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N-heterocyclic carbene-based mixed nickel (II) complex and application thereof

A nitrogen heterocycle and complex technology, applied in the field of organic synthesis preparation, can solve problems such as expensive catalysts, avoid the use of external ligands, be beneficial to large-scale synthesis and use, and have the effects of low price

Active Publication Date: 2019-10-15
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In the past ten years, there have been some reports on the reaction catalyzed by nickel-based catalysts, but there are few reports involving the hydroheteroarylation of arylvinyl compounds and indole compounds. At the same time, there are expensive catalysts in the prior art. question

Method used

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  • N-heterocyclic carbene-based mixed nickel (II) complex and application thereof
  • N-heterocyclic carbene-based mixed nickel (II) complex and application thereof
  • N-heterocyclic carbene-based mixed nickel (II) complex and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment one: Ni[P(OEt) 3 ]{[RNC(CH 3 )C(CH 3 )NR]C}Br 2 (R = 2,4,6-trimethylphenyl) synthesis

[0034] Under argon protection, nitrogen heterocyclic carbene [RNC(CH 3 )C(CH 3 )NR]C (0.3325 g, 1.0 mmol) was added to a tetrahydrofuran solution of di(triethylphosphite)nickel(II) bromide (0.5508 g, 1.0 mmol), reacted at room temperature for 3 hours, and removed the solvent in vacuo , wash the residue with n-hexane, extract the residue with toluene, transfer the supernatant and remove the solvent toluene to obtain a red solid as a divalent nickel (II) complex with a yield of 87%.

[0035] The product was subjected to elemental analysis, and the results are shown in Table 1:

[0036]

[0037] The product was characterized by NMR, and the results are as follows:

[0038]Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 7.06 (s, 4...

Embodiment 2

[0039] Embodiment two: Ni[P(OEt) 3 ]{[RNC(CH 3 )C(CH 3 )NR]C}Br 2 (R = 2,6-Diisopropylphenyl) Synthesis

[0040] Under argon protection, nitrogen heterocyclic carbene [RNC(CH 3 )C(CH 3 )NR]C (0.4167 g, 1.0 mmol) was added to a tetrahydrofuran solution of bis(triethylphosphite) nickel(II) bromide (0.5508 g, 1.0 mmol), reacted at room temperature for 3 hours, and removed the solvent in vacuo , wash the residue with n-hexane, extract the residue with toluene, transfer the clear liquid and remove the solvent toluene to obtain a red solid as a divalent nickel (II) complex with a yield of 85%.

[0041] Carry out elemental analysis to product, the result is shown in the following table:

[0042]

[0043] The product was characterized by NMR, and the results are as follows:

[0044] Dissolve the product in C 6 D. 6 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 7.53 (t,...

Embodiment 3

[0045] Embodiment three: Ni[P(OEt) 3 ]{[RNC(CH 3 )C(CH 3 )NR]C}Br 2 (R = 2,4,6-trimethylphenyl)-catalyzed hydroheteroarylation of N-methylindole-3-formaldehyde imine with styrene

[0046] Under the protection of argon, the catalyst (35.9 mg, 0.05 mmol, 10 mol%), potassium methylate (35.1 mg, 0.5 mmol), N-methylindole-3-formaldehyde imine (132.2 mg, 0.5 mmol), styrene (86 microliters, 0.75 mmol), toluene (1.5 ml) as solvent, at 130 o C for 48 hours, stop the reaction with water, add dilute hydrochloric acid (2 mol / L, 1 ml) for acidification, the reaction product is extracted with ethyl acetate, separated and purified by column chromatography (the volume ratio of ethyl acetate / petroleum ether is 1:5 mixed solvent as developer), the yield was 95%.

[0047] Dissolve the product in CDCl 3 Medium (about 0.4 mL), seal the tube, measure and characterize on a Unity Inova-400 NMR instrument at room temperature: 1 H NMR (400 MHz, CDCl 3 ): δ 10.31 (s, 1H), 8.43 (dd, J = 6.1, 2....

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Abstract

The invention discloses an n-heterocyclic carbene-based mixed nickel (II) complex and application thereof. The n-heterocyclic carbene-based mixed nickel (II) complex adopts a molecular formula of Ni[P(OEt)3]{[RNC(CH3)C(CH3)NR]C}Br2, (R is 2,4,6-trimethylphenyl or 2,6-diisopropyl phenyl); the n-heterocyclic carbene-based mixed nickel (II) complex can be applied to synthesis of a 2-benzylindole-3-formaldehyde compound, and with the mixed nickel (II) complex as a catalyst, the 2-benzylindole-3-formaldehyde compound is synthesized through a hydrogen heteroarylation reaction of an aryl vinyl compound and an indole-3-formaldehyde imine compound in the presence of potassium methoxide. By a method provided by the invention, the air-stable, cheap and easily-obtained divalent nickel (II) complex isused as the catalyst for the first time, use of a sensitive Grignard reagent and a zero-valent metal complex is avoided, and preparation of the 2-benzylindole-3-formaldehyde compound through the hydrogen heteroarylation reaction of the aryl vinyl compound, which is achieved by a nickel-based catalyst and oriented by imine, is a first case.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis preparation, in particular to a method for synthesizing 2-benzyl indole-3-carbaldehyde compounds, in particular to a nitrogen heterocyclic carbene mixed nickel (II) complex and its application. Background technique [0002] The indole skeleton and its derivatives not only widely exist in natural products and bioactive molecules, but also are general structural units for the construction of drug molecules and organic optoelectronic materials. The development of their preparation methods is always attracting attention. In indole derivatives, the alkylation of the β-position on the indole skeleton can be achieved by methods such as Friedel-Crafts alkylation, allylation and Michael addition reaction (see Bandini, M.; Eichholzer, A. Angew. Chem., Int. Ed . 2009, 48 ,9608). However, there are still relatively few methods for the alkylation of the α-position on the indole skeleton, and usual...

Claims

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Application Information

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IPC IPC(8): C07F15/04B01J31/22C07D209/12C07D409/06
CPCC07F15/04B01J31/2273C07D209/12C07D409/06B01J2531/847B01J2531/0233B01J2531/0238
Inventor 孙宏枚吴沁家
Owner SUZHOU UNIV
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