Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method of compounding eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation

A technology for the synthesis of octahydrobinaphthol, which is applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., to achieve the effects of high yield, convenient operation, and simple post-treatment

Inactive Publication Date: 2013-06-05
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
View PDF1 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis of optically pure octahydrobinaphthol derivatives through catalytic hydrogenation of binaphthol derivatives with efficient catalysts is still a challenging issue.

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 of compounding eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation
  • Method of compounding eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation
  • Method of compounding eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1: optimization of conditions

[0030] Add cyclooctadiene rhodium chloride (1.3 mg, 0.0025 mmol), substrate 1a (716 mg, 0.25 mmol) to a 10 mL reaction flask in air, MS (50 mg) and isopropanol (3 ml), put the reaction flask into a high-pressure reactor, feed hydrogen at 50 atmospheres, and react at 80° C. for 16 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows:

[0031]

[0032] The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 1.

[0033] Table 1. Hydrogenation of binaphthol 1a

[0034]

Embodiment 2

[0035] Embodiment 2: rhodium catalytic hydrogenation synthesis octahydrobinaphthol derivative 2

[0036] Add cyclooctadiene rhodium chloride (1.3 mg, 0.0025 mmol), substrate 1 (0.25 mmol) to a 10 mL reaction flask in air, MS (50 mg) and isopropanol (3 ml), put the reaction flask into a high-pressure reactor, feed hydrogen at 50 atmospheres, and react at 80° C. for 16 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows, and the reaction formula is as follows:

[0037]

[0038] The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 2.

[0039] Table 2. Rhodium-catalyzed hydrogenation synthesis of octahydrobinaphthol derivatives 2

[0040]

[0041] The experimental data of each compound are as follows:

[0042] (S)-2,2'-dihydroxy-5,5',6,6',7,7',8,8'-octahydro-1,1'-dinaphthyl(H 8 -BINOL)(2a).(Known compound, ...

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 of compounding an eight-hydrogen binaphthol derivative through rhodium catalytic hydrogenation. A catalytic system used in the method is rhodium coordination compounds. A reaction is conducted under the conditions that temperatures are in a range of 0-100 DEG C, solvents are different alcohol, the pressure is in a range of (1-100) *1.01325*10<5>Pa, the ratio of zymolyte to catalysts is 100:1, metal precursor used is the rhodium coordination compounds, and additives used are different types of molecular sieves, alumina, aliquat 336, polyvinyl pyrrolidone (PVP) and tetrabutylammonium bromide. Hydrogenation is conducted on an optically pure binaphthol derivative to obtain the corresponding eight-hydrogen binaphthol derivative, wherein enantiomeric excess of the eight-hydrogen binaphthol derivative is kept to be larger than 99%. The method of compounding the eight-hydrogen binaphthol derivative through the rhodium catalytic hydrogenation is simple, convenient and practical to use, good in regioselectivity, and high in productivity. The reaction has green atom economy and is environment-friendly.

Description

technical field [0001] The invention relates to a method for obtaining high-enantiopure octahydrobinaphthol derivatives by hydrogenating a rhodium homogeneous system. Background technique [0002] Chiral octahydrobinaphthol derivatives are important synthetic raw materials in organic catalysis and organic synthesis. 8 -BINOL-based chiral ligands also play an important role in asymmetric synthesis and catalysis [a) McDougal, N.T.; Schaus, S.E.A.J.Am.Chem.Soc.2003, 125, 12094-12095.b) Au -Yeung, T.T.-L.; Chan, S.-S.; Chan, A.S.C.Adv.Synth.Catal.2003, 345, 537-555], however, there is little literature on the synthesis of octahydrobinaphthol derivatives reports. In 1978, the Cram group reported the first case of H 8 -BINOL synthesized, they use expensive PtO 2 As a catalyst, 94% yield can be obtained by reacting at room temperature for 7 days, and the configuration of the product is completely maintained [Cram, D.J.; Helgeson, R.C.; Peacock, S.C.; Kaplan, L.J.; Domeier, L.A....

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): C07C39/14C07C37/00
Inventor 周永贵陈木旺余长斌
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com