Nitrogen-heterocyclic carbene mixed nickel(ii) complexes and their applications

A technology of nitrogen heterocycles and complexes, which is applied in the field of organic synthesis and preparation, can solve the problems of expensive catalysts, avoid the use of external ligands, and achieve the effects of single and clear catalyst structure and simple synthesis

Active Publication Date: 2022-04-15
SUZHOU UNIV
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  • 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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  • Nitrogen-heterocyclic carbene mixed nickel(ii) complexes and their applications
  • Nitrogen-heterocyclic carbene mixed nickel(ii) complexes and their applications
  • Nitrogen-heterocyclic carbene mixed nickel(ii) complexes and their applications

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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 a nitrogen-heterocyclic carbene mixed type nickel (II) complex and its application. The molecular formula is Ni[P(OEt) 3 ]{[RNC(CH 3 )C(CH 3 )NR]C}Br 2 (R is 2,4,6-trimethylphenyl or 2,6-diisopropylphenyl), which can be used to synthesize 2-benzyl indole-3-formaldehyde compounds, with the mixed type of the present invention Synthesis of 2-benzyl indole-3-formaldehydes through the hydroheteroarylation reaction of arylethenes and indole-3-formaldehyde imines in the presence of potassium methoxide with nickel(II) complexes as catalysts compound. The method provided by the invention uses the air-stable, cheap and easy-to-get divalent nickel (II) complex as a catalyst for the first time, avoiding the use of sensitive Grignard reagents and zero-valent metal complexes, which is realized by nickel-based catalysts , the first example of the preparation of 2-benzyl indole-3-carbaldehydes by imine-directed, hydroheteroarylation of arylvinyls.

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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Patent Type & Authority Patents(China)
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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