Method for synthesizing allylamine compound from alkyne

Abstract

The invention discloses a method for synthesizing an allylamine compound from alkyne, and belongs to the technical field of organic decarboxylation application. According to the method, a carboxylic acid compound which is cheap and easy to obtain is used as a raw material, alpha-amino free radicals are generated through a visible light induced decarboxylation process, then the free radicals and phenylacetylene are subjected to a selective addition reaction, and an allylamine skeleton structure is efficiently constructed. The allylamine compound can be efficiently synthesized under the synergistic effect of alkali and the photocatalyst.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of organic decarboxylation, in particular to a method for synthesizing allylamine compounds from alkynes. BACKGROUND

[0002] Allylamine compounds are a class of organic molecules with alpha, beta-unsaturated amine structures, which have important values in the fields of medicine, sustainable agriculture and functional materials. In medicinal chemistry, allylamine compounds are widely used as key pharmacophores in the synthesis of antibacterial (such as antifungal drugs such as naftifine and terbinafine), antitumor and central nervous system drugs (such as NMDA receptor modulators); in agricultural chemistry, their derivatives can be used as fungicides and plant growth regulators; in addition, the allylamine structure can also be used in polymer materials (such as photocurable resins, conductive polymers) and organic catalysis (such as chiral amine catalysts).

[0003] The traditional synthesis methods of allylamine compounds mainly include allyl nucleophilic substitution reaction (such as the attack of amine on allyl halide), allyl amination reaction (such as Tsuji-Trost reaction) and reductive amination (condensation of alpha, beta-unsaturated aldehyde / ketone and amine and hydrogenation), but these methods usually rely on noble metal catalysts (such as Pd, Ru), strong base conditions or highly active halogenated hydrocarbons, which can cause high cost, poor functional group compatibility and problems of insufficient control of regioselectivity and stereoselectivity. In addition, some methods need to use toxic reagents (such as halogenated hydrocarbons or excessive reducing agents), which do not meet the requirements of green chemistry and limit their application in the synthesis of complex molecules (such as chiral drugs). SUMMARY

[0004] Technical problems solved: In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for synthesizing allylamine compounds, which uses alkynes and carboxylic acid compounds as raw materials and can efficiently synthesize allylamine compounds under mild reaction conditions.

[0005] Technical scheme: The method for synthesizing allylamine compounds from alkynes according to the present application specifically comprises the following steps: (1) adding a photosensitizer, a base, an organic solvent, an alkyne compound and a carboxylic acid compound into a reaction container, and then stirring the reaction under certain temperature, gas atmosphere and light conditions.

[0006] (2) After the reaction is completed, the reaction liquid is concentrated under reduced pressure to remove the solvent, and the crude product is obtained, which is separated and purified by column chromatography to obtain the allylamine compound.

[0007] The structure of the alkyne compound is any one of the following structures: , , , , , , , , , , , , , , , , , , , , , , .

[0008] The structure of the carboxylic acid compound is any one of the following: , , , , , , .

[0009] Preferably, the photosensitizer in step (1) of the present invention is one of 4CzIPN, 4CzPN, 4DPAIPN, Ir(ppy)3, Ir(ppy)2(dtbbpy)PF6.

[0010] Preferably, the alkali in step (1) of the present invention is one of sodium carbonate, potassium carbonate, cesium carbonate, cesium acetate, potassium hydroxide, potassium phosphate, and dipotassium hydrogen phosphate.

[0011] Preferably, the organic solvent in step (1) of the present invention is one of acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, dimethyl sulfoxide, and toluene.

[0012] Preferably, the temperature in step (1) of the present invention is 20~50℃.

[0013] Preferably, the gas atmosphere in step (1) of the present invention is an air atmosphere, a nitrogen atmosphere, or an argon atmosphere.

[0014] Preferably, the illumination conditions in step (1) of the present invention are blue light, sunlight, violet light, and ultraviolet light.

[0015] Preferably, in step (1) of the present invention, the amount of alkyne compound used is 0.1 mmol / mL based on solvent volume, the amount of photosensitizer used is 1% to 10% molar equivalent of alkyne compound, the amount of base used is 100% to 300% molar equivalent of alkyne compound, and the amount of carboxylic acid compound used is 120% to 400% molar equivalent of alkyne compound.

[0016] Preferably, in step (2) of the present invention, the determination of the end of the reaction is made by monitoring the reaction process using thin-layer chromatography and gas chromatography-mass spectrometry, and the reaction is determined to be ended when the alkyne compounds are completely consumed.

[0017] Preferably, in step (2) of the present invention, silica gel powder is used as the stationary phase for column chromatography separation and purification, and ethyl acetate and petroleum ether are used as eluents for elution and purification.

[0018] All reagents used in this invention are commercially available analytical grade.

[0019] Mechanism of the invention: The carboxylic acid compound undergoes deprotonation under alkaline conditions to generate carboxylate intermediate 1. Carboxylate intermediate 1 then undergoes a single-electron transfer with an excited-state photosensitizer to generate carbon dioxide, free radical intermediate 2, and a reduced-state photosensitizer. Free radical intermediate 2 further reacts with an alkyne compound to form a new free radical intermediate 3. The new free radical intermediate 3 undergoes an electron transfer with the reduced-state photosensitizer to generate intermediate 4 and regenerate the ground-state photosensitizer. Finally, intermediate 4 undergoes a protonation reaction to obtain the target product.

[0020] Compared with the prior art, the present invention provides a method for synthesizing allylamine compounds from alkynes, which has the following beneficial effects: (1) The reaction is carried out under mild conditions, and can be carried out efficiently at room temperature or near room temperature (20~50℃).

[0021] (2) It has high atom economy. The carboxyl group is removed in the form of CO2 in the reaction (the only byproduct). The substrate conversion is achieved through photocatalytic cycling. No stoichiometric oxidant or reducing agent is required, which avoids the environmental pollution problems of heavy metal residues (such as Ag and Cu) or strong oxidants (such as persulfate and high-valent iodine reagent) that are common in traditional methods.

[0022] (3) Catalysts are usually inexpensive organic photosensitizers (such as 4CzIPN) or non-toxic metal complexes (such as Ir(ppy)3), which are in line with the twelve principles of green chemistry and have unique value in environmentally sensitive fields such as drug synthesis and biomass conversion. Attached Figure Description

[0023] Figure 1 This is a reaction mechanism diagram of the present invention. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.02 eq.), potassium hydroxide (1.5 eq.), tetrahydrofuran (0.1 mol / L), phenylacetylene (1 eq.) and N-Boc-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain a nitrogen atmosphere and a temperature of 25°C. Stir the reaction under 10W 430nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0026] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 87%, Z:E = 92:8).

[0027] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.36 –7.29 (m, 3H), 7.25 – 7.11 (m, 2H), 6.40 (d, J = 11.8 Hz, 1H), 5.62 (d, J = 10.6Hz, 1H), 4.73 (s, 1H), 3.56 – 3.36 (m, 2H), 2.28 – 2.08 (m, 1H), 1.98 – 1.88(m, 1H), 1.87 – 1.76 (m, 2H), 1.45 – 1.24 (m, 9H). 13 C NMR (101 MHz, CDCl3) δ154.69, 137.00, 134.94, 128.82, 128.14, 126.77, 79.16, 54.97, 33.91, 28.59,28.53, 28.45, 23.88.

[0028] The reaction mechanism of this invention is as follows: Figure 1 As shown, taking the raw materials of this embodiment as an example, PC represents a photosensitizer, PC* represents an excited-state photosensitizer, PC-. represents a reduced-state photosensitizer, and SET represents single-electron transfer; N-Boc-proline undergoes deprotonation under alkaline conditions to generate carboxylate intermediate 1; intermediate 1 then undergoes single-electron transfer with excited-state photosensitizer B to generate carbon dioxide, free radical intermediate 2, and reduced-state photosensitizer C; free radical intermediate 2 further reacts with phenylacetylene to form a new free radical intermediate 3; electron transfer occurs between intermediate 3 and reduced-state photosensitizer C to generate intermediate 4 and regenerate ground-state photosensitizer A; finally, intermediate 4 undergoes a protonation reaction to obtain the target product.

[0029] Example 2 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzPN (0.05 eq.), potassium carbonate (2 eq.), acetonitrile (0.1 mol / L), methyl 4-carboxylate phenylacetylene (1 eq.) and N-Boc-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain an argon atmosphere and a temperature of 35°C. Stir the reaction under 10W 390nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0030] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 80%, Z:E = 87:13).

[0031] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.00 (d, J =8.1 Hz, 2H), 7.48 – 7.29 (m, 2H), 6.43 (d, J = 11.9 Hz, 1H), 5.71 (s, 1H), 4.69(s, 1H), 3.91 (s, 3H), 3.57 – 3.36 (m, 2H), 2.22 (s, 1H), 1.91 – 1.74 (m,3H), 1.28 (s, 9H). 13C NMR (101 MHz, CDCl3) δ 166.91, 154.57, 141.66, 136.99, 129.90, 129.47, 128.73, 128.33, 54.88, 52.06, 33.81, 28.48.

[0032] Example 3 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.1 eq.), potassium carbonate (1.5 eq.), 1,4-dioxane (0.1 mol / L), p-chlorophenylacetylene (1 eq.) and N-Boc-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain a nitrogen atmosphere and a temperature of 50°C. Stir the reaction under 10W 390nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0033] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 75%, Z:E = 77:23).

[0034] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.31 (dd, J = 15.5, 7.5 Hz, 3H), 7.20 (s, 1H), 6.35 (d, J = 11.9 Hz, 1H), 5.61 (s, 1H), 4.66 (s, 1H), 3.50 – 3.41 (m, 2H), 2.26 – 2.11 (m, 1H), 1.91 (s, 1H), 1.90 –1.81 (m, 2H), 1.36 (d, J = 53.7 Hz, 9H). 13 C NMR (101 MHz, CDCl3) δ 154.60,135.64, 135.43, 134.94, 132.54, 130.09, 128.81, 128.33, 128.13, 126.75,79.26, 28.58, 28.51, 28.46.

[0035] Example 4 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzPN (0.2 eq.), potassium phosphate (1.5 eq.), toluene (0.1 mol / L), p-methoxyphenylacetylene (1 eq.) and N-Boc-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain an argon atmosphere and a temperature of 40°C. Stir the reaction under 10W 390nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0036] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 70%, Z:E = 86:14).

[0037] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 8.0 Hz, 1H), 6.98 – 6.70 (m, 3H), 6.38 (d, J = 11.7 Hz, 1H), 5.60 (d, J = 14.8Hz, 1H), 4.73 (s, 1H), 3.81 (s, 3H), 3.44 (q, J = 9.2, 8.0 Hz, 2H), 2.20 (s,1H), 1.93 (dq, J = 16.3, 9.3, 8.0 Hz, 1H), 1.87 – 1.75 (m, 2H), 1.47 – 1.27 (m, 9H). 13 C NMR (101 MHz, CDCl3) δ 159.36, 154.68, 138.39, 135.26, 129.34, 129.09,121.40, 114.54, 112.90, 111.65, 79.18, 55.21, 55.19, 55.06, 28.58, 28.52,28.47, 23.89.

[0038] Example 5 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.3 eq.), cesium carbonate (1.5 eq.), acetonitrile (0.1 mol / L), 2-ethynthiophene (1 eq.) and N-Boc-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain an argon atmosphere and a temperature of 30°C. Stir the reaction under 10W 430nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0039] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 70%, Z:E = 80:20).

[0040] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3δ 7.25 – 7.07(m, 1H), 7.05 – 6.84 (m, 2H), 6.49 (t, J = 15.8 Hz, 1H), 5.51 (s, 1H), 4.93 (d, J = 6.4 Hz, 1H), 3.55 – 3.26 (m, 2H), 2.33 – 2.00 (m, 1H), 1.82 (ddd, J = 43.2,13.3, 6.8 Hz, 3H), 1.50 – 1.28 (m, 9H). 13 C NMR (101 MHz, CDCl3) δ 154.69,139.68, 133.58, 127.67, 126.86, 125.40, 123.79, 122.79, 79.26, 55.71, 33.18,28.51, 24.00.

[0041] Example 6 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Ir(ppy)2(dtbbpy)PF6 (0.1 eq.), dipotassium hydrogen phosphate (1.5 eq.), tetrahydrofuran (0.1 mol / L), diphenylacetylene (1 eq.) and N-Boc-proline (2 eq.) were added sequentially to a transparent glass or quartz reaction flask (tube). The reaction was carried out under an argon atmosphere and at a temperature of 20°C. The reaction was stirred under 10W 450nm LED irradiation. The reaction progress was monitored by TLC and GC-MS.

[0042] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 70%, Z:E = 70:30).

[0043] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ (dd, J =18.4, 5.3 Hz, 9H), 7.14 – 7.03 (m, 1H), 6.51 (s, 1H), 5.09 (dd, J = 8.4, 5.7Hz, 1H), 3.55 – 3.41 (m, 1H), 2.99 (dd, J = 13.4, 6.5 Hz, 1H), 2.35 – 2.18 (m,1H), 1.99 (dd, J = 13.0, 6.5 Hz, 1H), 1.64 (d, J = 11.5 Hz, 2H), 1.32 (s, 10H). 13 CNMR (101 MHz, CDCl3) δ 144.43, 141.61, 137.21, 129.54, 129.10, 128.94,128.09, 128.03, 127.17, 126.78, 57.02, 47.19, 33.50, 28.53, 23.64.

[0044] Example 7 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Ir[(dF(CF3)ppy)]2(dtbbpy)2PF5 (0.07 eq.), cesium carbonate (2 eq.), acetone (0.1 mol / L), methyl propynate (1 eq.) and N-Boc-proline (2 eq.) were added sequentially to a transparent glass or quartz reaction flask (tube). The reaction was carried out under a nitrogen atmosphere and a temperature of 40 °C, and stirred under 10 W 450 nm LED irradiation. The reaction progress was monitored by TLC and GC-MS.

[0045] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 80%, Z:E > 99:1).

[0046] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 6.34 –6.07 (m, 1H), 5.75 (d, J = 11.4 Hz, 1H), 5.28 (d, J = 7.4 Hz, 1H), 3.71 (s, 3H), 3.59 – 3.32 (m, 2H), 2.32 (d, J = 10.3 Hz, 1H), 1.85 (d, J = 2.9 Hz, 2H), 1.66(s, 1H), 1.42 (d, J = 25.3 Hz, 9H). 13 C NMR (101 MHz, CDCl3) δ 166.40, 154.65, 152.77, 117.64, 79.48, 55.35, 51.22, 46.58, 32.82, 28.30, 24.04.

[0047] Example 8 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.05 eq.), potassium carbonate (1.5 eq.), 2-MeTHF (0.1 mol / L), phenylacetylene (1 eq.) and N-Cbz-proline (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Stir the reaction in air at 45°C under 10 W 365 nm LED illumination. Monitor the reaction progress using TLC and GC-MS.

[0048] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 83%, Z:E = 88:12).

[0049] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.26 (m, 6H), 7.19 (dd, J = 30.1, 7.2 Hz, 4H), 6.43(tt, J = 26.9, 13.8 Hz, 1H), 5.63 (t, J = 10.4 Hz, 1H), 5.20 – 4.98 (m, 2H), 4.81(d, J = 10.4 Hz, 1H), 3.52 (d, J = 7.0 Hz, 2H), 2.30 – 2.05 (m, 1H), 1.95 (d, J =7.2 Hz, 1H), 1.85 (dd, J = 8.5, 5.2 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 155.19,136.92, 129.53, 129.30, 128.69, 128.56, 128.39, 128.33, 128.27, 126.96,126.26, 79.28, 48.69, 30.49, 28.52, 28.50, 28.19, 25.49, 19.83.

[0050] Example 9 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzPN (0.05 eq.), sodium carbonate (2 eq.), DMF (concentration 0.1 mol / L), phenylacetylene (1 eq.) and 2-tetrahydrofuran carboxylic acid (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Stir the reaction under argon atmosphere at 50°C and irradiate with a 10W 415nm LED. Monitor the reaction progress using TLC and GC-MS.

[0051] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 77%, Z:E = 83:17).

[0052] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) 1H NMR (400MHz, CDCl3) δ 7.37 (t, J = 6.6 Hz, 1H), 7.31 (q, J = 7.2 Hz, 3H), 7.24 – 7.16 (m,1H), 6.64 – 6.52 (m, 1H), 5.71 (dd, J = 11.6, 8.9 Hz, 1H), 4.66 (q, J = 7.8 Hz,1H), 4.04 – 3.91 (m, 1H), 3.91 – 3.73 (m, 1H), 2.19 – 2.06 (m, 1H), 1.97(dtt, J = 19.6, 12.5, 6.7 Hz, 2H), 1.76 – 1.64 (m, 1H). 13 C NMR (101 MHz, CDCl3)δ 136.73, 132.88, 131.52, 130.54, 130.47, 128.86, 128.53, 128.19, 127.52,127.14, 126.49, 79.70, 75.09, 68.21, 68.11, 32.96, 32.43, 26.42, 25.95.

[0053] Example 10 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.02 eq.), cesium carbonate (1.5 eq.), acetonitrile (0.1 mol / L), phenylacetylene (1 eq.) and BOC-N-methyl-L-alanine (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain a nitrogen atmosphere and a temperature of 30°C. Stir the reaction under 10W 390nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0054] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 50%, Z:E = 75:25).

[0055] The NMR data of the allylamine product prepared in this embodiment are as follows: 1H NMR (400 MHz, CDCl3) δ 7.43 –7.27 (m, 4H), 7.25 – 7.21 (m, 1H), 6.46 (dd, J = 29.0, 13.9 Hz, 1H), 5.61 (dd, J = 11.6, 9.0 Hz, 1H), 5.09 (s, 1H), 2.75 (d, J = 21.3 Hz, 3H), 1.49 (s,3H), 1.39 (s, 6H), 1.31 (d, J = 6.9 Hz, 1H), 1.22 (d, J = 6.7 Hz, 2H). 13 C NMR(101 MHz, CDCl3) δ 155.24, 136.65, 131.16, 131.00, 130.27, 128.78, 128.59,128.28, 127.53, 127.19, 126.34, 79.37, 28.54, 28.42, 19.28.

[0056] Example 11 The reaction equation for this embodiment is as follows: The specific experimental steps are as follows: (1) Add 4CzIPN (0.02 eq.), cesium carbonate (1.5 eq.), toluene (0.1 mol / L), phenylacetylene (1 eq.) and pyroglutamic acid (2 eq.) to a transparent glass or quartz reaction flask (tube) in sequence. Maintain a nitrogen atmosphere and a temperature of 30°C. Stir the reaction under 10W 460nm LED irradiation. Monitor the reaction progress using TLC and GC-MS.

[0057] (2) After the reaction was completed, the solvent was removed from the reaction solution by rotary evaporator under reduced pressure. Ethyl acetate: petroleum ether = 30:1 was used as the eluent, and the product was purified by column chromatography to obtain allylamine (yield 40%, Z:E = 77:23).

[0058] The NMR data of the allylamine product prepared in this embodiment are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.34 (dt, J = 21.3, 7.1 Hz, 4H), 7.19 (d, J = 7.1 Hz, 2H), 6.62 (d, J = 11.5 Hz, 1H), 5.63(dd, J= 11.4, 9.4 Hz, 1H), 4.64 (td, J = 9.7, 8.4, 5.4 Hz, 1H), 2.47 – 2.40 (m,2H), 2.40 – 2.36 (m, 1H), 1.99 – 1.93 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ178.05, 136.02, 132.51, 131.95, 128.53, 128.47, 127.58, 51.64, 30.26, 28.87.

[0059] This invention provides a simple, economical, and environmentally friendly new synthetic route for allylamine derivatives.

[0060] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing allylamine compounds from alkynes, characterized in that, Specifically, the following steps are included: (1) Add photosensitizer, alkali, organic solvent, alkyne compound and carboxylic acid compound to the reaction vessel, and then stir the reaction under certain temperature, gas atmosphere and light conditions; (2) After the reaction is completed, the reaction solution is concentrated under reduced pressure to remove the solvent and obtain a crude product. The crude product is then purified by column chromatography to obtain allylamine compounds. The structure of the alkyne compound is any one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； The structure of the carboxylic acid compound is any one of the following: 、 、 、 、 、 、 。 2. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The photosensitizer mentioned in step (1) is one of 4CzIPN, 4CzPN, 4DPAIPN, Ir(ppy)3, and Ir(ppy)2(dtbbpy)PF6.

3. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The alkali mentioned in step (1) is one of sodium carbonate, potassium carbonate, cesium carbonate, cesium acetate, potassium hydroxide, potassium phosphate, and dipotassium hydrogen phosphate.

4. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The organic solvent mentioned in step (1) is one of acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, dimethyl sulfoxide, and toluene.

5. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The temperature mentioned in step (1) is 20~50℃.

6. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The gas atmosphere mentioned in step (1) is an air atmosphere, a nitrogen atmosphere, or an argon atmosphere.

7. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, The lighting conditions mentioned in step (1) are blue light, sunlight, violet light, and ultraviolet light.

8. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, In step (1), the amount of alkyne compound used is 0.1 mmol / mL based on solvent volume, the amount of photosensitizer used is 1%~10% molar equivalent of alkyne compound, the amount of base used is 100~300% molar equivalent of alkyne compound, and the amount of carboxylic acid compound used is 120%-400% molar equivalent of alkyne compound.

9. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, In step (2), the reaction is considered complete when the alkyne compounds are completely consumed, based on the monitoring of the reaction process using thin-layer chromatography and gas chromatography-mass spectrometry.

10. The method for synthesizing allylamine compounds from alkynes according to claim 1, characterized in that, In step (2), the column chromatography separation and purification uses silica gel powder as the stationary phase and ethyl acetate and petroleum ether as eluents for elution and purification.

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