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CN114478351A - Method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compound - Google Patents

Method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compound Download PDF

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CN114478351A
CN114478351A CN202210074585.6A CN202210074585A CN114478351A CN 114478351 A CN114478351 A CN 114478351A CN 202210074585 A CN202210074585 A CN 202210074585A CN 114478351 A CN114478351 A CN 114478351A
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indole
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CN114478351B (en
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孙宏枚
孟蝶蝶
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Suzhou University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04Indoles; Hydrogenated indoles
    • C07D209/10Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12Radicals substituted by oxygen atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member

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Abstract

The invention discloses a novel method for synthesizing an alpha-alkyl substituted indole-3-formaldehyde compound, which is characterized in that under the existence of magnesium chips, an iron (III) complex containing 1, 3-di (2, 4, 6-trimethylphenyl) imidazole cation is used as a catalyst, and the alpha-alkyl substituted indole-3-formaldehyde compound is synthesized through the hydrogen heteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine. Compared with the prior art, the method avoids using sensitive and flammable Grignard reagent and additive TMEDA, thereby having higher safety and atom economy, and simultaneously having higher applicability of the substrate, which is the first example of the hydrogen heteroaromatic reaction realized by the iron catalyst under the action of magnesium chips.

Description

Method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compound
Technical Field
The invention belongs to the technical field of organic synthesis and preparation, and particularly relates to a novel method for synthesizing an alpha-alkyl substituted indole-3-formaldehyde compound.
Background
The alpha-alkyl substituted indole-3-formaldehyde is an important structural fragment, widely exists in natural products, medicaments and bioactive molecules, and has important synthetic value. During the last decade, transition metal-catalyzed hydroheteroaromatization of arylethenes and indoles has evolved gradually into a new method for synthesizing alpha-alkyl substituted indoles due to 100% atom economy. However, only two reports are reported in the literature concerning iron-based catalysts. In 2015, the Yoshikai group consisted in the presence of the sensitive flammable grignard reagent cyclohexylmagnesium chloride (CyMgCl) and an excess of additive N, N' -Tetramethylethylenediamine (TMEDA), with iron acetylacetonate (fe (acca)3) And imidazole salt SIXyl ∙ HCl (SIXyl is 1, 3-di (2, 6-dimethylphenyl) imidazoline cation) as a catalytic system, so that the hydrogen heteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine is realized. In 2017, Ackermann topic groups on sensitive and flammable Grignard reagents CyMgCl andin the presence of an excess of additive TMEDA, in the form of Fe (acca)3And chiral imidazole salt as a catalytic system, so that the enantioselective hydroheteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine is realized. It can be seen that the presently reported iron-based catalyst-catalyzed hydroarylation of arylethenes with indoles all require the use of sensitive and flammable grignard reagents and an excess of additive TMEDA to allow the reaction to proceed, which limits the functional group tolerance (e.g., intolerance to trifluoromethylstyrene, p-trimethylsilylstyrene, p-morpholinostyrene, 2-vinylpyridine, and 2-vinylbenzofuran), and reduces the atom economy of the reaction. Therefore, it is necessary to develop a new preparation method to improve the safety and industrial applicability of the synthesis of α -alkyl substituted indole-3-carbaldehyde compounds.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compounds, which takes an iron (III) complex containing 1, 3-di (2, 4, 6-trimethylphenyl) imidazole cation as a catalyst in the presence of magnesium chips, and synthesizes the alpha-alkyl substituted indole-3-formaldehyde compounds through the hydrogen heteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine.
The invention adopts the following technical scheme:
a method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compounds comprises the following steps of reacting a catalyst, magnesium, indole-3-formaldehyde imine, aryl ethylene and a solvent in an inert gas atmosphere, and then acidifying to obtain alpha-alkyl substituted indole-3-formaldehyde compounds; specifically, after the reaction, diluted hydrochloric acid is used for acidification, ethyl acetate is used for extraction, and the alpha-alkyl substituted indole-3-formaldehyde compound is obtained through column chromatography separation and purification and can be subjected to quantitative analysis. The catalyst is an iron (III) complex containing 1, 3-bis (2, 4, 6-trimethylphenyl) imidazole cation.
Application of iron (III) complex containing 1, 3-di (2, 4, 6-trimethylphenyl) imidazole cation in reaction for synthesizing alpha-alkyl substituted indole-3-formaldehyde compounds.
In the invention, the iron (III) complex containing 1, 3-di (2, 4, 6-trimethylphenyl) imidazole cation is [ HIMes][FeBr4]The chemical structural formula is as follows:
Figure 524347DEST_PATH_IMAGE001
in the present invention, indole-3-carbaldehyde imine is represented by the following chemical structural formula:
Figure 924498DEST_PATH_IMAGE002
R1is one of hydrogen, methyl, methoxy and fluorine; r2Is methyl or benzyl.
In the present invention, the arylethenes are represented by the following chemical structural formula:
Figure 369386DEST_PATH_IMAGE003
ar is aryl, substituted aryl, heterocyclic aryl; preferably, the arylstyrenes include styrene, o-methoxystyrene, m-methoxystyrene, p-methylstyrene, p-trifluoromethylstyrene, p-trimethylsilylstyrene, p-diphenylaminostyrene, p-morpholinostyrene, 2-vinylnaphthalene, 2-vinylpyridine or 2-vinylbenzofuran.
In the invention, the alpha-alkyl substituted indole-3-formaldehyde compound is expressed by the following chemical structural formula:
Figure 113351DEST_PATH_IMAGE004
wherein the stituent is derived from indole-3-formaldehyde imine and aryl ethylene.
In the technical scheme, the reaction temperature is 25-80 ℃, and the reaction time is 16-48 hours.
In the technical scheme, the inert gas is argon or nitrogen; the solvent is tetrahydrofuran, 2-methyltetrahydrofuran and the like.
In the technical scheme, the molar ratio of the catalyst, the magnesium, the indole-3-formaldehyde imine and the aryl ethylene is 0.03-0.08: 0.8-1: 1.2-1.6. In the preferred technical scheme, the dosage of the aryl ethylene is 1.5 times of that of the indole compound, the dosage of the magnesium is 1 time of that of the indole compound, and the dosage of the catalyst is 5 percent of the molar weight of the indole compound; the reaction temperature was 40 ℃ and the reaction time was 24 hours.
The reaction process for preparing the alpha-alkyl substituted indole-3-formaldehyde compound can be represented as follows:
Figure 225663DEST_PATH_IMAGE005
due to the application of the technical scheme, the invention has the following advantages:
1. in the presence of magnesium chips, the invention uses the iron (III) complex containing 1, 3-di (2, 4, 6-trimethylphenyl) imidazole cation as a catalyst to realize the hydrogen hetero-arylation reaction of aryl ethylene and indole-3-formaldehyde imine and provides a new method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compounds.
2. The preparation method disclosed by the invention has mild conditions, does not need sensitive and flammable Grignard reagents and excessive additives, has better substrate applicability, and is not only suitable for aryl ethylene containing electron donating substituent groups, but also suitable for aryl ethylene containing electron withdrawing substituent groups and heterocyclic olefin.
Detailed Description
The raw materials of the invention are commercial products, the specific operation method and the test method are conventional in the field, and the yield is the isolation yield (except in the table).
The invention is further described below with reference to examples:
the first embodiment is as follows: containing 1, 3-di (2, 4, 6-trimethylbenzeneBased) imidazolium cations (of the formula [ HIMes ]][FeBr4]),([HIMes]Is the synthesis of an iron (III) complex of 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium).
1, 3-bis (2, 4, 6-trimethylphenyl) imidazole bromide (0.38 g, 1.0 mmol) was added to a solution of iron tribromide (0.27 g, 0.9 mmol) in tetrahydrofuran, 60% oCThe reaction is carried out for 24 hours, the solvent is pumped out in vacuum, hexane is washed, the solvent is pumped out, tetrahydrofuran is used for extraction, the clear liquid is centrifuged and transferred, hexane is added into the clear liquid for recrystallization, and reddish brown solid powder is separated out at room temperature, and the yield is 85%. The chemical structural formula is as follows:
Figure 29671DEST_PATH_IMAGE006
elemental analysis of the product resulted in the following:
elemental analysis
Figure 227434DEST_PATH_IMAGE007
Iron complexes are not characterized as being nuclear magnetic due to their paramagnetic properties.
Complexes [ HIMes ]][FeBr4]In the form of ion pairs, in which the anion [ FeBr ]4]-It was characterized by Raman spectroscopy and was found to be at 204 cm-1Characteristic peaks are observed, and are consistent with the reports in the literature (Melissa, S.; Eric, R. S.; Eric, V. P.; Freeman, R. G.), Inorg. Chem., 2001, 40, 2298). Cationic moiety of the Complex [ HIMes]+The molecular ion peak is observed at 305.2011, theoretically 305.2012, and is consistent with theory. The obtained compound was confirmed to be the objective compound.
Example two [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and styrene
Under the protection of argon, catalysts are added into a reaction bottle in sequence(16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), styrene (86. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) as solvent in 40 mg/loReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 as a developing solvent), wherein the yield is 93 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.23 (s, 1H), 8.42 (d, J = 7.6 Hz, 1H), 7.31 – 7.21 (m, 10H), 7.14 (d, J = 8.1 Hz, 1H), 6.95 – 6.86 (m, 2H), 5.22 (s, 2H), 5.05 (q, J = 7.3, 6.8 Hz, 1H), 1.74 (d, J = 7.3 Hz, 3H)。
in the above-mentioned styrene andNthe results of the one-way change based on the reaction of-benzylindole-3-carboxaldehyde imine are as follows.
Figure 775090DEST_PATH_IMAGE008
Figure 741909DEST_PATH_IMAGE009
a Reaction conditions are as follows:N-benzylindole-3-carboxaldehyde imine (0.5 mmol), styrene (0.75 mmol), iron catalyst (5 mol%), additive (0.5 mmol), tetrahydrofuran (1.5 mL), 24 h, the yield of product was determined in the gas phase with n-dodecane as internal standard. b The isolation yield.
[HItBu][FeBr4]The chemical structural formula is as follows:
Figure 779136DEST_PATH_IMAGE010
example III [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and o-methoxy styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), o-methoxystyrene (100. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 25 mloReacting for 48 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent), wherein the yield is 96 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.21 (s, 1H), 8.44 (d, J = 7.7 Hz, 1H), 7.42 (d, J = 7.5 Hz, 1H), 7.28 (d, J = 3.7 Hz, 2H), 7.24 (d, J = 4.6 Hz, 3H), 7.02 – 6.97 (m, 3H), 6.76 (d, J = 8.2 Hz, 1H), 5.48 (s, 2H), 4.93 (q, J = 7.4 Hz, 1H), 3.61 (s, 3H), 1.66 (d, J = 7.4 Hz, 3H)。
example four [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and m-methoxy styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), m-methoxystyrene (100. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 25 mloReacting for 48 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 92 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, at room temperature at Unity Inova-4Characterization by measurement on a type 00 NMR instrument:1H NMR (400 MHz, CDCl3) δ 10.23 (s, 1H), 8.42 (d, J = 7.8 Hz, 1H), 7.31 (t, J = 7.8 Hz, 1H), 7.26 – 7.13 (m, 6H), 6.93 – 6.89 (m, 2H), 6.80 (d, J = 7.8 Hz, 1H), 6.77 – 6.72 (m, 2H), 5.24 (s, 2H), 5.02 (q, J = 7.4 Hz, 1H), 3.72 (s, 3H), 1.73 (d, J = 7.4 Hz, 3H)。
example five [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and p-methoxy styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), p-methoxystyrene (104. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added as solvents in sequence to a reaction flask in 40 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 92 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.23 (s, 1H), 8.44 (d, J = 7.8 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.27 – 7.25 (m, 3H), 7.24 – 7.21 (m, 1H), 7.14 (dd, J = 12.3, 8.3 Hz, 3H), 6.94 – 6.90 (m, 2H), 6.81 (d, J = 8.8 Hz, 2H), 5.24 (s, 2H), 5.00 (q, J = 7.4 Hz, 1H), 3.77 (s, 3H), 1.72 (d, J = 7.4 Hz, 3H)。
example six [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydro-heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and p-methylstyrene
Under argon protection, the catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), p-methylstyrene (99. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added sequentially to a reaction flaskAs solvent, in 40oReacting for 16 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 95%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.26 (s, 1H), 8.52 – 8.46 (m, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.27 (dt, J = 5.6, 2.6 Hz, 3H), 7.23 (d, J = 8.3 Hz, 1H), 7.17 (d, J = 8.2 Hz, 1H), 7.12 (s, 4H), 6.97 – 6.92 (m, 2H), 5.26 (s, 2H), 5.03 (q, J = 7.4 Hz, 1H), 2.33 (s, 3H), 1.75 (d, J = 7.4 Hz, 3H)。
EXAMPLE seven [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and p-trifluoromethyl styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), p-trifluoromethylstyrene (111. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in sequence as solvents in a reaction flask at 60 deg.CoReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 68 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.23 (s, 1H), 8.41 (d, J = 7.8 Hz, 1H), 7.50 (d, J = 8.2 Hz, 2H), 7.32 (t, J = 8.5 Hz, 3H), 7.27 – 7.23 (m, 4H), 7.20 (d, J = 8.2 Hz, 1H), 6.89 – 6.84 (m, 2H), 5.24 (s, 2H), 5.13 (d, J = 7.4 Hz, 1H), 1.79 (d, J = 7.3 Hz, 3H).
EXAMPLE eight [ HIMes][FeBr4]As catalyst, catalyzing N-benzylHydroheteroaromatization of benzylindole-3-carboxaldehyde imine with p-trimethylsilylstyrene
Under the protection of argon, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), trimethylsilylstyrene (154. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 40 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 92 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.26 (s, 1H), 8.47 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 7.7 Hz, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.27 – 7.22 (m, 6H), 7.18 (d, J = 8.1 Hz, 1H), 6.95 – 6.91 (m, 2H), 5.29 (s, 2H), 5.05 (q, J = 7.4 Hz, 1H), 1.78 (d, J = 7.4 Hz, 3H), 0.28 (s, 9H)。
EXAMPLE nine [ HIMes][FeBr4]As a catalyst, catalyzing the hydro-heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and p-diphenylaminostyrene
Under the protection of argon, a catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), p-diphenylaminostyrene (271.0 mg, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 40oReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 as a developing solvent), wherein the yield is 93 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, and tabulated at room temperature on a Unity Inova-400 NMR instrumentAnd (3) carrying out mark:1H NMR (400 MHz, CDCl3) δ 10.46 (s, 1H), 8.63 (d, J = 7.8 Hz, 1H), 7.48 (d, J = 7.7 Hz, 1H), 7.44 (dt, J = 5.9, 3.2 Hz, 4H), 7.39 (d, J = 7.3 Hz, 3H), 7.32 – 7.26 (m, 3H), 7.23 – 7.14 (m, 9H), 7.12 – 7.09 (m, 2H), 5.57 – 5.45 (m, 2H), 5.19 (q, J = 7.3 Hz, 1H), 1.93 (d, J = 7.3 Hz, 3H)。
example ten [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and p-morpholine styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), p-morpholinostyrene (142.0 mg, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvent, in 40 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 92 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.24 (s, 1H), 8.45 (d, J = 7.8 Hz, 1H), 7.34 – 7.25 (m, 4H), 7.22 (d, J = 7.2 Hz, 1H), 7.13 (dd, J = 15.1, 8.4 Hz, 3H), 6.92 (d, J = 5.0 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H), 5.25 (s, 2H), 4.98 (q, J = 7.3 Hz, 1H), 3.86 (s, 4H), 3.12 (s, 4H), 1.72 (d, J = 7.3 Hz, 3H).
EXAMPLE eleven [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydro-heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and 2-vinyl naphthalene
Under the protection of argon, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), 2-vinylnaphthalene (154 mg, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, and the mixture was stirred in a stirrer, a stirrer40 oReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent), wherein the yield is 88%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.30 (s, 1H), 8.47 (d, J = 7.9 Hz, 1H), 7.90 – 7.72 (m, 5H), 7.50 (dd, J = 6.7, 3.1 Hz, 2H), 7.36 (s, 1H), 7.28 – 7.23 (m, 4H), 7.19 (s, 1H), 6.92 (d, J = 7.8 Hz, 2H), 5.26 (d, J = 7.9 Hz, 3H), 1.89 (s, 3H)。
EXAMPLE twelve [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and 2-vinylpyridine
Under the protection of argon, a catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), 2-vinylpyridine (81. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 50 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (taking a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 as a developing solvent), wherein the yield is 72 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.24 (s, 1H), 8.45 (d, J = 7.9 Hz, 1H), 7.33 – 7.26 (m, 3H), 7.25 – 7.19 (m, 6H), 7.14 (d, J = 8.2 Hz, 1H), 6.91 (dd, J = 6.9, 2.4 Hz, 2H), 5.23 (s, 2H), 5.05 (q, J = 7.4 Hz, 1H), 1.75 (d, J = 7.4 Hz, 3H)。
EXAMPLE thirteen [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl indole-3-formaldehyde imine and 2-vinyl benzofuran
Under the protection of argon, a catalyst (33.8 mg, 0.05 mmol, 10 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzylindole-3-carboxaldehyde imine (169.6 mg, 0.5 mmol), 2-vinylbenzofuran (102. mu.l, 0.75 mmol) and tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents in 50 mloReacting for 48 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (taking a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 as a developing solvent), wherein the yield is 54%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3 δ 10.31 (s, 1H), 8.41 (d, J = 7.8 Hz, 1H), 7.48 (d, J = 6.7 Hz, 1H), 7.31 (dt, J = 13.3, 6.4 Hz, 3H), 7.24 – 7.18 (m, 6H), 6.96 (d, J = 6.3 Hz, 2H), 6.57 (s, 1H), 5.44 (s, 2H), 5.13 (q, J = 7.1 Hz, 1H)。
example fourteen [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-methylindole-3-formaldehyde imine and styrene
Under the protection of argon, a catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-methylindole-3-carboxaldehyde imine (132.2 mg, 0.5 mmol), styrene (86. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvents, in 40 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 90 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.26 (s, 1H), 8.42 – 8.37 (m, 1H), 7.34 – 7.23 (m, 8H), 5.20 (q, J = 7.4 Hz, 1H), 3.44 (s, 3H), 1.87 (d, J = 7.4 Hz, 3H)。
example fifteen [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl-5-methoxyindole-3-formaldehyde imine and styrene
Under the protection of argon, a catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-methyl-5-methoxyindole-3-carbaldehyde imine (185.1 mg, 0.5 mmol), styrene (86. mu.l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in this order as solvents to a reaction flask, and the mixture was dissolved in 40 ml of wateroReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent), wherein the yield is 91%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.18 (s, 1H), 7.97 (d, J = 2.5 Hz, 1H), 7.31 – 7.26 (m, 5H), 7.22 (d, J = 7.6 Hz, 3H), 7.04 (d, J = 8.9 Hz, 1H), 6.94 – 6.90 (m, 2H), 6.86 (dd, J = 8.9, 2.6 Hz, 1H), 5.21 (s, 2H), 4.98 (q, J = 7.4 Hz, 1H), 3.91 (s, 3H), 1.75 (d, J = 7.4 Hz, 3H)。
example sixteen [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydro-heteroaromatic reaction of N-benzyl-5-fluoro-indole-3-carboxaldehyde imine and styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-methyl-5-fluoro-indole-3-carbaldehyde imine (179.1 mg, 0.5 mmol), styrene (86 μ l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvent, in 40 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent), wherein the yield is 87%.
The product is processedDissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.17 (s, 1H), 8.10 (dd, J = 9.4, 2.6 Hz, 1H), 7.28 (d, J = 7.5 Hz, 5H), 7.25 – 7.19 (m, 3H), 7.07 – 7.03 (m, 1H), 6.95 (td, J = 9.0, 2.6 Hz, 1H), 6.91 – 6.87 (m, 2H), 5.21 (d, J = 1.3 Hz, 2H), 5.00 (q, J = 7.4 Hz, 1H), 1.75 (d, J = 7.4 Hz, 3H)。
example seventeen [ HIMes ]][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl-6-chlorine-indole-3-formaldehyde imine and styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-methyl-6-chloro-indole-3-carbaldehyde imine (187.1 mg, 0.5 mmol), styrene (86 μ l, 0.75 mmol), tetrahydrofuran (1.5 ml) were added in succession to a reaction flask as solvent, in 50 mloReacting for 24 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 is used as a developing agent) to obtain the yield of 80 percent.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.18 (s, 1H), 8.34 (d, J = 8.4 Hz, 1H), 7.31 – 7.27 (m, 5H), 7.21 (dd, J = 16.9, 7.5 Hz, 4H), 7.14 (d, J = 1.7 Hz, 1H), 6.89 (dd, J = 7.2, 2.4 Hz, 2H), 5.20 – 5.17 (m, 2H), 4.98 (q, J = 7.4 Hz, 1H), 1.74 (d, J = 7.4 Hz, 3H)。
EXAMPLE eighteen [ HIMes][FeBr4]Is used as a catalyst to catalyze the hydrogen heteroaromatic reaction of N-benzyl-7-methylindole-3-formaldehyde imine and styrene
Under argon protection, catalyst (16.9 mg, 0.025 mmol, 5 mol%), magnesium turnings (12.0 mg, 0.5 mmol), N-benzyl-7-methylindole-3-carboxaldehyde imine (177.1 mg, 0.5 mmol), styrene (86 μ l, 0.75 mmol) were added in sequence to a reaction flaskTetrahydrofuran (1.5 ml) as solvent at 80 deg.CoReacting for 16 hours at the temperature of C, quenching the reaction by water, adding diluted hydrochloric acid (2 mol/L, 1.5 ml) for acidification, extracting a reaction product by ethyl acetate, and separating and purifying by column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 5 as a developing solvent), wherein the yield is 86%.
The product was dissolved in CDCl3Medium (about 0.4 mL), sealed, characterized by measurement on a Unity Inova-400 NMR instrument at room temperature:1H NMR (400 MHz, CDCl3) δ 10.21 (s, 1H), 8.36 (d, J = 7.9 Hz, 1H), 7.31 – 7.26 (m, 5H), 7.20 (t, J = 7.6 Hz, 4H), 6.98 (d, J = 7.2 Hz, 1H), 6.85 (d, J = 6.1 Hz, 2H), 5.48 (d, J = 5.7 Hz, 2H), 4 .97 (q, J = 7.4 Hz, 1H), 2.44 (s, 3H), 1.69 (d, J = 7.3 Hz, 3H)。
in the prior art, for the hydrogen heteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine catalyzed by an iron catalyst, a sensitive and flammable Grignard reagent and an excessive additive TMEDA are needed to carry out the reaction, so that the tolerance of a functional group and the potential application value are limited. Therefore, the method for constructing the alpha-alkyl substituted indole-3-formaldehyde compound by using the iron (III) complex as the catalyst in the presence of magnesium chips and by using the hydrogen heteroaromatic reaction of aryl ethylene and indole-3-formaldehyde imine under mild conditions has obvious innovation, safety and better potential application value.

Claims (10)

1. A method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compounds is characterized by comprising the following steps of mixing a catalyst, magnesium, indole-3-formaldehyde imine, aryl ethylene and a solvent in an inert gas atmosphere, then reacting, and acidifying to obtain alpha-alkyl substituted indole-3-formaldehyde compounds; the catalyst is an iron (III) complex containing imidazole cations.
2. The method of claim 1, wherein the compound is acidified with hydrochloric acid.
3. The method of claim 1, wherein the catalyst is [ HIMes ]][FeBr4]。
4. The method for synthesizing α -alkyl substituted indole-3-carbaldehyde compounds according to claim 1, wherein the indole-3-carbaldehyde imine is represented by the following chemical structural formula:
Figure 342182DEST_PATH_IMAGE001
R1is one of hydrogen, methyl, methoxy and fluorine; r2Is methyl or benzyl;
the arylethenes are represented by the following chemical structural formula:
Figure 548035DEST_PATH_IMAGE002
ar is aryl, substituted aryl or heterocyclic aryl.
5. The method of claim 4, wherein the aryl group of the vinyl aromatic compound comprises styrene, o-methoxystyrene, m-methoxystyrene, p-methylstyrene, p-trifluoromethylstyrene, p-trimethylsilylstyrene, p-diphenylaminostyrene, p-morpholinostyrene, 2-vinylnaphthalene, 2-vinylpyridine, or 2-vinylbenzofuran.
6. The method for synthesizing the alpha-alkyl substituted indole-3-carbaldehyde compound according to claim 1, wherein the reaction temperature is 25-80 ℃ and the reaction time is 16-48 hours.
7. The method for synthesizing alpha-alkyl substituted indole-3-carbaldehyde compounds according to claim 1, wherein the molar ratio of the catalyst, magnesium, indole-3-carbaldehyde imine and aryl ethylene is 0.03-0.08: 0.8-1: 1.2-1.6.
8. The alpha-alkyl substituted indole-3-carbaldehyde compound prepared by the method for synthesizing the alpha-alkyl substituted indole-3-carbaldehyde compound according to claim 1.
9. The application of the iron (III) complex containing the imidazolium cation in the reaction of synthesizing the alpha-alkyl substituted indole-3-formaldehyde compound is characterized in that the iron (III) complex containing the imidazolium cation is [ HIMes ]][FeBr4]。
10. Use according to claim 9, characterized in that the reaction is carried out in the presence of magnesium.
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