 69.5μL), 1-((S)-4-isopropyl-4,5-dihydro-1-p-methoxyphenyl-1H-imidazol-2-yl)-3-hydroxy Benzene (0.25mmol, 77.6mg), continued to stir for 10 minutes, then rose to room temperature and stirred for 20 hours, added Et 3 N (0.5mmol, 69.5μL), NiCl 2 (0.25mmol, 32.0mg), heated to reflux for 6 hours; wherein the molar ratio of each reactant is Et 3 N: chiral diphenylprolinol: phosphine trichloride: 1-((S)-4-isopropyl-4,5-dihydro-1-...

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Abstract

The invention discloses a chiral PCN pincerlike metal compound derived from diphenyl prolinol and a synthesis method thereof. The chiral PCN pincerlike metal compound has a structural formula as follow: in the formula, M is metallic Pd (II) or Ni (II) ions, R1 and R2 are hydrogen, and alkyl of C1-C6 or phenyl substituted by alkyl, and X is halogen. In the invention, a series of chiral PCN pincerlike metal compounds derived from diphenyl prolinol can be synthesized by adopting one-pot phosphorylation / metallization reaction; and the synthesis method of the chiral PCN pincerlike palladium compound comprises the following steps of: performing phosphorylation reaction of m-hydroxyl imidazoline benzene compounds, and then directly adding metal salts in a reaction solution to further react without separating instable PCN ligands. The invention successfully realizes the C2-bit C-H bond activation of the ligand, simplifies the synthesis steps, ensures that the operation is simple, convenient and easy and the product yield is high, and provides a new approach for the synthesis of the unsymmetrical chiral PCN pincerlike metal compounds.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of organic compounds, and relates to a chiral PCN pincer metal compound derived from diphenylprolinol and a synthesis method. Background technique [0002] Common pincer metal compounds are usually composed of a tridentate ligand (Y, C, Y) and a metal center, where Y is a neutral two-electron donor, such as Y=NR 2 、PR 2 、0PR 2 , =NR, SR, C represents the carbon atom of the carbanion, and there is usually at least one metal-carbon σ bond between the ligand and the metal. Since Moulton and Shaw reported the first synthesis of PCP pincer metal compounds in 1976, people's interest in the synthesis, structure, reaction and application of novel pincer metal compounds has grown rapidly. For example, (1) pincer compounds can be used as homogeneous catalysts and chiral accelerators in chemical reactions, especially in the field of homogeneous catalysis, various forms of aryl PCP, NCN, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F19/00
Inventor 宋毛平牛俊龙王杰郝新奇龚军芳
Owner ZHENGZHOU UNIV