Unlock instant, AI-driven research and patent intelligence for your innovation.

Synthesis method of compound with phosphine chirality and axial chirality

A synthesis method and axial chirality technology, applied in the field of chiral phosphine compound synthesis, can solve problems such as few reports, and achieve the effects of convenient synthesis, high efficiency and good universality

Active Publication Date: 2021-12-03
YANGZHOU UNIV
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003]The buchwald phosphine ligand transition metal catalyzed coupling reaction has a good effect, and the preparation of buchwald phosphine ligand with phosphine chirality and axial chirality can be an important Symmetric catalysis offers opportunities, but research in this area is still poorly reported

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
  • Synthesis method of compound with phosphine chirality and axial chirality
  • Synthesis method of compound with phosphine chirality and axial chirality
  • Synthesis method of compound with phosphine chirality and axial chirality

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042]

[0043] Starting from 1a, reaction with 2a afforded 3a as a white solid in 56% yield, >20:1dr, 92% ee. DaicelIE-H chiral column was used to determine its ee value by high performance liquid chromatography. (HPLC: IE-H, 254nm, n-hexane / isopropanol=97:3, flow rate 1.0mL / min, 30°C, t r (times) = 20.3min,t r (main)=18.3min).[α] D 25 =-113°(c0.100, CH 2 Cl 2 ).

[0044] 1 H NMR (400MHz, CDCl 3 )δ7.70–7.60(m,2H),7.53–7.24(m,11H),7.18–7.11(m,2H),7.04–6.96(m,1H),6.93(d,J=7.6Hz,1H) ,6.84–6.68(m,5H),6.64–6.52(m,2H),6.45(d,J=7.6Hz,1H),5.91(t,J=7.6Hz,1H),1.11(d,J=14.8 Hz,9H). 13 C NMR (101MHz, CDCl 3 )δ148.5(d, J=5.4Hz), 140.5, 139.7(d, J=13.3Hz), 138.5(d, J=15.6Hz), 137.8, 137.4(d, J=3.3Hz), 136.8(d ,J=3.2Hz),135.62(d,J=10.9Hz),136.6(d,J=2.2Hz),135.6(d,J=11.0Hz),133.2,133.1,132.7(d,J=12.2Hz) ,132.1,132.0,131.8,131.6,131.2,130.9,130.6,130.28(d,J=89.9Hz),128.2(d,J=11.4Hz),128.0(d,J=90.4Hz),127.3(d,J =11.5Hz), 127.1(d, J=9.9Hz), 126.3(d, J=9.5Hz), 126.2, 126.1(d, J=...

Embodiment 1-2

[0045] Example 1-2: Same as Example 1, the difference is that the ligand L in the reaction is replaced by (The preparation method is the same as above), the yield is 50%, 13:1dr, 55%ee. Compared with the examples, compounds with axial chirality and phosphine chirality can also be synthesized, but the ee value is lower, that is, the ligand of this structure has lower efficiency in the catalytic reaction.

Embodiment 2

[0047]

[0048] Starting from 1b, reaction with 2a afforded 3b as a white solid in 50% yield, >20:1dr, 88%ee. DaicelAD-H chiral column was used to determine its ee value by high performance liquid chromatography. (HPLC: AD-H, 254nm, n-hexane / isopropanol 99:1, flow rate 1.0mL / min, 30°C, t r (minor) = 10.3min,t r (major)=8.5min).[α] D 25 =-66°(c0.11, CH 2 Cl 2 ).

[0049] 1 H NMR (400MHz, CDCl 3 )δ7.79–7.71(m,1H),7.66–7.60(m,1H),7.52–7.39(m,4H),7.39–7.30(m,2H),7.30–7.07(m,5H),7.06– 6.96(m,3H),6.93(d,J=7.6Hz,1H),6.82–6.69(m,4H),6.66–6.61(m,1H),6.52(dd,J=11.0,5.6Hz,2H) ,5.93(t,J=7.5Hz,1H),1.11(d,J=14.8Hz,9H). 13 C NMR (101MHz, CDCl 3 )δ164.3(dd, J=253.3Hz, 2.8Hz), 163.2(dd, J=255.7Hz, 3.3Hz), 149.8(dd, J=8.0Hz, 6.5Hz), 140.5, 139.8, 139.6, 138.5, 138.3, 137.5, 136.8, 134.2, 134.1, 134.0, 133.7 (dd, J = 12.7Hz, 8.5Hz), 132.0, 131.6 (d, J = 1.4Hz), 131.6, 131.3, 131.0, 130.5, 127.9 (dd, J =91.7Hz, 3.5Hz), 127.2(dd, J=12.4Hz, 8.3Hz), 126.3, 126.17(d, J=7.3Hz), 125.9(d...

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 synthesis method of a compound with phosphine chirality and axial chirality. The method comprises the following steps: in an organic solvent system, synthesizing by taking a diaryl phosphine oxide compound and diaryl alkyne as basic raw materials under the effect of an iridium catalyst, an oxidizing agent and a chiral amide ligand, and carrying out post-treatment on a reaction solution to obtain the compound with phosphine chirality and axial chirality. The diaryl phosphine oxide used in the reaction is simple and easy to synthesize, the universality of the substrate is better, the reaction operation is simple and convenient, and the efficiency is high. Synthesis of a ligand is relatively convenient, the ligand is combined with metal in the reaction, and the C-H bond on a benzene ring is selectively activated under the guidance of phosphine oxide of the substrate, so that the carbon-hydrogen bond activation arylation reaction among molecules is realized, and the compound with phosphine chirality and axial chirality is synthesized with medium or more yield and relatively high enantioselectivity. The obtained product can be used as a medical intermediate or a chiral ligand; and the trivalent phosphine obtained by further reducing the product can also be used as a chiral phosphine ligand.

Description

technical field [0001] The invention relates to the technical field of synthesis of chiral phosphine compounds, in particular to a synthesis method of compounds with phosphine chirality and axial chirality. Background technique [0002] Phosphine compounds are widely used in many fields such as catalysis, medicine, material chemistry, etc., especially chiral phosphine compounds, as a kind of ligand with excellent performance, show great excellent enantioselectivity. Since the successful preparation of the phosphine chiral ligand DIPAMP by Knowles and co-workers in the 1970s, various methods for the synthesis of chiral phosphine compounds have been developed. From the initial pure enantiomeric chiral phosphine compounds obtained by chiral resolution or different chiral auxiliary groups, to the recent years by asymmetric catalytic or kinetic resolution to obtain chiral phosphine compounds or Chiral phosphine ligands. Various examples have been reported one after another, bu...

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): C07F9/32C07F9/53B01J31/22C07D209/76
CPCC07F9/5325C07D209/76C07F9/32C07F9/3229C07F9/3264B01J31/2295C07B2200/07B01J2531/0266B01J2531/825
Inventor 段伟良张朝威
Owner YANGZHOU UNIV
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