A method for anti-markovnikov hydroamination of aromatic alkenes catalyzed by aluminum

Abstract

The application discloses a new type of organic aluminum catalyst catalyzed implementation of unactivated aromatic olefin anti-Markovnikov hydroamination addition, belongs to the field of organic chemistry. The aluminum catalyst is synthesized by using existing ligand and commercially available aluminum alkyl compound, and the synthesis step is simple and easy to operate. Under the action of the aluminum catalyst and the additive, aromatic olefin and different amines are reacted in an organic solvent, and a series of amine compounds are obtained with good regioselectivity and high yield. The application uses cheap and easily available main group metal aluminum catalyst, and synthesizes olefin anti-Markovnikov hydroamination addition product with excellent regioselectivity under relatively mild and simple reaction conditions.

Description

TECHNICAL FIELD

[0001] The method of the present application belongs to the field of organic chemistry, and uses a β-diketiminate ligand supported aluminum catalyst to achieve the hydroamination reaction of aromatic olefins. BACKGROUND

[0002] Amine compounds are important chemical substances, which have important effects in the fields of biology, medicine, materials and energy. So far, there are many synthetic methods for constructing C-N bonds, such as coupling amination reaction, addition reaction of amine and isocyanate, Diels-Alder reaction of nitrogen-containing olefin amine, reaction of hydroxylamine and aldehyde / ketone, alkylation of amine, olefin hydroamination reaction, etc. However, these synthetic methods have some defects, for example, they need noble metal catalysts or harsh reaction conditions, and even some methods have high requirements for reaction reagents, such as the need for pre-activated or some dangerous reactants. Therefore, it is necessary to develop a new efficient method for synthesizing amines. Compared with other types of C-N bond construction reactions, the hydroamination reaction of olefins is one of the most efficient, environmentally friendly and economical synthetic methods due to the easy availability of raw materials, atomic economy and environmental friendliness.

[0003] However, due to the low reactivity and electron cloud density of carbon-carbon double bond, it is difficult for unactivated olefins to undergo hydroamination reaction. At the same time, the regioselectivity of the reaction is a great challenge. Currently, researchers use catalytic hydrogenation technology to successfully synthesize a large number of N-containing organic compounds, and on the basis of achieving high yield, they can synthesize anti-Markovnikov hydrogenation addition products with high regioselectivity. However, these reactions usually use catalysts such as Ni (C. Lee, H. Kang, S. Hong, Chem. Sci. 2024, 15, 442-457.), Ru (J. Takaya, J. F. Hartwig, J. Am. Chem. Soc. 2005, 127, 16, 5756-5757.), Ir (K. Sedillo, F. Fan, R. R. Knowles, A. G. Doyle, J. Am. Chem. Soc. 2024, 146, 29, 20349-20356.), La (J.-S. Ryu, G. Y. Li, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 41, 12584-12605.), which not only increases the cost, but also makes the catalyst easy to deactivate and difficult to recover.

[0004] Therefore, it is of great value to develop a new type of catalyst with low cost, easy synthesis and greenness, especially for the catalysis of olefin anti-Markovnikov hydroamination reaction. SUMMARY

[0005] The application aims to provide a novel synthesis method of amine compounds, which has a cheap and easily available raw material, a green and environment-friendly catalyst, a good yield and a wide substrate range, and has certain industrial application prospect.

[0006] The application realizes one of the above-mentioned purposes by adopting the following technical scheme.

[0007] The application relates to a method for anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum, which comprises the following steps.

[0008] The catalyst [Al] and an additive are dissolved in an organic solvent, and then olefins and amine compounds Ar -NH2 are added in an inert gas 2 , and the reaction is carried out at a high temperature to obtain a reaction mixture, and the target product is obtained after post-treatment and purification.

[0009] Among them, Ar 1 , Ar 2 is an aryl group or a heteroaryl group.

[0010] The catalyst [Al] used is a compound with the following structural formula:

[0011]

[0012] The method provides a preparation method of the catalyst:

[0013] Under an inert atmosphere, an organic solution of a beta-diketiminate ligand LH and trimethylaluminum is reacted in an organic solvent at 0 DEG C, and the reaction mixture is reacted at room temperature to obtain a white turbid solution of an aluminum methyl compound stabilized by the beta-diketiminate ligand. The aluminum methyl compound stabilized by the beta-diketiminate ligand is filtered out from the system, washed with an organic solvent, and dried to obtain a white solid.

[0014] The beta-diketiminate ligand LH has the following structural formula:

[0015]

[0016] According to some preferred embodiments of the application, the reaction process is always under an inert atmosphere.

[0017] According to some preferred embodiments of the application, the reaction is carried out at 0 DEG C for 0.05-0.5 hours, and then at room temperature for 18-24 hours.

[0018] The preparation method according to claim 3, wherein the mass ratio of the beta-diketiminate ligand LH to the organic solution of trimethylaluminum is 1:1.2-1:3, and the concentration of trimethylaluminum in the organic solution of trimethylaluminum is 1 mol / L.

[0019] The preparation method according to claim 3, wherein the organic solvents are all selected from n-hexane.

[0020] The preparation method according to claim 3, wherein the ratio of the amount of substance of the substance containing the beta-diketiminate ligand LH to the volume of the organic solvent is 0.5 mmol / mL.

[0021] The reaction process is as follows:

[0022]

[0023] According to some preferred embodiments of the present application, the organic solvent is one or two of 1,4-dioxane, tetrahydrofuran, tert-butyl methyl ether, chlorobenzene, dimethyl sulfoxide; the ratio of the amount of substance of the amine compound to the volume of the organic solvent is 0.25-0.5 mmol / mL.

[0024] According to some preferred embodiments of the present application, the aluminum-catalyzed anti-Markovnikov hydroamination of aromatic alkenes is characterized in that the molar ratio of the amine compound to the alkene is 1:2-1:5.

[0025] According to some preferred embodiments of the present application, the aluminum-catalyzed anti-Markovnikov hydroamination of aromatic alkenes is characterized in that the molar amount of the catalyst [Al] is 1-15% of the molar amount of the amine compound.

[0026] According to some preferred embodiments of the present application, the aluminum-catalyzed anti-Markovnikov hydroamination of aromatic alkenes is characterized in that the conditions of the temperature-increasing reaction refer to a magnetic stirring mode, a temperature of 60°C or 90°C, and a time of 4-48 h.

[0027] The present application has the following beneficial effects:

[0028] 1. The alkene and the amine used in the present application are unactivated compounds, which are widely available and can significantly reduce production costs. Not only does it improve the operability of the reaction, but it also provides a new solution for green chemistry.

[0029] 2. The catalyst of the present application does not contain transition metals, but uses the main group metal aluminum, which is abundant, inexpensive and non-toxic, and has a simple preparation process, and has great potential for large-scale industrial application.

[0030] 3. The present application has universal applicability to a wide range of substrates and can generate anti-Markovnikov hydroamination products with good selectivity. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The present application is a schematic diagram of the structure of the catalyst obtained. DETAILED DESCRIPTION

[0032] The following detailed description will help to further understand the characteristics and advantages of the present application. The provided examples are only for illustrating the method of the present application, and do not limit other contents of the present application in any way. All reasonable variations and combinations included in the scope of the inventive concept of the present application fall within the protection scope of the present application.

[0033] 1. According to the technical solution of the present application, a preparation method of an aluminum catalyst [Al] for catalyzing anti-Markovnikov hydroamination of aromatic olefins comprises:

[0034] Under an inert atmosphere, an organic solution of a β-diketiminate ligand LH and trimethylaluminum is reacted in an organic solvent at 0°C, and then the reaction mixture is reacted at room temperature, and the reaction process is as follows:

[0035]

[0036] A white turbid solution of a β-diketiminate ligand-stabilized aluminum methyl compound is obtained. The β-diketiminate ligand-stabilized aluminum methyl compound is filtered out of the system and washed with an organic solvent, and a white solid is obtained after vacuum drying.

[0037] 2. Preparation of anti-Markovnikov hydroamination products from aromatic olefins and amines:

[0038] Under an inert gas protection, the catalyst [Al] and an additive are dissolved in an organic solvent, and then an olefin and an amine compound Ar 2 -NH2 are added, the molar ratio of the amine compound to the additive is 1:2, the molar amount of the catalyst [Al] is 1-15% of the molar amount of the amine compound, the ratio of the amount of substance of the amine compound to the volume of the organic solvent is 0.25-0.5 mmol / mL, the molar ratio of the amine compound to the olefin is 1:2-1:5, the magnetic stirring method is adopted, the temperature is 60°C or 90°C, the time is 4-48 h, and after the reaction is completed, the anti-Markovnikov hydroamination products are obtained after post-processing.

[0039] In the following examples, THF refers to tetrahydrofuran, Dioxane refers to 1,4-dioxane, and equiv. refers to the number of equivalents. The r value is defined as the yield ratio of the target product to the secondary anti-Markovnikov hydroamination addition product of the byproduct.

[0040] An internal standard is added after the reaction, and the yield and r value of the product are calculated by nuclear magnetic resonance hydrogen spectrum.

[0041] I. Preparation of the catalyst

[0042] Example 1

[0043] The catalyst was prepared by the following process:

[0044] The organic solution of trimethylaluminum was added dropwise into the organic solution of the β-diketiminate ligand LH in n-hexane at 0°C, and after stirring for 0.05-0.5 hours, the reaction mixture was slowly warmed to room temperature, and stirring was continued for 18-24 hours, and the filtrate was filtered to obtain a filter residue, which was washed with the organic solvent n-hexane until the product became a white solid.

[0045] The yield of the obtained catalyst crystal was 81%, and the results of the characterization of its structure by nuclear magnetic hydrogen spectrum and carbon spectrum were as follows:

[0046] 1 H NMR (400 MHz, Benzene-d6) δ 6.77 (t, J = 8.3 Hz, 2H), 6.23 (d, J = 8.3 Hz, 4H), 4.99 (s, 1H), 3.27 (s, 12H), 1.72 (s, 6H), -0.65 (s, 6H).

[0047] 13 C NMR (101 MHz, Chloroform-d) δ 168.02, 153.87, 124.59, 123.37, 104.19, 96.48, 55.16, 54.85, 21.64.

[0048] The filtrate was concentrated by filtration and crystallized at room temperature to obtain white crystals, and the diffraction data of the catalyst crystal obtained by a Bruker D8 Venture X-ray single crystal diffractometer and OLEX2 software showed that the aluminum center in the crystal formed a distorted six-membered ring structure with the ligand, two nitrogen atoms and two methyl carbon atoms cooperatively stabilized the aluminum atom, the central aluminum formed a four-coordinated positive trivalent metal center, which had catalytic activity, and the specific single crystal structure is shown in the accompanying Figure 1 .

[0049] II. Example of hydrogen amine reaction

[0050] Example 2.1

[0051] The catalytic reaction was carried out by the following process:

[0052] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of anti-Markovnikov hydroamination product and the ratio r of main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0053] The yield of anti-Markovnikov hydroamination product was 90%, and r = 91:9.

[0054] 1 H NMR (400 MHz, Chloroform-d) δ 7.20-6.89 (m, 7H), 6.60-6.45 (m, 1H), 6.42-6.29 (m, 2H), 3.37 (s, 1H), 3.11 (t, J = 7.1 Hz, 2H), 2.62 (t, J = 7.1 Hz, 2H).

[0055] 13 C NMR (101 MHz, Chloroform-d) δ 148.42, 139.79, 129.68, 129.18, 128.97, 126.78, 117.76, 113.35, 45.36, 35.84.

[0056] Example 2.2

[0057] The catalytic reaction was carried out by the following process:

[0058] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 2-methylaniline (0.0268 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydrogenation product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The relevant data of the obtained product are as follows:

[0059] The yield of the anti-Markovnikov hydrogenation product was 78%, and r = 78:0.

[0060] 1 H NMR (400 MHz, Chloroform-d) δ 7.29-7.00 (m, 6H), 6.94 (d, J = 7.2 Hz, 1H), 6.57 (d, J = 7.6 Hz, 2H), 3.42 (s, 1H), 3.34 (t, J = 7.0 Hz, 2H), 2.86 (t, J = 6.9 Hz, 2H), 1.92 (s, 3H).

[0061] 13 C NMR (101 MHz, Chloroform-d) δ 144.92, 138.34, 129.08, 129.07, 127.76, 127.74, 127.58, 127.57, 126.11, 125.41, 121.04, 115.98, 115.97, 108.85, 108.83, 43.92, 34.45, 16.25.

[0062] Example 2.3

[0063] The catalytic reaction was carried out by the following process:

[0064] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 2-methoxyaniline (0.0308 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of anti-Markovnikov hydroamination product and the ratio r of main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The relevant data of the obtained product are as follows:

[0065] The yield of anti-Markovnikov hydroamination product was 84%, and r = 84:0.

[0066] 1 H NMR (400 MHz, Chloroform-d) δ 7.32-7.03 (m, 5H), 6.79 (t, J = 7.6 Hz, 1H), 6.74-6.47 (m, 3H), 4.21 (s, 1H), 3.70 (s, 3H), 3.30 (t, J = 7.3 Hz, 2H), 2.84 (t, J = 7.3 Hz, 2H).

[0067] 13 C NMR (101 MHz, Chloroform-d) δ 145.87, 138.49, 136.99, 127.72, 127.46, 125.26, 120.30, 115.44, 108.92, 108.54, 54.37, 43.99, 34.65.

[0068] Example 2.4

[0069] The catalytic reaction was carried out by the following process:

[0070] In a 10 mL reaction vial, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added under inert gas protection, then 3-bromoaniline (0.0430 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction vial was reacted at 60 °C for 21 h. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3was used for dissolution, and the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After obtaining the results, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3for nuclear magnetic characterization, and the relevant data of the product obtained are as follows:

[0071] The yield of the anti-Markovnikov hydroamination product was 52%, and r = 95:5.

[0072] 1 H NMR (500 MHz, Chloroform-d) δ 7.31 (td, J = 8.0, 7.6, 1.9 Hz, 2H), 7.26-7.20 (m, 1H), 7.22-7.17 (m, 2H), 6.98 (td, J = 8.0, 1.5 Hz, 1H), 6.79 (dd, J = 7.9, 2.0 Hz, 1H), 6.71 (t, J = 2.0 Hz, 1H), 6.47 (dd, J = 8.2, 2.3 Hz, 1H), 3.70 (s, 1H), 3.34 (t, J = 7.0 Hz, 2H), 2.88 (t, J = 7.0 Hz, 2H).

[0073] 13 C NMR (126 MHz, Chloroform-d) δ 149.34, 138.99, 130.56, 128.81, 128.73, 126.62, 123.38, 120.17, 115.44, 111.72, 44.79, 35.34.

[0074] Example 2.5

[0075] The catalytic reaction was carried out by the following process:

[0076] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 3-methylaniline (0.0268 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydrogenation product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0077] The yield of the anti-Markovnikov hydrogenation product was 72%, and r = 96:4.

[0078] 1 H NMR (400 MHz, Chloroform-d) δ 7.27-7.06 (m, 5H), 6.98 (dd, J = 8.9, 7.4 Hz, 1H), 6.45 (d, J = 7.4 Hz, 1H), 6.32-6.34 (m, 2H), 3.51 (s, 1H), 3.29 (t, J = 7.0 Hz, 2H), 2.81 (t, J = 7.0 Hz, 2H), 2.18 (s, 3H).

[0079] 13 C NMR (101 MHz, Chloroform-d) δ 147.04, 138.34, 137.98, 128.11, 127.74, 127.55, 125.35, 117.38, 112.75, 109.12, 44.03, 34.54, 20.59.

[0080] Example 2.6

[0081] The catalytic reaction was carried out by the following process:

[0082] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 4-methylaniline (0.0268 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The relevant data of the obtained product are as follows:

[0083] The yield of the anti-Markovnikov hydroamination product was 83%, and r = 96:4.

[0084] 1 H NMR (400 MHz, Chloroform-d) δ 7.27-7.09 (m, 5H), 6.90 (d, J = 8.1 Hz, 2H), 6.54-6.40 (m, 2H), 3.54-3.34 (m, 1H), 3.29 (t, J = 7.0 Hz, 2H), 2.81 (t, J = 7.0 Hz, 2H), 2.15 (s, 3H).

[0085] 13 C NMR (101 MHz, Chloroform-d) δ 144.71, 138.38, 128.73, 127.75, 127.53, 125.64, 125.33, 112.19, 44.39, 34.51, 19.35.

[0086] Example 2.7

[0087] The catalytic reaction was carried out by the following process:

[0088] In an inert gas protection, a 10 mL reaction bottle was added with [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.), then 4-fluoroaniline (0.0278 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydrogenation product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The relevant data of the obtained product are as follows:

[0089] The yield of the anti-Markovnikov hydrogenation product was 78%, and r = 90:10.

[0090] 1 H NMR (400 MHz, Chloroform-d) δ 7.28-7.09 (m, 5H), 6.80 (t, J = 8.7 Hz, 2H), 6.54-6.36 (m, 2H), 3.45 (s, 1H), 3.27 (t, J = 7.0 Hz, 2H), 2.81 (t, J = 6.9 Hz, 2H).

[0091] 13 C NMR (101 MHz, Chloroform-d) δ 156.01, 153.67, 143.35, 143.33, 138.16, 127.67 (d, J = 13.2 Hz), 125.45, 114.65 (d, J = 22.2 Hz), 112.79 (d, J = 7.4 Hz), 44.65, 34.44.

[0092] 19 F NMR (376 MHz, Chloroform-d) δ -127.98.

[0093] Example 2.8

[0094] The catalytic reaction was carried out by the following process:

[0095] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 4- bromoaniline (0.0430 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0096] The yield of the anti-Markovnikov hydroamination product was 81%, and r = 92:8.

[0097] 1 H NMR (400 MHz, Chloroform-d) δ 7.27-7.04 (m, 7H), 6.43-6.29 (m, 2H), 3.58 (s, 1H), 3.25 (t, J = 7.0 Hz, 2H), 2.79 (t, J = 7.0 Hz, 2H).

[0098] 13 C NMR (101 MHz, Chloroform-d) δ 145.95, 137.98, 130.91, 127.71, 127.62, 125.49, 113.48, 107.91, 43.93, 34.26.

[0099] Example 2.9

[0100] The catalytic reaction was carried out by the following process:

[0101] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then 4- bromoaniline (0.0430 g, 0.25 mmol) and styrene (0.1302 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0102] The yield of the anti-Markovnikov aminohydrogenation product was 74%, r = 74:0.

[0103] 1 H NMR (400 MHz, Chloroform-d) δ 7.27 - 7.10 (m, 7H), 6.57 - 6.43 (m, 2H), 3.49 (s, 1H), 3.32 (t, J = 7.0 Hz, 2H), 2.84 (t, J = 7.0 Hz, 2H), 1.21 (s, 9H).

[0104] 13 C NMR (101 MHz, Chloroform-d) δ 144.67, 139.26, 138.41, 127.76, 127.55, 125.35, 125.01, 111.72, 44.30, 34.68, 32.83, 30.53.

[0105] Example 2.10

[0106] The catalytic reaction was carried out by the following process:

[0107] Under the protection of inert gas, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 2-methylstyrene (0.1477 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov aminohydrogenation product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The related data of the product obtained are as follows:

[0108] The yield of the anti-Markovnikov aminohydrogenation product was 88%, r = 90:10.

[0109] 1 H NMR (400 MHz, Chloroform-d) δ 7.14 - 7.06 (m, 6H), 6.63 (t, J = 7.3 Hz, 1H), 6.54 (d, J = 7.9 Hz, 2H), 3.61 (s, 1H), 3.29 (t, J = 7.3 Hz, 2H), 2.84 (t, J = 7.3 Hz, 2H), 2.26 (s, 3H).

[0110] 13C NMR (101 MHz, Chloroform-d) δ 147.04, 136.39, 135.29, 129.41, 128.27, 128.24, 125.52, 125.09, 116.42, 111.90, 42.85, 31.93, 18.37.

[0111] Example 2.11

[0112] The catalytic reaction was carried out by the following process:

[0113] Under the protection of inert gas, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 2-fluorostyrene (0.1527 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60 °C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0114] The yield of the anti-Markovnikov hydroamination product was 87%, and r = 92:8.

[0115] 1 H NMR (400 MHz, Chloroform-d) δ 7.22 - 6.89 (m, 6H), 6.67 - 6.59 (m, 1H), 6.58 - 6.52 (m, 2H), 3.65 (s, 1H), 3.33 (t, J = 7.1 Hz, 2H), 2.88 (t, J = 7.1 Hz, 2H).

[0116] 13 C NMR (101 MHz, Chloroform-d) δ 161.55, 146.89, 130.04 (d, J = 5.0 Hz), 128.27, 127.17 (d, J = 8.1 Hz), 125.23 (d, J = 16.1 Hz), 123.11 (d, J = 3.6 Hz), 116.45, 114.38 (d, J = 22.2 Hz), 111.88, 42.86, 28.17.

[0117] 19 F NMR (376 MHz, Chloroform-d) δ -118.42.

[0118] Example 2.12

[0119] The catalytic reaction was carried out by the following process:

[0120] Under the protection of inert gas, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 3-methylstyrene (0.1477 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60 °C for 24 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCh was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCh. The relevant data of the product obtained are as follows:

[0121] The yield of the anti-Markovnikov hydroamination product was 86%, and r = 93:7.

[0122] 1 H NMR (400 MHz, Chloroform-d) δ 7.20 - 6.86 (m, 6H), 6.67 - 6.47 (m, 3H), 3.56 (s, 1H), 3.29 (t, J = 7.0 Hz, 2H), 2.78 (t, J = 7.0 Hz, 2H), 2.25 (s, 3H).

[0123] 13 C NMR (101 MHz, Chloroform-d) δ 147.05, 138.20, 137.16, 128.53, 128.23, 127.45, 126.14, 124.76, 116.40, 111.98, 44.02, 34.44, 20.35.

[0124] Example 2.13

[0125] The catalytic reaction was carried out by the following process:

[0126] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 3-fluorostyrene (0.1527 g, 1.25 mmol) were added, and then 1 mL of Dioxane was added. After the addition was completed, the reaction bottle was reacted at 90°C for 4 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0127] The yield of the anti-Markovnikov hydroamination product was 70%, and r = 71:29.

[0128] 1 H NMR (400 MHz, Chloroform-d) δ 7.27-6.49 (m, 9H), 3.57 (s, 1H), 3.33 (t, J = 7.0 Hz, 2H), 2.83 (t, J = 7.0 Hz, 2H).

[0129] 13 C NMR (101 MHz, Chloroform-d) δ 163.22, 146.79, 140.89 (d, J = 7.3 Hz), 128.99 (d, J = 8.3 Hz), 128.31, 123.40 (d, J = 2.9 Hz), 116.62, 114.60 (d, J = 20.9 Hz), 112.31 (d, J = 21.0 Hz), 111.98, 43.76, 34.28.

[0130] 19 F NMR (376 MHz, Chloroform-d) δ -113.25.

[0131] Example 2.14

[0132] The catalytic reaction was carried out by the following process:

[0133] Inert gas protection, in a 10 mL reaction bottle, add [Al] catalyst (0.0107g, 10mmol%) and potassium tert-butoxide (0.0561g, 2equiv.), then add aniline (0.0233g, 0.25mmol) and 4-methylstyrene (0.1477g, 1.25mmol), then add 1mL of Dioxane. After the completion of the charge, the reaction bottle is reacted at 90°C for 18 hours. After the reaction is completed, the solvent is removed under vacuum, then toluene (internal standard) is added, dissolved in CDCl3, and the yield of the anti-Markovnikov hydrogenation product and the ratio r of the main and side products are quantitatively analyzed by nuclear magnetic hydrogen spectrum. After obtaining the results, the target product is separated and purified by column chromatography, and then characterized by nuclear magnetic resonance after dissolving in CDCl3. The relevant data of the product obtained are as follows:

[0134] The yield of the anti-Markovnikov hydrogenation product is 95%, and r = 95:0.

[0135] 1 H NMR (400 MHz, Chloroform-d) δ 7.15-6.87 (m, 6H), 6.70-6.44 (m, 3H), 3.55 (s, 1H), 3.27 (t, J = 7.0 Hz, 2H), 2.77 (t, J = 7.0 Hz, 2H), 2.24 (s, 3H).

[0136] 13 C NMR (101 MHz, Chloroform-d) δ 147.06, 135.15, 134.92, 128.26, 128.24, 127.64, 116.41, 111.98, 44.10, 34.05, 19.99.

[0137] Example 2.15

[0138] The catalytic reaction is carried out by the following process:

[0139] Inert gas protection, in a 10 mL reaction bottle, add [Al] catalyst (0.0107g, 10mmol%) and potassium tert-butoxide (0.0561g, 2equiv.), then add aniline (0.0233g, 0.25mmol) and 4-methylstyrene (0.1477g, 1.25mmol), then add 1mL of Dioxane. After the completion of the charge, the reaction bottle is reacted at 90°C for 18 hours. After the reaction is completed, the solvent is removed under vacuum, then toluene (internal standard) is added, dissolved in CDCl3, and the yield of the anti-Markovnikov hydrogenation product and the ratio r of the main and side products are quantitatively analyzed by nuclear magnetic hydrogen spectrum. After obtaining the results, the target product is separated and purified by column chromatography, and then characterized by nuclear magnetic resonance after dissolving in CDCl3. The relevant data of the product obtained are as follows:

[0140] The yield of the anti-Markovnikov aminohydrogenation product was 36%, r = 36:0.

[0141] 1 H NMR (400 MHz, Chloroform-d) δ 7.20 - 6.83 (m, 6H), 6.68 - 6.43 (m, 3H), 3.54 (s, 1H), 3.29 (t, J = 7.0 Hz, 2H), 2.79 (t, J = 7.0 Hz, 2H).

[0142] 13 C NMR (101 MHz, Chloroform-d) δ 161.83, 159.40, 146.87, 133.93 (d, J = 3.2 Hz), 129.17, 129.09, 128.29, 116.56, 114.34 (d, J = 21.2 Hz), 111.97, 44.07, 33.68.

[0143] 19 F NMR (376 MHz, Chloroform-d) δ -116.74.

[0144] Example 2.16

[0145] The catalytic reaction was carried out by the following process:

[0146] Under the protection of inert gas, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 4-methoxystyrene (0.1677 g, 1.25 mmol) were added, and 1 mL of Dioxane was added. After the addition was completed, the reaction bottle was reacted at 90°C for 34 hours. After the reaction was completed, the solvent was removed under vacuum, toluene (internal standard) was added, and then CDCl3 was used for dissolution, and the yield of the anti-Markovnikov aminohydrogenation product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCl3. The relevant data of the product obtained are as follows:

[0147] The yield of the anti-Markovnikov aminohydrogenation product was 93%, r = 94:6.

[0148] 1H NMR (400 MHz, Chloroform-d) δ 7.33 - 7.00 (m, 6 H), 6.70 - 6.46 (m, 3 H), 3.61 (s, 1 H), 3.32 (t, J = 7.0 Hz, 2 H), 2.82 (t, J = 7.0 Hz, 2 H), 1.25 (s, 9 H).

[0149] 13 C NMR (101 MHz, Chloroform-d) δ 148.26, 147.08, 135.17, 128.24, 127.42, 124.47, 116.40, 111.98, 44.01, 33.97, 33.40, 30.37.

[0150] Example 2.17

[0151] The catalytic reaction was carried out by the following process:

[0152] Under the protection of inert gas, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 2-vinylpyridine (0.1314 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of the anti-Markovnikov hydroamination product and the ratio r of the main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was dissolved in CDCl3 and then characterized by nuclear magnetic resonance. The relevant data of the obtained product are as follows:

[0153] The yield of the anti-Markovnikov hydroamination product was 49%, and r = 49:0.

[0154] 1 H NMR (400 MHz, Chloroform-d) δ 8.46 (d, J = 4.9 Hz, 1 H), 7.58 - 6.39 (m, 8 H), 3.91 (s, 1 H), 3.44 (t, J = 6.6 Hz, 2 H), 2.99 (t, J = 6.6 Hz, 2 H).

[0155] 13 C NMR (101 MHz, Chloroform-d) δ 158.78, 148.35, 147.17, 135.45, 128.19, 122.28, 120.42, 116.26, 111.91, 42.51, 36.45.

[0156] Example 2.18

[0157] The catalytic reaction was carried out by the following process:

[0158] In an inert gas protection, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added into a 10 mL reaction bottle, then aniline (0.0233 g, 0.25 mmol) and 2-vinylthiophene (0.1377 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 21 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCh was used for dissolution, and then the yield of anti-Markovnikov hydroamination product and the ratio r of main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, which was characterized by nuclear magnetic after being dissolved in CDCh. The relevant data of the obtained product are as follows:

[0159] The yield of anti-Markovnikov hydroamination product was 79%, and r = 87:13.

[0160] 1 H NMR (400 MHz, Chloroform-d) δ 7.21 - 6.40 (m, 8H), 3.68 (s, 1H), 3.35 (t, J = 6.8 Hz, 2H), 3.04 (t, J = 6.8 Hz, 2H).

[0161] 13 C NMR (101 MHz, Chloroform-d) δ 146.73, 140.73, 128.28, 125.94, 124.25, 122.83, 116.62, 112.05, 44.19, 28.72.

[0162] Example 2.19

[0163] The catalytic reaction was carried out by the following process:

[0164] In 10 mL reaction bottle, [Al] catalyst (0.0107 g, 10 mmol%) and potassium tert-butoxide (0.0561 g, 2 equiv.) were added under inert gas protection, then aniline (0.0233 g, 0.25 mmol) and 1,1-diphenylethylene (0.2253 g, 1.25 mmol) were added, and then 0.5 mL of THF and dioxane were added respectively. After the addition was completed, the reaction bottle was reacted at 60°C for 24 hours. After the reaction was completed, the solvent was removed under vacuum, then toluene (internal standard) was added, and then CDCl3 was used for dissolution, and then the yield of anti-Markovnikov hydroamination product and the ratio r of main and side products were quantitatively analyzed by nuclear magnetic hydrogen spectrum. After the results were obtained, column chromatography was used for separation and purification to obtain the target product, and then CDCl3 was used for dissolution and nuclear magnetic characterization, and the related data of the obtained product were as follows:

[0165] The yield of anti-Markovnikov hydroamination product was 63%, and r = 63:0.

[0166] 1 H NMR (400 MHz, Chloroform-d) δ 7.29-7.05 (m, 12H), 6.64 (t, J = 7.3 Hz, 1H), 6.52 (d, J = 7.9 Hz, 2H), 4.22 (t, J = 7.6 Hz, 1H), 3.67 (d, J = 7.7 Hz, 2H), 3.56 (s, 1H).

[0167] 13 C NMR (101 MHz, Chloroform-d) δ 146.81, 141.27, 128.27, 127.71, 127.14, 125.77, 116.65, 112.15, 49.27, 47.54.

[0168] The above examples are only preferred embodiments of the present application, and the protection scope of the present application is not limited to the above examples. Any technical solutions falling within the concept of the present application shall fall within the protection scope of the present application. It should be pointed out that, for ordinary skilled persons in the technical field, improvements and refinements without departing from the principles of the present application shall also be considered as the protection scope of the present application.

Claims

1. A method for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum, characterized in that: The method comprises the following steps: In inert gas, a catalyst [Al] of a specific structure, a potassium tert-butoxide additive is dissolved in dioxane single solvent or tetrahydrofuran and dioxane mixed solvent, then an olefin is added and an amine compound Ar 2 -NH2, after the reaction is completed by heating, a reaction mixture is obtained, and the target product is obtained by post-treatment and purification wherein Ar 1 , Ar 2 is aryl or heteroaryl, and the catalyst [Al] is a compound having the following structural formula:

2. The method of claim 1, wherein: The beta-diketimine ligand LH and the organic solution of trimethylaluminum are reacted in an organic solvent at 0 DEG C under an inert atmosphere, and then the reaction mixture is reacted at room temperature to obtain a white turbid solution of beta-diketimine ligand-stabilized aluminum methyl compound, the beta-diketimine ligand-stabilized aluminum methyl compound is filtered out of the system, washed with an organic solvent, and dried in vacuum to obtain a white solid.

3. The method of claim 2, wherein: The reaction process is always under an inert atmosphere.

4. The method of claim 2, wherein: The reaction is first carried out at 0 DEG C for 0.5 hours and then at room temperature for 18 hours.

5. The method of claim 2, wherein: The mass ratio of the beta-diketimine ligand LH to the organic solution of trimethylaluminum is 1:1.2-1:3, and the concentration of trimethylaluminum in the organic solution of trimethylaluminum is 1 mol / L.

6. The method of claim 2, wherein: The organic solvent is selected from n-hexane.

7. The method of claim 2, wherein: The mass of the beta-diketimine ligand LH to the volume of the organic solvent is 0.5 mmol / mL.

8. The process for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum according to claim 1, characterized by the fact that: The additive is potassium tert-butoxide, and the molar ratio of the amine compound to the potassium tert-butoxide additive is 1:

2.

9. The process for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum according to claim 1, characterized in that: The organic solvent is dioxane single solvent or a mixed solvent of tetrahydrofuran and dioxane, and the mass of the amine compound to the volume of the organic solvent is 0.25-0.5 mmol / mL.

10. The process for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum according to claim 1, characterized in that: The molar ratio of the amine compound to the olefin is 1:2-1:

5.

11. The process for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum according to claim 1, characterized in that: The molar amount of the catalyst [Al] is 1-15% of the molar amount of the amine compound.

12. The process for the anti-Markovnikov hydroamination of aromatic olefins catalyzed by aluminum according to claim 1, characterized in that: The heating reaction condition is that the magnetic stirring method is adopted, the temperature is 60 DEG C or 90 DEG C, and the time is 4-48 hours.

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