METHOD FOR PREPARING BENZYLAMINE DERIVATIVE THROUGH AMINATION OF BENZYLIC C-H BOND UNDER VISIBLE LIGHT-INDUCED NICKEL CATALYSIS

Abstract

A method for preparing a benzylamine derivative through amination of a benzylic CH bond under visible light-induced nickel catalysis is provided. The method includes: weighing and adding an amination reagent, a ruthenium or iridium photosensitizer, a nickel catalyst, a Lewis acid, and a ligand according to a molar ratio to a reaction vessel; under an inert gas atmosphere, adding a solvent, stirring, adding a benzyl-containing alkylate, and irradiating with a visible light source to allow a full reaction; and conducting separation and purification to obtain the benzylamine derivative. The method involves cheap and easily-available raw materials, and has relatively-extensive substrate applicability. In addition, the method has advantages such as mild reaction conditions, a high yield of a target product, small pollution, and a simple reaction operation and post-treatment, and thus is suitable for industrial production.

Claims

1. A method for preparing a benzylamine derivative through amination of a benzylic CH bond under a visible light-induced nickel catalysis, comprising: weighing and adding an amination reagent, a ruthenium or iridium photosensitizer, a nickel catalyst, a Lewis acid, and a ligand according to a molar ratio to a reaction vessel; under an inert gas atmosphere, adding a solvent to the reaction vessel, fully stirring, adding a benzyl-containing alkylate to the reaction vessel, and irradiating with a visible light source to allow a full reaction; and conducting separation and purification to obtain the benzylamine derivative with the following general structural formula: ##STR00032## wherein R.sup.1 is selected from one of hydrogen, C.sub.1-C.sub.4 alkyl, alkoxy, aryl, and halogen; R.sup.2 is selected from one of hydrogen, C.sub.1-C.sub.6 alkyl, and aryl; R.sup.3 is selected from one of C.sub.1-C.sub.3 alkyl and halogen; and R.sup.4 is selected from one of C.sub.1-C.sub.5 alkyl and aryl.

2. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein a molar ratio of the benzyl-containing alkylate, the amination reagent, the ruthenium or iridium photosensitizer, the nickel catalyst, the Lewis acid, and the ligand is 1:(1-5):(0.05-0.5):(0.05-0.5):(1-3):(0.05-0.25).

3. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein a general structural formula of the benzyl-containing alkylate is ##STR00033## and a general structural formula of the amination reagent is ##STR00034##

4. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein a wavelength of the visible light source is 400 nm to 475 nm.

5. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein the ruthenium or iridium photosensitizer is one of Ru(bpy).sub.3Cl.sub.2, Ru(bpy).sub.3(PF.sub.6).sub.2, Ir(ppy).sub.3, Ir(ppy).sub.2(dtbbpy)PF.sub.6, and Ir[dF(CF.sub.3)ppy)].sub.2(dtbbpy)PF.sub.6.

6. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein the Lewis acid is one of fluoroboric acid or boron trifluoride etherate.

7. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein the nickel catalyst is NiX.sub.2 or NiX.sub.2.Math.dme, wherein X is one of Cl, Br, and I.

8. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein the ligand is one of a bipyridine ligand or a phenanthroline ligand.

9. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein the solvent is one of acetonitrile, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, or N,N-dimethylformamide; and an inert gas is nitrogen or argon.

10. The method for preparing the benzylamine derivative through the amination of the benzylic CH bond under the visible light-induced nickel catalysis according to claim 1, wherein a product is purified by column chromatography or liquid chromatography (LC).

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0032] To make the objectives, features, and advantages of the present disclosure clear and comprehensible, specific implementations of the present disclosure will be described in detail below in conjunction with specific examples.

Example 1

[0033] Synthesis of N-benzyl-p-toluenesulfonamide

##STR00007##

[0034] P-toluenesulfonyl azide and toluene were adopted as raw materials. Reaction steps were as follows:

[0035] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, toluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0036] (2) The reaction was monitored by TLC until the reaction was completed.

[0037] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 83%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, J=7.9 Hz, 2H), 7.31 (d, J=7.9 Hz, 2H), 7.29-7.24 (m, 3H), 7.26-7.16 (m, 2H), 4.70 (brs, 1H), 4.12 (d, J=6.2 Hz, 2H), 2.44 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.69, 136.98, 136.39, 129.89, 128.84, 128.07, 128.01, 127.33, 47.42, 21.68.

Example 2

Synthesis of N-4-fluorobenzyl)p-toluenesulfonamide

##STR00008##

[0038] P-toluenesulfonyl azide and p-fluorotoluene were adopted as raw materials. Reaction steps were as follows:

[0039] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-fluorotoluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0040] (2) The reaction was monitored by TLC until the reaction was completed.

[0041] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 72%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.74 (d, J=8.0 Hz, 2H), 7.31 (d, J=8.0 Hz, 2H), 7.17 (dd, J=8.4, 5.4 Hz, 2H), 6.96 (t, J=8.5 Hz, 2H), 4.78 (t, J=6.4 Hz, 1H), 4.09 (d, J=6.2 Hz, 2H), 2.44 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 162.52 (d, J=246.7 Hz), 143.79, 136.97, 132.24 (d, J=3.6 Hz), 129.91, 129.76 (d, J=8.1 Hz), 127.29, 115.70 (d, J=21.7 Hz), 46.70, 21.68.

Example 3

[0042] Synthesis of N-(4-chlorobenzyl)p-toluenesulfonamide

##STR00009##

[0043] P-toluenesulfonyl azide and p-chlorotoluene were adopted as raw materials. Reaction steps were as follows:

[0044] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-chlorotoluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0045] (2) The reaction was monitored by TLC until the reaction was completed.

[0046] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 71%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.73 (d, J=8.1 Hz, 2H), 7.30 (d, J=8.1 Hz, 2H), 7.24 (d, J=8.5 Hz, 2H), 7.13 (d, J=8.5 Hz, 2H), 4.82 (t, J=6.4 Hz, 1H), 4.09 (d, J=6.3 Hz, 2H), 2.44 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.84, 136.92, 134.99, 133.90, 129.92, 129.35, 128.95, 127.28, 46.71, 21.68.

Example 4

[0047] Synthesis of N-(4-bromobenzyl)p-toluenesulfonamide

##STR00010##

[0048] P-toluenesulfonyl azide and p-bromotoluene were adopted as raw materials. Reaction steps were as follows:

[0049] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-bromotoluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0050] (2) The reaction was monitored by TLC until the reaction was completed.

[0051] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 81%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.72 (d, J=8.1 Hz, 2H), 7.38 (d, J=8.4 Hz, 2H), 7.29 (d, J=8.1 Hz, 2H), 7.07 (d, J=8.4 Hz, 2H), 4.88 (t, J=6.3 Hz, 1H), 4.07 (d, J=6.4 Hz, 2H), 2.44 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.84, 136.91, 135.52, 131.89, 129.92, 129.67, 127.27, 121.97, 46.74, 21.69.

Example 5

[0052] Synthesis of N-(2,4-difluorobenzyl)p-toluenesulfonamide

##STR00011##

[0053] P-toluenesulfonyl azide and 2,4-difluorotoluene were adopted as raw materials. Reaction steps were as follows:

[0054] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 2,4-difluorotoluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0055] (2) The reaction was monitored by TLC until the reaction was completed.

[0056] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 76%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.70 (d, J=8.1 Hz, 2H), 7.27 (d, J=8.1 Hz, 2H), 7.25-7.20 (m, 1H), 6.87-6.52 (m, 2H), 4.84 (t, J=6.5 Hz, 1H), 4.17 (d, J=6.5 Hz, 2H), 2.42 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 162.78 (dd, J=249.3, 11.7 Hz), 160.84 (dd, J=249.3, 11.7 Hz), 143.75, 137.00, 131.21 (dd, J=9.5, 5.7 Hz), 129.82, 127.20, 119.78 (dd, J=14.6, 3.7 Hz), 111.53 (dd, J=21.1, 3.6 Hz), 103.96 (t, J=25.4 Hz), 40.89 (d, J=3.5 Hz), 21.63.

Example 6

[0057] Synthesis of N-(2-trifluoromethylbenzyl)p-toluenesulfonamide

##STR00012##

[0058] P-toluenesulfonyl azide and 2-methylbenzotrifluoride were adopted as raw materials. Reaction steps were as follows:

[0059] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 2-methylbenzotrifluoride (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0060] (2) The reaction was monitored by TLC until the reaction was completed.

[0061] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 83%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.75 (d, J=8.4 Hz, 2H), 7.59 (t, J=7.8 Hz, 2H), 7.50 (t, J=8.1 Hz, 1H), 7.38 (t, J=7.6 Hz, 1H), 7.31 (d, J=7.9 Hz, 2H), 4.79 (t, J=6.6 Hz, 1H), 4.30 (d, J=6.6 Hz, 2H), 2.44 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.85, 136.97, 135.04, 132.50, 130.96, 129.94, 128.19 (q, J=30.5 Hz), 128.16, 127.24, 127.23, 126.13 (q, J=5.4 Hz), 124.33 (q, J=273.9 Hz), 43.89, 21.69.

Example 7

[0062] Synthesis of N-(2-methylbenzyl)p-toluenesulfonamide

##STR00013##

[0063] P-toluenesulfonyl azide and o-xylene were adopted as raw materials. Reaction steps were as follows:

[0064] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, o-xylene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0065] (2) The reaction was monitored by TLC until the reaction was completed.

[0066] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 55%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.77 (d, J=7.9 Hz, 2H), 7.32 (d, J=7.9 Hz, 2H), 7.23-7.08 (m, 4H), 4.44 (t, J=6.0 Hz, 1H), 4.09 (d, J=5.9 Hz, 2H), 2.45 (s, 3H), 2.25 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.71, 136.89, 134.00, 130.78, 129.89, 129.01, 128.43, 127.36, 126.36, 45.58, 21.70, 18.93.

Example 8

[0067] Synthesis of N-(4-methylbenzyl)p-toluenesulfonamide

##STR00014##

[0068] P-toluenesulfonyl azide and p-xylene were adopted as raw materials. Reaction steps were as follows:

[0069] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-xylene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0070] (2) The reaction was monitored by TLC until the reaction was completed.

[0071] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 50%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, J=7.9 Hz, 2H), 7.31 (d, J=7.9 Hz, 2H), 7.10-7.06 (m, 4H), 4.57 (t, J=6.1 Hz, 1H), 4.07 (d, J=6.0 Hz, 2H), 2.44 (s, 3H), 2.31 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.62, 137.85, 137.00, 133.33, 129.86, 129.50, 128.00, 127.34, 47.19, 21.67, 21.22.

Example 9

[0072] Synthesis of N-(4-phenylbenzyl)p-toluenesulfonamide

##STR00015##

[0073] P-toluenesulfonyl azide and 4-methylbiphenyl were adopted as raw materials. Reaction steps were as follows:

[0074] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 4-methylbiphenyl (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0075] (2) The reaction was monitored by TLC until the reaction was completed.

[0076] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 49%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.77 (d, J=7.9 Hz, 2H), 7.59 (d, J=7.8 Hz, 1H), 7.54 (d, J=7.6 Hz, 2H), 7.50 (d, J=7.9 Hz, 2H), 7.43 (t, J=7.7 Hz, 2H), 7.36 (d, J=7.3 Hz, 1H), 7.31 (d, J=8.1 Hz, 2H), 7.26 (d, J=7.3 Hz, 1H), 4.75 (brs, 1H), 4.17 (d, J=5.9 Hz, 2H), 2.43 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 143.71, 141.07, 140.64, 135.39, 129.90, 128.95, 128.47, 127.61, 127.55, 127.47, 127.35, 127.23, 127.18, 47.15, 21.68.

Example 10

[0077] Synthesis of N-(4-tert-butylbenzyl)p-toluenesulfonamide

##STR00016##

[0078] P-toluenesulfonyl azide and 4-tert-butyltoluene were adopted as raw materials. Reaction steps were as follows:

[0079] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 4-tert-butyltoluene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0080] (2) The reaction was monitored by TLC until the reaction was completed.

[0081] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 49%). Analytical data of the product was as follows: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.75 (d, J=7.9 Hz, 2H), 7.29 (d, J=7.9 Hz, 4H), 7.11 (d, J=7.9 Hz, 2H), 4.64 (t, J=6.6 Hz, 1H), 4.09 (d, J=6.0 Hz, 2H), 2.43 (s, 3H), 1.28 (s, 9H); .sup.13C NMR (101 MHz, CDCl.sub.3) 151.16, 143.56, 137.06, 133.33, 129.84, 127.80, 127.34, 125.74, 47.11, 34.66, 31.42, 21.67.

Example 11

##STR00017##

[0082] P-toluenesulfonyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0083] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0084] (2) The reaction was monitored by TLC until the reaction was completed.

[0085] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 74%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.43 (d, 3H, J=7.0 Hz), 2.39 (s, 3H), 4.46 (dq, 1H, J=6.5, 7.0 Hz), 4.69 (d, 1H, J=6.5 Hz), 7.07-7.13 (m, 2H), 7.17-7.23 (m, 5H), 7.61 (dd, 2H, J=1.6, 6.8 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.5, 23.5, 53.5, 125.9, 126.8, 127.3, 128.3, 129.2, 137.3, 141.7, 142.9.

Example 12

##STR00018##

[0086] P-toluenesulfonyl azide and p-ethylanisole were adopted as raw materials. Reaction steps were as follows:

[0087] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-ethylanisole (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0088] (2) The reaction was monitored by TLC until the reaction was completed.

[0089] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 85%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.39 (d, 3H, J=7.0 Hz), 2.39 (s, 3H), 3.74 (s, 3H), 4.40 (dq, 1H, J=7.0 Hz), 5.06 (d, 1H, J=7.0 Hz), 6.70 (dd, 2H, J=2.2, 9.5 Hz), 7.00 (dd, 2H, J=2.2, 9.5 Hz), 7.18 (d, 2H, J=8.4 Hz), 7.61 (d, 2H, J=8.4 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.5, 23.5, 53.1, 55.2, 113.7, 127.0, 127.2, 129.3, 134.0, 137.5, 142.8, 158.6.

Example 13

##STR00019##

[0090] P-toluenesulfonyl azide and p-bromoethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0091] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, p-bromoethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0092] (2) The reaction was monitored by TLC until the reaction was completed.

[0093] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 61%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.37 (d, 3H, J=6.8 Hz), 2.40 (s, 3H), 4.41 (dq, 1H, J=7.0, 6.8 Hz), 5.37 (d, 1H, J=7.0 Hz), 6.96 (d, 2H, J=8.6 Hz), 7.16 (d, 2H, J=8.1 Hz), 7.26 (d, 2H, J=8.1 Hz), 7.57 (d, 2H, J=8.6 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.5, 23.4, 53.1, 121.0, 126.9, 127.8, 129.3, 131.3, 137.2, 140.9, 143.2.

Example 14

##STR00020##

[0094] P-toluenesulfonyl azide and cumene were adopted as raw materials. Reaction steps were as follows:

[0095] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, cumene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0096] (2) The reaction was monitored by TLC until the reaction was completed.

[0097] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 70%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.61 (s, 6H), 2.37 (s, 3H), 5.38 (s, 1H), 7.12-7.19 (m, 5H), 7.25-7.31 (m, 2H), 7.56 (d, 2H, J=8.6 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.5, 29.8, 58.5, 125.4, 126.8 (2C), 127.9, 129.1, 139.6, 142.4, 145.0.

Example 15

##STR00021##

[0098] P-toluenesulfonyl azide and butylbenzene were adopted as raw materials. Reaction steps were as follows:

[0099] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, butylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0100] (2) The reaction was monitored by TLC until the reaction was completed.

[0101] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 73%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 0.82 (t, 3H, J=7.3 Hz), 1.12-1.28 (m, 2H), 1.62-1.77 (m, 2H), 2.34 (s, 3H), 4.27 (dt, 1H, J=7.3 Hz), 5.06 (d, 1H, J=7.3 Hz), 6.98-7.02 (m, 2H), 7.08-7.15 (m, 5H), 7.53 (d, 2H, J=8.4 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 13.5, 19.1, 21.4, 39.7, 58.1, 126.5, 127.0, 127.2, 128.3, 129.2, 137.7, 141.0, 142.8.

Example 16

##STR00022##

[0102] P-toluenesulfonyl azide and tetrahydronaphthalene were adopted as raw materials. Reaction steps were as follows:

[0103] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, tetrahydronaphthalene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0104] (2) The reaction was monitored by TLC until the reaction was completed.

[0105] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 76%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.69-1.86 (m, 4H), 2.46 (s, 3H), 2.57-2.81 (m, 2H), 4.41-4.47 (m, 1H), 4.69 (d, 1H, J=7.6 Hz), 6.93 (d, 11H, J=7.6 Hz), 7.02-7.16 (m, 3H), 7.34 (d, 2H, J=8.6 Hz), 7.82 (d, 2H, J=8.6 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 19.2, 21.7, 28.9, 30.8, 51.9, 126.2, 127.0, 127.5, 128.7, 129.1, 129.6, 135.4, 137.4, 137.9, 143.2.

Example 17

##STR00023##

[0106] P-toluenesulfonyl azide and dihydroindene were adopted as raw materials. Reaction steps were as follows:

[0107] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, dihydroindene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0108] (2) The reaction was monitored by TLC until the reaction was completed.

[0109] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 88%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 1.71-1.82 (m, 1H), 2.29-2.40 (m, 1H), 2.46 (s, 3H), 2.71-2.80 (m, 1H), 2.85-2.91 (m, 1H), 4.66 (d, 1H, J=8.6 Hz), 4.82 (dt, 1H, J=8.6, 7.3 Hz), 7.06-7.21 (m, 4H), 7.34 (d, 2H, J=8.6 Hz), 7.84 (d, 2H, J=8.6 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.6, 30.0, 34.7, 58.7, 124.0, 124.7, 126.7, 127.0, 128.1, 129.7, 138.0, 141.8, 142.7, 143.3.

Example 18

##STR00024##

[0110] P-toluenesulfonyl azide and diphenylmethane were adopted as raw materials. Reaction steps were as follows:

[0111] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, diphenylmethane (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0112] (2) The reaction was monitored by TLC until the reaction was completed.

[0113] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 96%). Analytical data of the product was as follows: .sup.1H NMR (270 MHz, CDCl.sub.3) 2.36 (s, 3H), 5.25 (br s, 1H), 5.56 (d, 1H, J=7.3 Hz), 6.81-7.49 (m, 12H), 7.55 (d, 2H, J=6.5 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.5, 61.4, 127.1, 127.3, 127.4, 128.4, 129.2, 137.3, 140.4, 143.0.

Example 19

##STR00025##

[0114] P-toluenesulfonyl azide and 1,3-dihydrobenzofuran were adopted as raw materials. Reaction steps were as follows:

[0115] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 1,3-dihydrobenzofuran (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0116] (2) The reaction was monitored by TLC until the reaction was completed.

[0117] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 88%). Analytical data of the product was as follows: .sup.1HNMR (270 MHz, CDCl.sub.3) 2.45 (s, 3H), 4.91 (d, 1H, J=12.7 Hz), 5.00 (d, 1H, J=12.7 Hz), 5.21 (d, 1H, J=10.3 Hz), 6.54 (d, 1H, J=10.3 Hz), 7.19-7.39 (m, 6H), 7.86 (d, 2H, J=8.4 Hz). .sup.13C NMR (68 MHz, CDCl.sub.3) 21.6, 72.0, 88.9, 121.0, 122.9, 127.1, 128.0, 129.4, 129.5, 136.5, 138.5, 139.1, 143.3.

Example 20

##STR00026##

[0118] P-toluenesulfonyl azide and 1,3-dihydrobenzofuran were adopted as raw materials. Reaction steps were as follows:

[0119] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-toluenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, 1,3-dihydrobenzofuran (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0120] (2) The reaction was monitored by TLC until the reaction was completed.

[0121] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 88%). Analytical data of the product was as follows: .sup.1HNMR (270 MHz, CDCl.sub.3) 2.45 (s, 3H), 4.91 (d, 1H, J=12.7 Hz), 5.00 (d, 1H, J=12.7 Hz), 5.21 (d, 1H, J=10.3 Hz), 6.54 (d, 1H, J=10.3 Hz), 7.19-7.39 (m, 6H), 7.86 (d, 21, J=8.4 Hz); .sup.13C NMR (68 MHz, CDCl.sub.3) 21.6, 72.0, 88.9, 121.0, 122.9, 127.1, 128.0, 129.4, 129.5, 136.5, 138.5, 139.1, 143.3.

Example 21

##STR00027##

[0122] Benzenesulfonyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0123] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and benzenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0124] (2) The reaction was monitored by TLC until the reaction was completed.

[0125] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 66%). Analytical data of the product was as follows: .sup.1HNMR (600 MHz, CDCl.sub.3): 7.73 (d, J=7.6 Hz, 2H), 7.51-7.47 (m, 1H), 7.40-7.36 (m, 2H), 7.21-7.16 (m, 3H), 7.11-7.06 (m, 2H), 5.05 (d, J=7.1 Hz, 1H), 4.53-4.47 (m, 1H), 1.44 (d, J=6.8 Hz, 3H); .sup.13CNMR (150 MHz, CDCl.sub.3): 141.7, 140.5, 132.3, 128.8, 128.5, 127.5, 127.0, S6 126.0, 53.7, 23.6.

Example 22

##STR00028##

[0126] P-methoxybenzenesulfonyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0127] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-methoxybenzenesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0128] (2) The reaction was monitored by TLC until the reaction was completed.

[0129] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 66%). Analytical data of the product was as follows: .sup.1HNMR (600 MHz, CDCl.sub.3): 7.66 (d, J=8.8 Hz, 2H), 7.22-7.16 (m, 3H), 7.13-7.09 (m, 2H), 6.84 (d, J=8.8 Hz, 2H), 5.24 (d, J=7.1 Hz, 1H), 4.49-4.40 (m, 1H), 3.83 (s, 3H), 1.42 (d, J=6.8 Hz, 3H); .sup.13CNMR (150 MHz, CDCl.sub.3): 162.5, 142.0, 132.1, 129.1, 128.4, 127.3, 126.1, 113.9, 55.5, 53.6, 23.6.

Example 23

##STR00029##

[0130] P-methanesulfonyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0131] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-methanesulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0132] (2) The reaction was monitored by TLC until the reaction was completed.

[0133] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 45%). Analytical data of the product was as follows: .sup.1HNMR (600 MHz, CDCl.sub.3): 7.40-7.33 (m, 4H), 7.33-7.29 (m, 1H), 4.98 (d, J=6.3 Hz, 1H), 4.69-4.60 (m, 1H), 2.62 (s, 3H), 1.55 (d, J=7.1 Hz, 3H); BC NMR (150 MHz, CDCl.sub.3): 142.3, 128.9, 128.0, 126.2, 53.7, 41.7, 24.0.

Example 24

##STR00030##

[0134] P-trichloroethoxyformyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0135] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-trichloroethoxyformyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0136] (2) The reaction was monitored by TLC until the reaction was completed.

[0137] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 45%). Analytical data of the product was as follows: .sup.1H NMR (600 MHz, CDCl.sub.3): 7.29 (d, J=8.5 Hz, 2H), 6.91 (d, J=8.5 Hz, 2H), 4.96 (d, J=6.8 Hz, 1H), 4.73-4.67 (m, 1H), 4.46 (d, J=10.8 Hz, 1H), 4.43 (d, J=10.8 Hz, 1H), 3.81 (s, 3H), 1.62 (d, J=6.8 Hz, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 159.4, 133.3, 127.5, 114.3, 93.3, 78.0, 55.3, 54.4, 22.6.

Example 25

##STR00031##

[0138] P-trichloroethoxysulfonyl azide and ethylbenzene were adopted as raw materials. Reaction steps were as follows:

[0139] (1) Tris(2-phenylpyridine)iridium (Ir(ppy).sub.3, 0.004 mmol), nickel dibromide (NiBr.sub.2.Math.dme, 0.04 mmol), 2,9-dimethyl-1,10-phenanthroline (0.048 mmol), and p-trichloroethoxysulfonyl azide (0.4 mmol) were added to a reaction flask, and the reaction flask was evacuated and subjected to gas replacement three times to make the reaction flask in an inert gas atmosphere. Under the protection of the inert gas atmosphere, acetonitrile (1 mL) was added, boron trifluoride etherate (0.2 mmol) was added dropwise, stirring was conducted for 5 min to allow thorough mixing, ethylbenzene (0.2 mmol) was added, and irradiation was conducted with a 475 nm blue LED lamp to allow a reaction at room temperature for 24 h.

[0140] (2) The reaction was monitored by TLC until the reaction was completed.

[0141] (3) A crude product obtained after the reaction was completed was separated through column chromatography (ethyl acetate:petroleum ether=1:20) to obtain a target product (yield: 54%). Analytical data of the product was as follows: .sup.1HNMR (600 MHz, CDCl.sub.3): 7.49 (d, J=4.9 Hz, 1H), 7.42 (d, J=3.7 Hz, 1H), 7.25-7.18 (m, 3H), 7.15 (d, J=7.6 Hz, 2H), 6.94 (t, J=4.3 Hz, 1H), 5.30 (d, J=6.8 Hz, 1H), 4.60-4.52 (m, 1H), 1.48 (d, J=6.8 Hz, 3H); .sup.13CNMR (150 MHz, CDCl.sub.3): 141.7, 141.6, 132.2, 131.7, 128.5, 127.5, 127.1, 126.0, 54.0, 23.5.