Check patentability & draft patents in minutes with Patsnap Eureka AI!

Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction

A hydrogenation reaction, asymmetric technology, applied in chemical instruments and methods, preparation of organic compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of ruthenium catalytic precursor activity and enantioselectivity reduction, etc. problem, to achieve the effect of efficient synthesis

Inactive Publication Date: 2012-01-11
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
View PDF5 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in these existing asymmetric hydrogenation reaction methods, there are obvious deficiencies: the slight changes in the stereostructure and steric electronic effect of the chiral bisphosphine ligand usually lead to significant changes in the activity and enantioselectivity of the ruthenium catalytic precursor. reduce

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
  • Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction
  • Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction
  • Method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Add phenyl ruthenium dichloride (〔RuCl 2 beneze〕 2 ) (0.05mmol, 25mg), bridged chiral bisphosphine ligand (Rax)-BuP (0.105mmol, 64.3mg), N,N-dimethylformamide 6mL, under nitrogen protection, 100 ℃, stirring reaction. After the solution was cooled to room temperature, chiral diamine (R, R)-DPEN (0.105 mmol, 23 mg) was added, the reaction was continued to stir at this temperature, the solvent was distilled off under reduced pressure, dichloromethane was added to dissolve the solid, and the solution was concentrated , Add hexane to the concentrated solution to produce a brownish yellow precipitate, filter, and distill the solvent from the filtrate under reduced pressure to obtain a khaki solid as a ruthenium catalyst precursor. Ruthenium catalyst precursor 31 pNMR (CDCl 3 , 202MHz) δ=47.5ppm (s).

[0029] Add ruthenium catalytic precursor (0.0025mmol, 2.5mg), potassium tert-butoxide 0.114mmol, methanol 1mL to 100mL Schlenk bottle, stir and dissolve at room temperature,...

Embodiment 2

[0031] The ruthenium catalyst precursor and potassium tert-butoxide are as in Example 1, 1 mL of isopropanol, stirred and dissolved at room temperature, added acetophenone (2.5 mmol, 0.29 mL), transferred to a 30 mL stirred autoclave, hydrogen atmosphere, 2 MPa, 28 The reaction was stirred at °C for 18 hours. The hydrogen in the kettle was emptied, concentrated under reduced pressure after flash column chromatography, the reaction conversion rate was 99wt% as measured by gas chromatography, and the product was 75% ee(S)-phenethyl alcohol.

Embodiment 3

[0033] Ruthenium catalyst precursor and potassium butoxide as in Example 1, n-butanol 1mL, stirred and dissolved at room temperature, added acetophenone (2.5mmol, 0.29mL), transferred to a 30mL autoclave with stirring, hydrogen atmosphere, 1MPa, 20 The reaction was stirred at °C for 22 hours. The hydrogen in the kettle was emptied, concentrated under reduced pressure after flash column chromatography, the reaction conversion rate was 99wt% as measured by gas chromatography, and the product was 81% ee(S)-phenylethanol.

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 discloses a method for synthesizing chiral secondary alcohol through asymmetric hydrogenation reaction, which is characterized in that phenyl ruthenium dichloride and chiral bridged biphosphine (Rax)-BuP and chiral diamine (R, R)-DPEN take reaction to prepare catalyst precursors, prochiral ketones and hydrogen gas are used as reactants, potassium tert-butoxide is used as auxiliary agents, and the chiral secondary alcohol is synthesized in one step through the asymmetric hydrogenation reaction in low-carbon alcohol solvents. The maximum reactant conversion rate can reach 99 wt percent, and the highest product corresponding selectivity can reach 92 percent.

Description

technical field [0001] The invention relates to a method for synthesizing chiral secondary alcohols by asymmetric hydrogenation reaction. Background technique [0002] Chiral secondary alcohols are important intermediates for the synthesis of optically active drugs, and the catalytic asymmetric hydrogenation of latent chiral ketones is one of the most effective methods to obtain chiral secondary alcohols. In the asymmetric hydrogenation method for the synthesis of chiral secondary alcohols, the key to obtain catalytic activity and enantioselectivity is the chiral ligand. The patent (EP-A-071826) discloses a C 2 Atropisomeric binaphthyl bisphosphine ligands (BINAP, Tol-BINAP, Xylyl-BINAP, H8-BINAP) with symmetry axis, and chiral diamine DPEN or DAIPEN, catalyst precursor prepared with ruthenium, in latent hand In the asymmetric hydrogenation reaction of sex ketone, the product chiral alcohol with higher yield and enantioselectivity was given; in 1995, Noyori et al. reported...

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): C07B41/02C07C29/145C07C33/22C07C33/20C07C33/46C07C41/26C07C43/23B01J31/24
Inventor 王来来崔玉明赵庆鲁
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
Features
  • R&D
  • Intellectual Property
  • Life Sciences
  • Materials
  • Tech Scout
Why Patsnap Eureka
  • Unparalleled Data Quality
  • Higher Quality Content
  • 60% Fewer Hallucinations
Social media
Patsnap Eureka Blog
Learn More

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

© 2025 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com