Eureka AIR delivers breakthrough ideas for toughest innovation challenges, trusted by R&D personnel around the world.

Indole framework based center chirality sulfonamides monophosphine ligand and preparation method

A sulfenamide and chiral technology, which is applied in the preparation of central chiral sulfenamide monophosphine ligands, ligands and their preparation fields, can solve the problems of long synthetic routes, harsh reaction conditions, expensive raw materials, etc., and achieve high Reactivity and stereoselectivity, good application prospects, easy to modify the effect

Active Publication Date: 2015-05-13
苏州凯若利新材料科技有限公司
View PDF2 Cites 13 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method has great difficulties in synthesizing all configurational isomers. It needs to be based on raw materials of different chiral configurations, and a single product of this raw material configuration is constructed, and because the synthetic route is longer and the raw materials More expensive and toxic reagents such as chloromethyl methyl ether are used in the reaction, so that the reaction conditions are relatively harsh, and problems such as by-products harmful to the environment and residues of toxic compounds will be produced during the reaction

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
  • Indole framework based center chirality sulfonamides monophosphine ligand and preparation method
  • Indole framework based center chirality sulfonamides monophosphine ligand and preparation method
  • Indole framework based center chirality sulfonamides monophosphine ligand and preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl)(phenyl)methyl)-1-hydrogen- Synthesis of tert-butylsulfinamide [1a(R,R)]

[0026]

[0027] Among them, N 2 for nitrogen.

[0028] The first step: in a 500mL three-necked flask, add N-methyl-2-bromo-3-indole formaldehyde (50mmol) and diphenylphosphine (50mmol), add 150mL toluene under nitrogen atmosphere, add four Triphenylphosphinepalladium (2.5mmol), stirred at 50°C for 12h, the yield was 50%.

[0029]

[0030] The second step: in a 500mL three-necked flask, add N-methyl-2-diphenylphosphine-3-indolecarbaldehyde (50mmol) and (R)-(+)-tert-butylsulfinamide (50mmol ), added 150 mL of tetrahydrofuran under a nitrogen atmosphere, added tetraethyl titanate (100 mmol), stirred at 50° C. for 10 h, and the yield was 70%. 1 H NMR (400MHz, CDCl 3 ,ppm):δ=9.05(d,J=3.6Hz,1H),8.50(d,J=8.0Hz,1H),7.47–7.25(m,13H),3.53(s,3H),1.24(s, 8H). 13 C NMR (100MHz, CDCl 3 ,ppm):δ=158.16,157.99,141.56,141.24,140.15,133....

Embodiment 2

[0033] Example 2 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl)(phenyl)methyl)-1-hydrogen- Synthesis of tert-butylsulfinamide [1a(R,S)]

[0034]

[0035] Other operations refer to Example 1, the nucleophile used is phenylmagnesium bromide, and the yield is 63%. 1 H NMR (400MHz, CDCl 3 , ppm): δ=7.79(d, J=8.1Hz, 1H), 7.51(t, J=8.4Hz, 4H), 7.42–6.99(m, 14H), 6.73(dd, J=8.2, 3.8Hz, 1H), 4.17(d, J=3.8Hz, 1H), 3.22(s, 3H), 1.19(s, 9H). 13 C NMR (100MHz, CDCl 3 ,ppm):δ=142.92,140.26,135.10,135.00,134.30,134.22,131.87,131.77,131.70,131.59,130.92,130.62,128.68,128.64,128.63,128.58,128.35,128.14,128.11,127.97,127.68,126.96, 126.88, 125.51, 125.44, 123.46, 121.59, 119.39, 109.64, 56.50, 56.28, 55.52, 32.46, 22.83. 31 P NMR (162MHz, CDCl 3 , ppm): δ=-34.99. IR (neat): 2920, 1456, 1056, 911, 741, 696; HRMS (ESI): calculated for C 32 h 33 N 2 OPS[M+Na] + :547.1943,found:547.1947.[α] D 20 =-125.9 (c=0.50, CHCl 3 ).

Embodiment 3

[0036] Example 3 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl)(methyl)methyl)-1-hydrogen- Synthesis of tert-butylsulfinamide [1b(R,S)]

[0037]

[0038] Other operations refer to Example 1, the nucleophile is methylmagnesium bromide reagent, and the total yield is 70%. 1 H NMR (400MHz, CDCl 3 ,ppm): δ=7.87(d,J=8.1Hz,1H),7.46(d,J=7.6Hz,2H),7.40–7.21(m,8H),7.12(d,J=8.0Hz,1H) ,5.49(d,J=4.3Hz,1H),3.92–3.71(m,1H),3.24(d,J=1.5Hz,3H),1.71(d,J=6.7Hz,3H),1.11(s, 9H). 13 C NMR (100MHz, CDCl 3 ,ppm):δ=140.16,135.28,135.18,134.63,134.54,131.81,131.64,131.46,129.77,129.59,129.49,129.30,128.70,128.64,128.58,128.14,128.10,125.19,125.11,123.38,121.07,119.16, 109.72, 55.18, 49.30, 49.10, 32.33, 32.30, 24.96, 22.65. 31 P NMR (162MHz, CDCl 3 , ppm): δ=-34.98. IR (neat): 2959, 1433, 1362, 1052, 908, 740, 695; HRMS (ESI): calculated for C 27 h 31 N 2 OPS[M+Na] + :485.1787,found:485.1774.[α] D 20 =-117.6 (c=0.50, CHCl 3 ).

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 an indole framework based center chirality sulfonamides monophosphine ligand and a preparation method thereof. The monophosphine ligand adopts the structure of a formula I, and is prepared through adopting 2-halogenated indole formaldehyde (ketone) to obtain 2-disubstituted phosphine indole formaldehyde (ketone), and taking the 2-disubstituted phosphine indole formaldehyde (ketone) and chirality sulfonamide as raw materials to react with a nucleophilic reagent or a reducing reagent to prepare the compound of the formula I; optical pure compounds of four configurations of (R,R), (R,S), (S,S) and (S,R) can be obtained conveniently through adopting different chirality sulfonamides and different nucleophilic reagents. The monophosphine ligand is simple in framework, convenient to synthesize, easy to transform, can be applied to various metal catalyzed asymmetric reactions as well as the tertiary phosphine catalyzed reaction, and has good application prospect.(The formula I is shown in the description).

Description

technical field [0001] The invention relates to a ligand in the technical field of chemical engineering and a preparation method thereof, in particular to a preparation method of a central chiral sulfinamide monophosphine ligand based on an indole skeleton. Background technique [0002] In asymmetric synthesis, the catalytic system of chiral ligand and metal coordination is the key to the efficient and high enantioselective synthesis of target products, and the ligand is the source of chiral induction and regulation. How to design and synthesize chiral ligands with high selectivity and high catalytic activity is one of the research hotspots of organic chemists today. Chiral phosphine-containing compounds are a very important class of chiral ligands, which are widely used in asymmetric reactions catalyzed by transition metals. At present, a variety of chiral phosphine compounds have been applied to the production and research and development of chiral chemicals. As early as...

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): C07F9/572
Inventor 张俊良刘路唐斌
Owner 苏州凯若利新材料科技有限公司
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
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