Naphthofuran-structure-containing biaryl monophosphine ligands, and preparation method and application thereof

A kind of technology of biaryl mono-phosphine ligand, applied in the field of biaryl monophosphine ligand and preparation thereof

Active Publication Date: 2016-09-28
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although many monophosphine ligands have been reported, due to the diversity of substrates and reactions, the requirements for ligands are also diverse. Therefore, it is urgent to develop phosphine ligands with different structures to meet different reaction types. needs

Method used

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  • Naphthofuran-structure-containing biaryl monophosphine ligands, and preparation method and application thereof
  • Naphthofuran-structure-containing biaryl monophosphine ligands, and preparation method and application thereof
  • Naphthofuran-structure-containing biaryl monophosphine ligands, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Embodiment 1 biaryl monophosphine ligand

[0049] In this embodiment, the biaryl monophosphine ligand represented by the formula ((+)-8A) is taken as an example to introduce its preparation process.

[0050]

[0051] (1), use compound shown in formula ((+)-1) to prepare compound shown in formula ((+)-2)

[0052]

[0053]Under the protection of nitrogen, dissolve 1.0g (2.13mmol) of the compound represented by formula ((+)-1) in 50mL of ethanol, add 10mL of 4mol / L dilute hydrochloric acid, react at 80°C for 7h, spin dry the ethanol under reduced pressure, and then add Dissolve in 100mL of water, extract 3 times with ethyl acetate, combine the organic phases, wash with saturated brine, dry over anhydrous magnesium sulfate, and remove the solvent under reduced pressure to obtain 850mg of product formula ((+)-2) The shown compound, yield: 93%, product analysis result: [α] D 17 +47.5 (c=0.1, CHCl 3 ), 1 H NMR (400MHz, CDCl 3 )δ8.48(1H,s),8.10(1H,d,J=12.0Hz),7.93(1...

Embodiment 2

[0076]

[0077] In the glove box, Sm1 (0.1mmol, 1.0equiv), Sm2 (0.2mmol, 2.0equiv), K 3 PO 4 (0.3mmol, 3.0equiv), Pd 2 (dba) 3 (1.0% mmol), (±)-8A (2.0% mmol) and toluene (4.0 mL) were placed in a 25 mL one-necked bottle, and stirred at 80° C. for 1 hour under nitrogen protection. Product result analysis: 1 H NMR (400MHz, CDCl 3 )δ8.05-8.01(3H,m),7.95(1H,d,J=8.0Hz),7.69(1H,t,J=4.0Hz),7.52-7.49(3H,m),7.40-7.23(5H ,m),3.81(3H,s). 13 C NMR (101MHz, CDCl 3 )δ154.6, 134.6, 134.3, 133.7, 133.0, 129.5, 129.0, 128.5, 128.2, 127.8, 126.2, 125.7, 125.6, 125.5, 123.6, 123.2, 113.8, 56.8.

Embodiment 3

[0079]

[0080] In the glove box, Sm1 (0.1mmol, 1.0equiv), Sm3 (0.2mmol, 2.0equiv), K 3 PO 4 (0.3mmol, 3.0equiv), Pd 2 (dba) 3 (1.0% mmol), (±)-8A (2.0% mmol) and isopropanol (4.0 mL) were placed in a 25 mL one-necked bottle, and stirred at 80° C. for 4 hours under nitrogen protection. Product result analysis: 1 H NMR (400MHz, CDCl 3 )δ8.70-8.68 (1H, m), 8.66 (1H, s), 7.97 (1H, d, J = 12.0Hz), 7.87 (1H, t, J = 4.0Hz), 7.76-7.73 (1H, m ),7.50-7.45(2H,m),7.42-7.38(3H,m),3.87(3H,s). 13 C NMR (101MHz, CDCl 3 )δ154.1, 151.8, 148.2, 138.6, 133.3, 130.0, 128.9, 128.1, 126.8, 124.5, 123.7, 123.1, 133.3, 56.5.

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Abstract

The invention discloses naphthofuran-structure-containing biaryl monophosphine ligands, and a preparation method and application thereof. The biaryl monophosphine ligands are compounds disclosed the chemical structural formula (VIII) or antipodes or racemates thereof. According to the biaryl monophosphine ligands, the furan ring is introduced and forms a conjugated structure with the dinaphthalene, thereby increasing the steric hindrance of the phosphine ligands (including antipodes or racemates thereof) and the cloud density of the aromatic ring, and enhancing the stability of the complexes. The steric hindrance of the ligands is regulated, so that the ligands have novel structure. The preparation process comprises the steps of Sonogashira reaction, intramolecular cyclization, C-P coupling reaction and the like. The synthesis method is simple; and the obtained ligands have the advantages of high activity, favorable selectivity and the like when being used for Suzuki-Miyuara reaction.

Description

technical field [0001] The invention belongs to the field of chemical catalysis, and in particular relates to a class of biaryl monophosphine ligands containing naphthofuran structures and a preparation method and application thereof. Background technique [0002] In catalytic reactions, the coordination of substrates, catalysts and ligands is very important, and small changes in ligand structures often have a series of effects on the activity, selectivity and kinetics of catalytic reactions. [0003] The outer electron configuration of the ground state of the phosphorus atom is 3s 2 threesome 3 , which takes the inequality sp 3 The hybrid orbital forms three σ bonds with three substituents (alkyl, aryl or alkoxy, aryloxy) respectively. Electronic effect and steric effect are two important aspects of organophosphine ligands affecting catalytic reactions. In recent years, in the design process of ligands, a series of electron-rich and large steric hindrance phosphine ligan...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/655B01J31/24C07B37/04C07C41/30C07C43/20C07D213/30C07C1/32C07C15/24C07D215/20
CPCC07B37/04C07C1/321C07C41/30C07D213/30C07D215/20C07F9/65517B01J31/2447C07C2531/24B01J2231/4211B01J2231/4227
Inventor 邱立勤周自洪
Owner SUN YAT SEN UNIV
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