Near-infrared photocatalytic coupling method of 2-benzene-1,2,3,4-tetrahydroisoquinoline compounds with nucleophiles

Abstract

This invention discloses a near-infrared photocatalytic coupling method for 2-benzene-1,2,3,4-tetrahydroisoquinoline compounds with nucleophiles. The method uses (MV)Bi₂I₈ type perovskite as a catalyst, wherein the organic portion of the catalyst, MV… 2+ The product is a methyl viologen cation. 2-Benzene-1,2,3,4-tetrahydroisoquinoline compounds are reacted with nucleophiles (dimethyl malonate, nitromethane, ethyl nitrosyl acetate) under light irradiation at room temperature or in air to undergo cross-dehydrogenation coupling reactions to obtain the corresponding product. This invention is simple to operate, operates under mild conditions, and uses readily available catalysts. It successfully achieves cross-dehydrogenation coupling between substrates using only near-infrared light, and yields high product yields.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysis, and particularly relates to a method for cross-dehydrogenative coupling of 2-benzo-1,2,3,4-tetrahydroisoquinoline compounds with nucleophiles by using (MV)Bi2I8(MV 2+ = methyl viologen cation) perovskite-like as near-infrared photocatalyst. BACKGROUND

[0002] Tetrahydroisoquinoline compounds are the skeleton of many natural products, and the formation of C-C bond is of great significance to organic synthesis. Cross-dehydrogenative coupling refers to the cross-coupling reaction of C-H bond of two different reaction substrates to form C-C bond, which saves a step or even multiple steps of preparation of functionalized reaction substrates. Therefore, cross-dehydrogenative coupling reaction has the advantages of high efficiency, atom economy and environmental friendliness, and meets the concept of green synthesis.

[0003] Photocatalysis has become an important branch of catalytic reaction due to its clean and green characteristics. Near-infrared photocatalysts are relatively rare and very ideal, because they have lower energy requirements and higher low-energy light fluxes obtained when consuming the same amount of electricity compared with ultraviolet photocatalysts, and can avoid the consumption of light by substrates or products in the synthesis of high conjugated systems.

[0004] Common photocatalysts include organic dyes (Rhodamine B, Eosin Y), inorganic semiconductors (TiO2, ZnS, CdS) and transition metal (Ru, Ir, Rh, Pt) complexes. However, organic dyes are usually not reusable; inorganic semiconductors generally have a large band gap and low light utilization; transition metal complexes are expensive and have harsh reaction conditions. Among potential photoactive materials, halide perovskites are an excellent candidate material, which have shown good prospects for light energy conversion, for example, they have strong light absorption capacity, long excited state lifetime, effective separation and transport of carriers. In addition, the biggest advantage of halide perovskites is that the band gap can be easily adjusted by halogen, which is easy to achieve excitation by near-infrared light, and is an easy-to-obtain near-infrared photocatalyst. SUMMARY

[0005] The purpose of the present application is to overcome the shortcomings of low light penetration in visible light catalysis and light loss caused by absorption of high conjugated structure organic substrates and products in the visible light region, and to provide a method for cross-dehydrogenative coupling of 2-benzo-1,2,3,4-tetrahydroisoquinoline compounds with nucleophiles by near-infrared light.

[0006] In order to achieve the above-mentioned purpose, the present application provides a method for cross-dehydrogenative coupling of 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds and nucleophiles under near-infrared light catalysis. The method is to use (MV)Bi2I8 perovskite as a near-infrared light catalyst to catalyze the cross-dehydrogenative coupling reaction of 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds and nucleophiles. The specific method is as follows: 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds represented by formula I, nucleophiles NuH, (MV)Bi2I8 perovskite, and a solvent are added to a quartz tube, and the cross-dehydrogenative coupling reaction is carried out under near-infrared light irradiation to obtain the coupling product represented by formula II.

[0007]

[0008] In the formula, R 1 , R 2 Each independently represents any one of hydrogen, fluorine, chlorine, bromine, C1-C6 alkyl, and C1-C4 alkoxy; preferably R 1 represents hydrogen or bromine, and R 2 represents any one of hydrogen, fluorine, chlorine, bromine, methyl, methoxy, and tert-butyl.

[0009] The above-mentioned nucleophile NuH is any one of dimethyl malonate, nitromethane, and ethyl nitroacetate.

[0010] In the above-mentioned method, the molar ratio of 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds to nucleophiles NuH is preferably 1:5-15.

[0011] In the above-mentioned method, the amount of (MV)Bi2I8 perovskite added is preferably 1%-5% of the molar amount of 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds. In the (MV)Bi2I8 perovskite, MV 2+ represents a methyl viologen cation. The (MV)Bi2I8 perovskite is prepared by the method in the reference "Adv. Opt. Mater. 2023, 2203148". The specific preparation method is as follows: 4,4'-dipyridyl, bismuth iodide, and hydriodic acid are added to a polytetrafluoroethylene liner in a molar ratio of 1:2:35-40, and methanol is added. Stirring is carried out at room temperature to completely mix them. Then, the polytetrafluoroethylene liner containing the mixture is sealed in a stainless steel reaction kettle, and the reaction is carried out at 110-130°C for 48-72 hours. After the reaction is completed, the reaction kettle is slowly cooled to room temperature. The obtained dark red crystals are washed with methanol and then dried to obtain the (MV)Bi2I8 perovskite.

[0012] In the above-mentioned method, the solvent is preferably isopropyl alcohol or tert-butyl alcohol.

[0013] Further, in the above method, the cross-dehydrogenative coupling reaction is preferably carried out under near-infrared light irradiation, at room temperature, in an air atmosphere, and the reaction time is 12-24 hours.

[0014] Compared with the prior art, the present application has the following advantages:

[0015] Based on the characteristics of the (MV)Bi2I8 perovskite that the band gap is narrow and the excited state can be achieved by using near-infrared light, the present application realizes the cross-dehydrogenative coupling reaction between 2-phenyl-1,2,3,4-tetrahydroisoquinoline compounds and nucleophilic reagents under near-infrared light irradiation. The method is simple in operation, mild in conditions, and the catalyst is easy to prepare. The cross-dehydrogenative coupling between substrates is successfully realized by using only near-infrared light, and the yield of the product is high. Due to the high penetration of near-infrared light, it is expected to overcome the defect that photocatalysis cannot be used in large-scale reactions. In addition, from the perspective of energy, it is more energy-saving to excite the lowest energy electrons for photocatalytic reaction. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a single crystal diffraction pattern of the (MV)Bi2I8 perovskite.

[0017] Figure 2 is a simulated XRD pattern of the (MV)Bi2I8 perovskite and XRD patterns before and after the reaction.

[0018] Figure 3 is an ultraviolet-visible-near-infrared absorption spectrum of the (MV)Bi2I8 perovskite. DETAILED DESCRIPTION

[0019] The present application will be further described in detail below in combination with the drawings and examples, but the scope of protection of the present application is not limited to these examples.

[0020] The preparation method of the (MV)Bi2I8 perovskite used in the following examples is as follows: 0.5 mmol of bismuth iodide, 1 mmol of 4,4'-dipyridyl, 18 mmol of hydroiodic acid and 10 mL of methanol are added to a polytetrafluoroethylene liner, and stirred at room temperature for 2 hours to completely mix; then the polytetrafluoroethylene liner containing the mixture is sealed in a stainless steel reaction kettle, and reacted at 120℃ for 60 hours; after the reaction is completed, the reaction kettle is slowly cooled to room temperature, and the dark red crystals obtained are washed with methanol to remove the excess acid on the surface of the crystals, and then dried at 60℃ for 6 hours to obtain the (MV)Bi2I8 perovskite.

[0021] In order to determine the specific structure of the (MV)Bi2I8 perovskite, single crystal testing is performed on the (MV)Bi2I8 perovskite, and the results are shown in Figure 1 The (MV)Bi2I8 perovskite is composed of [Bi4I 16 ] 4-Tetranuclear cluster and two MVs 2+ Cationic component, [Bi4I 16 ] 4- Units are connected by μ 2 - and μ 3 - I ions to four [BiI6] 3- octahedra to form a tetranuclear Bi cluster. MV 2+ Cations are located around the inorganic cluster to balance the charge of the inorganic cluster.

[0022] To determine the purity of the prepared (MV)Bi2I8 perovskite, the (MV)Bi2I8 perovskite was subjected to XRD analysis and compared with the XRD pattern simulated from the single crystal structure. Figure 2 The comparison of the XRD test results of the (MV)Bi2I8 perovskite and the simulated pattern. It is found by comparison that the two patterns are consistent, indicating that the pure (MV)Bi2I8 perovskite is successfully prepared.

[0023] To illustrate the stability of the perovskite, the XRD pattern of the (MV)Bi2I8 perovskite after reaction was tested. The specific operation method is: 0.209 g (1 mmol) of 2-phenyl-1, 2, 3, 4-tetrahydroisoquinoline, 32.4 mg (0.02 mmol) of (MV)Bi2I8 perovskite, 1.15 mL (10 mmol) of dimethyl malonate were added to a quartz tube, and 5 mL of isopropanol or tert-butanol was added as solvent; the reaction mixture was stirred at room temperature and irradiated with a 10W 700nm monochromatic LED lamp for 12 hours, the catalyst was washed and centrifuged, dried at 60℃ for 6 hours, and then the (MV)Bi2I8 perovskite after reaction was subjected to XRD test. Figure 2 The XRD pattern of the (MV)Bi2I8 perovskite after reaction in isopropanol or tert-butanol. The pattern shows that the structure of the (MV)Bi2I8 perovskite is basically maintained after reaction in isopropanol or tert-butanol.

[0024] To determine whether the prepared (MV)Bi2I8 perovskite can be excited by near-infrared light, solid ultraviolet-visible-near-infrared spectrum analysis was performed on the (MV)Bi2I8 perovskite. Figure 3 The ultraviolet-visible-near-infrared absorption spectrum of the (MV)Bi2I8 perovskite. It can be seen from the spectrum that the (MV)Bi2I8 perovskite has absorption to 700nm near-infrared light.

[0025] Example 1

[0026] 2-(2-phenyl-1, 2, 3, 4-tetrahydroisoquinolin-1-yl) dimethyl malonate with the following structure was synthesized

[0027]

[0028] Into a quartz tube was placed 20.93 mg (0.1 mmol) of 2-benz-1,2,3,4-tetrahydroisoquinoline, 3.24 mg (0.002 mmol) of (MV)Bi2I8perovskite, 0.115 mL (1 mmol) of dimethyl malonate, and 1 mL of isopropanol. The reaction mixture was stirred at room temperature and irradiated using a 10 W 700 nm monochromatic LED lamp for 12 hours. The reaction was monitored by TLC. The reaction mixture was concentrated under vacuum to remove the solvent isopropanol. The residue was purified by column chromatography using 20:1 volume ratio of petroleum ether and ethyl acetate as eluent to obtain 2-(2-benz-1,2,3,4-tetrahydroisoquinolin-1-yl)dimethyl malonate in 88% yield with spectral data as: 1 H NMR (600 MHz, CDC13) δ 7.24-7.15 (m, 4H), 7.14-7.07 (m, 2H), 6.98 (d, J = 7.8 Hz, 2H), 6.76 (t, J = 7.2 Hz, 1H), 5.70 (d, J = 9.6 Hz, 1H), 3.95 (d, J = 9.6 Hz, 1H), 3.73-3.59 (m, 2H), 3.65 (s, 3H) 3.55 (s, 3H), 3.13-3.01 (m, 1H), 2.89-2.85 (m, 1H); 13 C NMR (151 MHz, CDC13) δ 168.40, 167.51, 148.89, 135.78, 134.90, 129.22, 129.09, 127.74, 127.16, 126.16, 118.74, 115.31, 59.22, 58.29, 52.65, 52.59, 42.29, 26.17.

[0029] Example 2

[0030] Synthesis of 2-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)dimethyl malonate

[0031]

[0032] In this example, 2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinoline was used instead of 2-benz-1,2,3,4-tetrahydroisoquinoline in Example 1 in equimolar amount. The other steps were same as in Example 1 to obtain 2-(2-(4-fluorophenyl)-1,2,3,4-tetrahydroisoquinolin-1-yl)dimethyl malonate in 75% yield with spectral data as: 1H NMR (600 MHz, CDC13) δ 7.21-7.17 (m, 2H), 7.13-7.10 (m, 2H), 6.90 (d, J = 6.9 Hz, 4H), 5.55 (d, J = 9.6 Hz, 1H), 3.94 (d, J = 9.6 Hz, 1H), 3.71-3.65 (m, 1H), 3.65 (s, 3H), 3.68-3.53 (m, 1H), 3.58 (s, 3H), 3.05-2.99 (m, 1H), 2.85-2.80 (m, 1H); 13 C NMR (151 MHz, CDC13) δ 168.30, 167.50, 156.68 (d, J = 237.9 Hz), 145.65 (d, J = 1.8 Hz), 135.40, 134.73, 129.20, 127.79, 127.14, 126.22, 117.38 (d, J = 7.6 Hz), 115.58 (d, J = 22.1 Hz), 59.24, 58.95, 52.64, 43.01, 25.78.

[0033] Example 3

[0034] Synthesis of 2-(2-(4-chlorophenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester

[0035]

[0036] In this example, 2-(4-chlorophenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline in Example 1, and other procedures were the same as in Example 1 to give 2-(2-(4-chlorophenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester in a yield of 51% with the following spectral data: 1 H NMR (600 MHz, CDC13) δ 7.21-7.17 (m, 2H), 7.13-7.10 (m, 2H), 6.90 (d, J = 6.9 Hz, 4H), 5.55 (d, J = 9.6 Hz, 1H), 3.94 (d, J = 9.6 Hz, 1H), 3.71-3.65 (m, 1H), 3.65 (s, 3H), 3.68-3.53 (m, 1H), 3.58 (s, 3H), 3.05-2.99 (m, 1H), 2.85-2.80 (m, 1H); 13C NMR (151 MHz, CDCI3) δ 168.26, 167.41, 147.44, 135.54, 134.68, 129.07, 129.04, 127.94, 127.13, 126.34, 123.42, 116.25, 59.17, 58.27, 52.74, 52.73, 42.61, 26.16.

[0037] Example 4

[0038] Synthesis of dimethyl 2-(2-(4-bromophenyl)-l,2,3,4-tetrahydroisoquinolin-l- yl)propanedioate

[0039]

[0040] In this example, 2-(4-bromophenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline in Example 1 in an equimolar amount, and the other procedures were the same as in Example 1 to give dimethyl 2-(2-(4-bromophenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)propanedioate in a yield of 35% with the following spectral data: 1 H NMR (600 MHz, CDCI3) δ 7.32-7.26 (m, 2H), 7.21-7.16 (m, 2H), 7.15-7.09 (m, 2H), 6.85 (d, J = 9.0 Hz, 2H), 5.64 (d, J = 9.3 Hz, 1H), 3.91 (d, J = 9.6 Hz, 1H), 3.69-3.62 (m, 1H), 3.66 (s, 3H), 3.57-3.51 (m, 1H), 3.55 (s, 3H), 3.10-2.99 (m, 1H), 2.93-2.88 (m, 1H); 13 C NMR (151 MHz, CDCI3) δ 168.25, 167.39, 147.85, 135.55, 134.67, 131.94, 129.05, 127.97, 127.14, 126.36, 116.61, 110.62, 59.15, 58.17, 52.75, 52.73, 42.55, 26.21.

[0041] Example 5

[0042] Synthesis of dimethyl 2-(2-(p-tolyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)propanedioate

[0043]

[0044] In this example, 2-(3-methoxyphenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline used in Example 1 in an equimolar amount, and other steps were the same as in Example 1 to obtain 2-(2-(3-methoxyphenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester in a yield of 55% with spectral data of: 1 H NMR (600 MHz, CDC13) δ 7.21 - 7.12 (m, 2H), 7.12 - 7.06 (m, 2H), 7.01 (d, J = 8.3 Hz, 2H), 6.89 (d, J = 8.7 Hz, 2H), 5.61 (d, J = 9.3 Hz, 1H), 3.96 (d, J = 9.3 Hz, 1H), 3.69 - 3.59 (m, 2H), 3.64 (s, 3H), 3.57 (s, 3H), 3.07 - 3.01 (m, 1H), 2.82 - 2.77 (m, 1H), 2.22 (s, 3H); 13 C NMR (151 MHz, CDC13) δ 168.42, 167.57, 146.88, 135.65, 134.91, 129.72, 129.17, 128.27, 127.63, 127.19, 126.05, 115.97, 59.26, 58.66, 52.62, 52.56, 42.40, 25.85, 20.40.

[0045] Example 6

[0046] Synthesis of 2-(2-(3-methoxyphenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester

[0047]

[0048] In this example, 2-(3-methoxyphenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline used in Example 1 in an equimolar amount, and other steps were the same as in Example 1 to obtain 2-(2-(3-methoxyphenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester in a yield of 55% with spectral data of: 1H NMR (600 MHz, CDC13) δ 7.23-7.15 (m, 2H), 7.15-7.06 (m, 2H), 6.97-6.93 (m, 1H), 6.82 (d, J = 8.1 Hz, 1H), 6.80-6.73 (m, 2H), 5.41 (d, J = 9.0 Hz, 1H), 3.99 (d, J = 9.0 Hz, 1H), 3.81 (s, 3H), 3.64-3.47 (m, 8H), 3.56 (s, 3H), 3.55 (s, 3H), 2.92-2.81 (m, 1H), 2.70-2.63 (m, 1H); 13 C NMR (151 MHz, CDC13) δ 168.51, 167.79, 153.03, 139.63, 135.79, 135.22, 129.40, 127.33, 126.97, 125.91, 123.57, 122.16, 120.85, 111.77, 59.43, 59.00, 55.51, 52.40, 52.35, 43.08, 26.32.

[0049] Example 7

[0050] Synthesis of 2-(2-(4-(tert-butyl)phenyl)-l,2,3,4-tetrahydroisoquinolin-l- yl)malonic acid dimethyl ester

[0051]

[0052] In this example, 2-(4-(tert-butyl)phenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline in Example 1, and other procedures were the same as in Example 1 to give 2-(2-(4-(tert-butyl)phenyl)-l,2,3,4-tetrahydroisoquinolin-l- yl)malonic acid dimethyl ester in 95% yield with the following spectral data: 1 H NMR (600 MHz, CDC13) δ 7.23-7.15 (m, 2H), 7.15-7.06 (m, 2H), 6.97-6.93 (m, 1H), 6.82 (d, J = 8.1 Hz, 1H), 6.80-6.73 (m, 2H), 5.41 (d, J = 9.0 Hz, 1H), 3.99 (d, J = 9.0 Hz, 1H), 3.81 (s, 3H), 3.64-3.47 (m, 8H), 3.56 (s, 3H), 3.55 (s, 3H), 2.92-2.81 (m, 1H), 2.70-2.63 (m, 1H); 13C NMR (151 MHz, CDCI3) δ 168.41, 167.60, 146.68, 141.54, 135.75, 134.92, 129.16, 127.62, 127.18, 126.03, 125.96, 115.37, 59.24, 58.73, 52.62, 52.56, 42.13, 33.92, 31.54, 25.96.

[0053] Example 8

[0054] Synthesis of 2-(2-(3,4-dimethylphenyl)-l,2,3,4-tetrahydroisoquinolin-l- yl)malonic acid dimethyl ester

[0055]

[0056] In this example, 2-(3,4-dimethylphenyl)-l,2,3,4-tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline in Example 1 in an equimolar amount, and other procedures were the same as in Example 1 to give 2-(2-(3,4-dimethylphenyl)-l,2,3,4-tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester in a yield of 74% with the following spectral data: 1 H NMR (600 MHz, CDCI3) δ 7.22-7.17 (m, 1 H), 7.17-7.12 (m, 1 H), 7.11-7.05 (m, 2 H), 6.95 (d, J = 8.4 Hz, 1 H), 6.78 (d, J = 2.7 Hz, 1 H), 6.75-6.70 (m, 1 H), 5.60 (d, J = 9.3 Hz, 1 H), 3.97 (d, J = 9.6 Hz, 1 H), 3.69-3.60 (m, 2 H), 3.64 (s, 3 H), 3.59 (s, 3 H), 3.08-2.99 (m, 1 H), 2.81-2.73 (m, 1 H), 2.20 (s, 3 H), 2.13 (s, 3 H); 13 C NMR (151 MHz, CDCI3) δ 168.41, 167.60, 146.68, 141.54, 135.75, 134.92, 129.16, 127.62, 127.18, 126.03, 125.96, 115.37, 59.24, 58.73, 52.62, 52.56, 42.13, 33.92, 31.54, 25.96.

[0057] Example 9

[0058] Synthesis of 2-(5-bromo-2-(4-methoxyphenyl)-l,2,3,4-tetrahydroisoquinolin-l- yl)malonic acid dimethyl ester having the following structural formula

[0059]

[0060] In this example, equimolar 5-bromo-2-(4-methoxyphenyl)-l,2,3,4- tetrahydroisoquinoline was used instead of 2-phenyl-l,2,3,4-tetrahydroisoquinoline used in Example 1, and the reaction time was extended to 24 hours. The other procedures were the same as in Example 1 to give 2-(5-bromo-2-(4-methoxyphenyl)-l,2,3,4- tetrahydroisoquinolin-l-yl)malonic acid dimethyl ester in a yield of 54% with the following spectral data: 1 H NMR (600 MHz, CDC13) δ 7.47 = 7.41 (m, 1H), 7.19 (d, J = 7.8 Hz, 1H), 6.99 (t, J = 7.8 Hz, 1H), 6.93 - 6.88 (m, 2H), 6.79 - 6.85 (m, 2H), 5.44 (d, J = 9.3 Hz, 1H), 3.97 (d, J = 9.6 Hz, 1H), 3.73 (s, 3H), 3.67 - 3.61 (m, 2H), 3.64 (s, 3H), 3.63 (s, 3H), 2.95 - 2.83 (m, 1H), 2.82 - 2.68 (m, 1H); 13 C NMR (151 MHz, CDC13) δ 168.30, 167.48, 153.80, 143.24, 137.75, 134.58, 131.79, 127.24, 126.56, 125.85, 118.87, 114.66, 59.63, 58.97, 55.70, 52.78, 52.70, 42.55, 26.40.

[0061] Example 10

[0062] Synthesis of l-(nitro)-2-phenyl-l,2,3,4-tetrahydroisoquinoline having the following structural formula

[0063]

[0064] In this example, equimolar nitromethane was used instead of malonic acid dimethyl ester used in Example 1, and the other procedures were the same as in Example 1 to give l-(nitro)-2-phenyl-l,2,3,4-tetrahydroisoquinoline in a yield of 55% with the following spectral data: 1HNMR (600 MHz, CDC13) δ 7.30-7.10 (m, 6H), 6.97 (d, J = 8.1 Hz, 2H), 6.84 (t, J = 7.2 Hz, IH), 5.54 (t, J = 7.2 Hz, IH), 4.85 (dd, J = 11.7, 7.8 Hz, IH), 4.55 (dd, J = 12.0, 6.6 Hz, IH), 3.69-3.55 (m, 2H), 3.10-3.05 (m, IH), 2.78 (dt, J = 16.5, 5.1 Hz, IH); 13 C NMR (151 MHz, CDC13) δ 148.56, 135.41, 133.06, 129.64, 129.32, 128.25, 127.13, 126.82, 119.55, 115.23, 78.90, 58.31, 42.18, 26.57.

[0065] Example 11

[0066] Synthesis of ethyl 2-nitro-2-(2-phenyl-l,2,3,4-tetrahydroisoquinolin-l- yl)acetate

[0067]

[0068] In this example, ethyl nitroacetate was used instead of dimethyl malonate in Example 1, and the reaction time was extended to 24 hours. The other procedures were the same as in Example 1. Ethyl 2-nitro-2-(2-phenyl-l,2,3,4-tetrahydroisoquinolin-l-yl)acetate was obtained in 83% yield, and the spectral data were as follows: 1 HNMR (600 MHz, CDC13) δ 7.30-7.10 (m, 6H), 6.97 (d, J = 8.1 Hz, 2H), 6.84 (t, J = 7.2 Hz, IH), 5.54 (t, J = 7.2 Hz, IH), 4.85 (dd, J = 11.7, 7.8 Hz, IH), 4.55 (dd, J = 12.0, 6.6 Hz, IH), 3.69-3.55 (m, 2H), 3.10-3.05 (m, IH), 2.78 (dt, J = 16.5, 5.1 Hz, IH); 13C NMR (151 MHz, CDCI3) δ 163.28, 162.83, 148.73, 148.19, 135.66, 135.05, 133.39, 131.67, 129.47, 129.43, 129.07, 128.81, 128.54, 127.69, 127.16, 127.00, 126.41, 120.29, 119.39, 116.54, 114.84, 92.61, 91.66, 63.27, 63.21, 59.84, 59.00, 43.62, 42.72, 26.78, 26.09, 13.78.

[0069] Example 12

[0070] Recovery experiment

[0071] Recovery experiment

[0072] To reduce the impact of loss when the catalyst is recovered, the reaction was scaled up. 104.65 mg (0.5 mmol) of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, 16.2 mg (0.01 mmol) of (MV)Bi2I8 perovskite, 0.575 mL (5 mmol) of dimethyl malonate were added to a quartz tube, then 3 mL of t-butanol was added, the reaction mixture was stirred at room temperature and irradiated with a 10W 700 nm monochromatic LED lamp for 12 hours. 0.5 mmol (34.76 mg) of dibromomethane was added as an internal standard, after mixing evenly, a drop of supernatant was taken and added to 0.5 mL of deuterated chloroform, and the reaction yield was tested by nuclear magnetic hydrogen spectrum. The sample after the reaction was completely transferred to a centrifuge tube, washed and centrifuged to collect the catalyst for the next reaction. The catalyst was reused three times, and the yield of the target product was 77%, 75%, and 68%, respectively.

Claims

1. A method for photocatalytic coupling of 2-benzo-1,2,3,4-tetrahydroisoquinolines with nucleophiles using near infrared light, characterized in that: The cross-dehydrogenative coupling reaction of 2-benzene-1,2,3,4-tetrahydroisoquinoline compounds shown in formula I, nucleophilic reagent NuH, (MV)Bi2I8 perovskite and solvent is carried out under near-infrared light irradiation to obtain coupling products shown in formula II; wherein R 1 , R 2 each independently represents any one of hydrogen, fluorine, chlorine, bromine, C1-C6 alkyl, C1-C4 alkoxy; The nucleophilic reagent NuH is any one of dimethyl malonate, nitromethane and ethyl nitroacetate. In the (MV)Bi2I8 perovskite, MV 2+ represents a methylviologen cation.

2. The method for near-infrared photocatalytic coupling of 2-benzo-1,2,3,4- tetrahydroisoquinolines with nucleophiles according to claim 1, characterized in that: R represents hydrogen or bromine, 1 R represents hydrogen or bromine, 2 R represents hydrogen, fluorine, chlorine, bromine, methyl, methoxy, tert-butyl.

3. The method for near-infrared photocatalytic coupling of 2-benzo-1,2,3,4- tetrahydroisoquinolines with nucleophiles according to claim 1 or 2, characterized in that: The molar ratio of the 2-benzene-1,2,3,4-tetrahydroisoquinoline compound to the nucleophilic reagent NuH is 1:5-15.

4. The method for near-infrared photocatalytic coupling of 2-benzo-1,2,3,4- tetrahydroisoquinolines with nucleophiles according to claim 1 or 2, characterized in that: The (MV)Bi2I8 perovskite is added in an amount of 1%-5% of the molar amount of the 2-benzene-1,2,3,4-tetrahydroisoquinoline compound.

5. The method for near-infrared photocatalytic coupling of 2-benzo-1,2,3,4- tetrahydroisoquinolines with nucleophiles according to claim 1 or 2, characterized in that: The solvent is isopropyl alcohol or tert-butyl alcohol.

6. The method for near-infrared photocatalytic coupling of 2-benzo-1,2,3,4- tetrahydroisoquinolines with nucleophiles according to claim 1 or 2, characterized in that: The cross-dehydrogenative coupling reaction is carried out under near-infrared light irradiation at room temperature in an air atmosphere, and the reaction time is 12-24 hours.

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