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Chiral bis[N,O] palladacycle and synthesizing method thereof

A synthesis method and complex technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve problems such as difficult synthesis and derivatization, and relatively large influence of ligand branched electronic effects and steric hindrance effects , to achieve good yield, easy operation and good chemical selectivity

Active Publication Date: 2018-10-16
SUZHOU UNIV
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Problems solved by technology

In the prior art, the introduction of large steric hindrance groups in the coupling reaction is still a difficult problem in synthesis. At the same time, chiral bis[N,O]cyclopalladium complexes may be widely used in the field of asymmetric catalysis, so it is necessary for this The derivatization of cyclopalladium-like complexes is particularly important; however, the existing methods are greatly affected by the electronic effect and steric hindrance effect of the ligand branch chain, and its synthesis and derivatization are still a difficult problem

Method used

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  • Chiral bis[N,O] palladacycle and synthesizing method thereof
  • Chiral bis[N,O] palladacycle and synthesizing method thereof
  • Chiral bis[N,O] palladacycle and synthesizing method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031]

[0032] Under nitrogen atmosphere, Pd(OAc) 2 (80.6 mg, 0.36 mmol, 1.2 equiv), reactant 1 (157.0 mg, 0.3 mmol), AgOAc (210.4 mg, 1.26 mmol, 4.2 equiv) were placed in anhydrous toluene (3.0 mL), stirred at room temperature for 15 minutes, then Add reactant 2a (275.4 mg, 1.35 mmol, 4.5 equiv) and react at 100°C for 16 hours. The system was directly separated by petroleum ether / ethyl acetate (5 / 1) column chromatography to obtain 178.6 mg of yellow solid 3a, yellow solid The yield is 64%, 235-236℃.

[0033] Analysis of product 3a, the results are as follows: [ α ]25 D = +398.3 (c 0.40, CHCl 3 ); 1 H NMR(400 MHz, CDCl 3 ) δ 7.88 (s, 2H), 7.41 (s, 2H), 7.25– 7.20 (m, 10 H), 7.04 (d, J = 6.4 Hz, 2H), 6.95 (s, 2H), 6.77 (d, J = 6.4 Hz, 2H), 6.54 (s, 4H), 6.30(d, J = 6.0 Hz, 4H), 5.41 (s, 2H), 3.59 – 3.32 (m, 2H), 1.28 (dd, J = 12.0,6.8 Hz, 12H), 1.16 (t, J = 6.8 Hz, 12H); 13 C NMR (101 MHz, CDCl 3 ) δ 169.59,162.19, 142.30, 142.22, 141.70, 141.60, 134.61, 130.74, 129.15, 128.6...

Embodiment 2

[0036]

[0037] Under nitrogen atmosphere, Pd(OAc) 2 (80.6 mg, 0.36 mmol, 1.2 equiv), reactant 1 (157.0 mg, 0.3 mmol), AgOAc (210.4 mg, 1.26 mmol, 4.2 equiv) were placed in anhydrous toluene (3.0 mL), stirred at room temperature for 15 minutes, then Add reactant 2b (321.2 mg, 1.35 mmol, 4.5 equiv) and react at 100°C for 16 hours. The system was directly separated by petroleum ether / ethyl acetate (5 / 1) column chromatography to obtain 207.9 mg of yellow solid 3b, yellow solid The yield is 64%, 227-228℃.

[0038] Analysis of product 3b, the results are as follows: [ α ]25 D = +410.39 (c 0.39, CHCl 3 ); 1 H NMR(400 MHz, CDCl 3 ) δ 7.88 (s, 2H), 7.43 (s, 2H), 7.28 (dd, J = 8.0, 4.0 Hz,6H), 7.05 (d, J = 7.6 Hz, 2H), 7.01 – 6.94 (m, 2H), 6.90 (d, J = 7.2 Hz, 2H), 6.58 (s, 4H), 6.35–6.25 (m, 2H), 6.19 (s, 2H), 5.26 (s, 2H), 3.68 – 3.50 (m,2H), 1.39 (dd, J = 6.8, 2.4 Hz, 1H), 1.22 (dd, J = 22.8, 6.8 Hz, 1H); 13 C NMR(101 MHz, CDCl 3 ) δ 169.11, 162.20, 140.63, 140.49, 140.10, 135.12...

Embodiment 3

[0041]

[0042] Under nitrogen atmosphere, Pd(OAc) 2 (80.6 mg, 0.36 mmol, 1.2 equiv), reactant 1 (157.0 mg, 0.3 mmol), AgOAc (210.4 mg, 1.26 mmol, 4.2 equiv) were placed in anhydrous toluene (3.0 mL), stirred at room temperature for 15 minutes, then Add reactant 2c (380.4 mg, 1.35 mmol, 4.5 equiv) and react at 100°C for 16 hours. The system was directly separated by petroleum ether / ethyl acetate (5 / 1) column chromatography to obtain 268.3 mg of yellow solid 3c, yellow solid The yield is 72%, 217-218℃.

[0043] Analysis of product 3c, the results are as follows:[ α ]25 D = +393.5 (c 0.42, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 ) δ 7.77 (s, 2H), 7.53 (s, 2H), 7.38 (d, J = 8.4 Hz, 4H), 7.28 –7.18 (m, 2H), 7.05 (s, 2H), 7.02 – 6.97 (m, 2H), 6.89 – 6.83 (m, 2H), 6.47(s, 4H), 6.34 – 6.19 (m, 2H), 6.07 (s, 2H), 5.19 (s, 2H), 3.60– 3.48 (m, 2H), 1.36 (d, J = 6.8 Hz, 12H), 1.17 (dd, J = 24.0, 6.4 Hz, 12H); 13 C NMR (101 MHz, CDCl 3 ) δ 169.10, 162.21, 140.59, 140.53, 140.44, 134.95, 131.03...

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Abstract

The invention discloses chiral bis[N,O] palladacycle and a synthesizing method thereof. The method includes: allowing an iodobenzene derivative and a (1R,2R)-1,2-diphenyl ethylenediamine derivative which serve as the reactants to have reaction in an organic solvent in the presence of Pd(II) complex and a silver compound to obtain the chiral bis[N,O] palladacycle. The method has the advantages thatmethod is an efficient method for synthesizing the large-steric-hindrance and structure-modifiable chiral bis[N,O] palladacycle; the method is high in product yield, good in selectivity, high in catalyst catalyzing efficiency, mild in reaction condition, simple to operate and significant to the synthesis of the large-steric-hindrance and structure-modifiable chiral bis[N,O] palladacycle, and thesubstrate needed by the method is easy to synthesize, cheap and easy to obtain.

Description

Technical field [0001] The present invention relates to the synthesis of a chiral bis[N,O] palladium complex, in particular to a chiral bis[N,O] palladium complex and a catalytic synthesis method thereof. Background technique [0002] [N,O] cyclopalladium complexes exhibit special physical and chemical properties, and have been applied in the fields of biology, functional materials and catalysis, and have broad application prospects. Many cyclic palladium compounds and cyclic palladium complexes with amino acids or amino acid Schiff bases as ligands have antibacterial and anti-cancer activities. They have been widely used in medicine and biochemical research, and they are more and more popular. s concern. Since the introduction of heavy metal ions can produce higher fluorescence quantum efficiency, cyclopalladium complexes are widely used in the field of photoluminescence. The modified cyclopalladium complexes may become liquid crystal molecules, exhibit liquid crystal properti...

Claims

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Application Information

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IPC IPC(8): C07C231/12C07C233/56
CPCC07C231/12C07C233/56
Inventor 王兴旺陈俊波
Owner SUZHOU UNIV
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