Preparation and application of a large sterically hindered trivalent rhodium imine complex

A technology of large steric hindrance and rhodium imine, applied in the preparation of organic compounds, preparation of amino hydroxyl compounds, rhodium organic compounds, etc., to achieve the effect of high atom economy, simple preparation method and stable physical and chemical properties

Active Publication Date: 2020-12-29
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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  • Preparation and application of a large sterically hindered trivalent rhodium imine complex
  • Preparation and application of a large sterically hindered trivalent rhodium imine complex
  • Preparation and application of a large sterically hindered trivalent rhodium imine complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Embodiment 1: the synthesis of the trivalent rhodium imine complex of large steric hindrance containing rhodium-nitrogen double bond structure

[0025]

[0026] At –78°C, n-BuLi (1.6M) in n-hexane (0.50 mL, 0.8 mmol) was slowly added dropwise to 5 mL of diisopropyl-substituted phenyldipyrrole C 21 h 26 N 2 (183.0mg, 0.60mmol) in tetrahydrofuran solution, continue to stir at this temperature for 1 hour after the dropwise addition, slowly rise to room temperature and continue to react for 1 hour, then add the monovalent rhodium precursor cyclooctadiene rhodium chloride dimerization Body [(COD)RhCl] 2 (148.0mg, 0.30mmol), continue to react at room temperature for 3 hours. Then the phenylazide PhN 3 (107.0mg, 0.90mmol) was added to the reaction system and reacted at room temperature for 3 hours. After the reaction, stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by silica gel column chromatography (eluent: petrol...

Embodiment 2

[0028] Embodiment 2: trivalent rhodium imine complexes catalyze the anti-Martensoyl hydroamination reaction of olefins

[0029]

[0030] The catalyst prepared in Example 1 was used to catalyze the reverse Martensohydroamination reaction of olefins: 5 mL of imine complex containing trivalent rhodium (0.001 mmol, 5.0 mg) was added to styrene (1 mmol, 104 mg) and aniline (1 mmol, 93 mg). ) in toluene solution, the reaction temperature is 25°C, and the reaction time is 70 minutes. After the end, the reaction solution is concentrated, and directly separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate (v / v)=8:1) , dried until the mass remains unchanged, and the corresponding amine compound C 14 h 15 N (185mg, yield 88%), 1 H NMR (400MHz, CDCl 3 ,25℃):δ=7.40-7.32(m,2H),7.28-7.20(m,5H),6.81-6.74(m,1H),6.70(d,2H),3.75(br s,1H),3.45 (t, J=6.8Hz, 2H), 2.99 (t, J=6.8Hz, 2H); elemental analysis: C 85.24, H 7.66, N 7.10 (theoretical); C 85.26, H 7.61, N...

Embodiment 3

[0031] Embodiment 3: trivalent rhodium imine complexes catalyze the anti-Martensitic hydroamination reaction of olefins

[0032]

[0033] The catalyst prepared in Example 1 was used to catalyze the reverse Martensohydroamination reaction of olefins: 5 mL of imine complex containing trivalent rhodium (0.002 mmol, 10.0 mg) was added to styrene (1 mmol, 104 mg) and aniline (1 mmol, 93 mg). ) in toluene solution, the reaction temperature is 25°C, and the reaction time is 60 minutes. After the completion, the concentrated reaction solution is directly separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate (v / v)=8:1), Dry until the mass remains constant to obtain the corresponding amine compound C 15 h 17N (192 mg, yield 91%), 1 H NMR (400MHz, CDCl 3 ,25℃):δ=7.42-7.33(m,1H),7.29-7.23(m,5H),6.80-6.74(m,1H),6.65(d,2H),3.75(br s,1H),3.45 (t, J = 6.8Hz, 2H), 2.99 (t, J = 6.8Hz, 2H), 2.32 (s, 3H); elemental analysis: C 85.26, H 8.11, N 6.63 (theoretic...

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Abstract

The invention provides a large-steric-hindrance trivalent rhodium imide complex containing a rhodium-nitrogen dual-key structure. The large-steric-hindrance trivalent rhodium imide complex is characterized by including the following structure shown in the description. A synthesis technology is simple and green, and has excellent selectivity and a high yield. The large-steric-hindrance trivalent rhodium imide complex has the features of stable physical and chemical properties and thermal stability, and has excellent activity and regional selectivity in an anti-Markovnikov hydroamination reaction of olefins.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and specifically relates to a trivalent rhodium-imine complex with a rhodium-nitrogen double bond structure containing large steric hindrance, a preparation method and an application thereof. Background technique [0002] Linear amine compounds are an important class of fine chemical intermediates, which are widely used in the synthesis of pesticides, medical supplies and functional materials. Therefore, the efficient and cheap synthesis of such compounds has always been one of the focuses 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 ato...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/00B01J31/22C07C209/60C07C211/48C07C211/52C07C213/00C07C217/84
CPCB01J31/1815B01J2531/822C07C209/60C07C213/00C07F15/008C07C211/48C07C211/52C07C217/84
Inventor 姚子健高永红云雪静靳永旭邓维
Owner SHANGHAI INST OF TECH
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