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Trivalent iridium imine complex containing iridium nitrogen double bond, preparation method and application thereof

A technology for complexes and amine compounds, which is applied in the field of synthetic chemistry and achieves the effects of simple preparation method, high thermal stability and good regioselectivity

Active Publication Date: 2020-12-08
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Traditional synthetic methods such as the reduction of nitro or cyano compounds and the Hofmann degradation of amides have many shortcomings in terms of ease of operation, availability of raw materials, selectivity of the reaction, and atom economy.

Method used

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  • Trivalent iridium imine complex containing iridium nitrogen double bond, preparation method and application thereof
  • Trivalent iridium imine complex containing iridium nitrogen double bond, preparation method and application thereof
  • Trivalent iridium imine complex containing iridium nitrogen double bond, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: the synthesis of the trivalent iridium imine compound containing iridium nitrogen double bond

[0023]

[0024] At -78°C, n-BuLi (1.6M) n-hexane solution (0.50mL, 0.8mmol) was slowly added dropwise to phenyldipyrrole C 15 h 14 N 2 (127.0mg, 0.57mmol) in tetrahydrofuran solution, stirred at this temperature for 1 hour, slowly rose to room temperature and continued to react for 1 hour, then added monovalent iridium precursor cyclooctadiene iridium chloride dimer [(COD) IrCl] 2 (188.0mg, 0.28mmol), continue to react at room temperature for 3 hours. Then the phenylazide PhN 3 (50.0mg, 0.42mmol) was added to the reaction system and reacted for another 3 hours. After the reaction, stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (petroleum ether / dichloromethane (v / v)=8:1) to obtain the dark red target product trivalent iridium Amine complex C 21 h 18 IrN 3 (115 mg, 81% yiel...

Embodiment 2

[0027] Example 2: Trivalent iridium imine complexes catalyze the trans-Malkovamination of olefins

[0028]

[0029] The catalyst prepared in Example 1 was used to catalyze the trans-Martensoyl hydroamination of olefins: to styrene (1mmol, 104mg) and aniline (1mmol, 93mg) was added an imine complex containing trivalent iridium (0.001mmol, 5.0mg) toluene solution, the reaction temperature is 25°C, and the reaction time is 90 minutes. After the end, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the quality remains unchanged, and the corresponding amine compound C is obtained. 14 h 15 N (177 mg, 88% yield), elemental analysis: C 85.24, H 7.66, N 7.10 (theoretical); C 85.33, H 7.69, N 7.12 (actual).

Embodiment 3

[0030] Example 3: Trivalent iridium imine complexes catalyze the trans-Malkovamination of olefins

[0031]

[0032] The catalyst prepared in Example 1 was used to catalyze the trans-Martensoyl hydroamination reaction of olefins: to styrene (1mmol, 104mg) and aniline (1mmol, 93mg) was added an imine complex containing trivalent iridium (0.002mmol, 10.0mg) toluene solution, the reaction temperature is 40°C, and the reaction time is 80 minutes. After the end, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the quality remains unchanged, and the corresponding amine compound C is obtained. 15 h 17 N (190 mg, 90% yield), elemental analysis: C 85.26, H 8.11, N 6.63 (theoretical); C 85.19, H 8.19, N 6.73 (actual).

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Abstract

The invention belongs to the technical field of synthetic chemistry, and in particular relates to a trivalent iridium imine complex containing iridium nitrogen double bonds, a preparation method and an application of the trivalent iridium imine complex. A binuclear iridium compound cyclooctadiene iridium chloride dimer [ (COD) IrCl ]2 is taken as a raw material, and the binuclear iridium compoundiridium(I) cyclooctadiene chloride, dimer [ (COD) IrCl ]2 reacts with phenyl dipyrrole compounds under an alkaline condition to obtain a precursor containing a monovalent iridium complex, and the precursor is oxidized into the trivalent iridium imine compound containing the iridium nitrogen double bonds by using an azide oxidation method. The synthesis process is simple and green, and has excellent selectivity and higher yield. The trivalent iridium imine complex has the characteristics of stable physical and chemical properties, thermal stability and the like, and shows excellent activity andregioselectivity (anti-Markovnikov's rule) in hydroamination of olefins.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and specifically relates to a trivalent iridium imine compound containing iridium nitrogen double bonds, a preparation method and an application thereof. Background technique [0002] Linear amine compounds can be converted into important chemical intermediates through various known reactions, so they are widely used in the synthesis of pesticides, cosmetics, and medical supplies. Therefore, the synthesis of amine compounds has always been one of the focuses of research in the field of chemistry. Traditional synthetic methods such as reduction of nitro or cyano compounds, Hofmann degradation of amides, etc. have many shortcomings in terms of ease of operation, availability of raw materials, reaction selectivity and atom economy. The hydroamination reaction avoids the generation of by-products such as salts (such as halogen salts, etc.), and theoretically every atom in the two raw mat...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/00B01J31/22C07C209/60C07C211/48C07C211/52C07C213/08C07C217/84
CPCB01J31/1815B01J2531/0241B01J2531/827C07B2200/09C07C209/60C07C213/08C07F15/004C07C211/48C07C211/52C07C217/84
Inventor 姚子健樊晓楠林楠邓维
Owner SHANGHAI INST OF TECH
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