Allyl-containing alpha-quaternary carbon secondary amine compounds and synthesis of oxazine compounds containing a quaternary carbon center

Abstract

The application discloses an alpha-quaternary carbon secondary amine compound containing an allyl group and synthesis of oxazine compounds containing a quaternary carbon center. The application prepares the alpha-quaternary carbon secondary amine compound containing the allyl group through a light / palladium synergistic catalytic imine reduction allylation reaction; and further halogenation cyclization reaction with a halogenation reagent to synthesize the oxazine compound containing the quaternary carbon center. The method uses imine and an allyl electrophilic reagent as substrates, dissolves a light catalyst, a palladium catalyst, a biphosphine ligand, a non-metallic reducing agent and an alkali in dichloromethane and the like solvents, and catalyzes the imine reduction allylation reaction under blue light irradiation; and further reaction with the halogenation reagent at room temperature to obtain the oxazine compound containing the quaternary carbon center. The application has the characteristics of mild reaction condition, high yield and wide substrate range. The target molecule of the application has important potential application value in the fields of medicine and medicinal chemistry.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology and is a method for synthesizing oxazine compounds containing quaternary carbon centers. Specifically, it involves the reductive allylation of imines, α-quaternary carbon secondary amines containing allyl groups, and the subsequent synthesis of oxazine compounds containing quaternary carbon centers. Specifically, it involves a two-step synthesis using imines, an allyl electrophilic reagent, and a halogenating reagent as reactants, reacting at room temperature under blue light irradiation to obtain oxazine compounds containing quaternary carbon centers. This method utilizes a photo / palladium co-catalyzed strategy to achieve the allylation reaction through imine reduction, followed by a halogenation cyclization reaction with a halogenating reagent, resulting in the efficient and highly selective synthesis of oxazine compounds containing quaternary carbon centers. Background Technology

[0002] Over the past two decades, reductive cross-electrophilic coupling has developed rapidly, becoming one of the most efficient and stereoselective methods for constructing carbon-carbon and carbon-heterobonds. This type of method efficiently synthesizes the desired product through the reductive coupling of two stable electrophiles (such as halides or halide-like compounds), avoiding the preliminary step of converting the halide into a highly reactive organometallic reagent. Therefore, it has the advantages of simple operation and high step economy. Furthermore, π-allylpalladium is an important organometallic intermediate in transition metal palladium-catalyzed organic reactions. For example, Trost et al. achieved η... 3 - Allyl palladium undergoes electrophilic substitution with either a "soft" or "hard" nucleophile. Furthermore, the nucleophilic η... 1 -Allylpalladium species can be derived from η 3 -Allyl palladium species are generated via low-valent metals or transmetallic reagents, which then react with nucleophiles to form branched allyl products. Recently, with the rapid development of photocatalysis, it has become apparent that radicals generated by visible light photocatalysis can also react with n-terminal plasmas. 3 - Allyl palladium coordination generates a Pd(III) complex, which is then reduced and eliminated with high selectivity to yield the branched allyl product. However, to date, η 3 There are few reports of linear allylated products formed by reacting allyl palladium intermediates with electrophilic reagents.

[0003] Therefore, we propose a photo / palladium co-catalyzed imine reductive allylation reaction to selectively generate linear allylated products, which then undergo halogenation cyclization with halogenating reagents to synthesize oxazine compounds containing quaternary carbon centers. However, this strategy still faces several challenging issues. First, there is the compatibility problem between the photoredox continuous single-electron transfer (SSET) of imines and the palladium-catalyzed oxidative addition reaction. Second, the self-coupling of α-amino carbon radicals and the protonation of α-amino carbanions are competing reactions in this strategy. Finally, there is the selective cyclization with halogenating reagents to generate five-membered and six-membered rings. This approach is based on current methods for constructing C(sp...) compounds via reductive coupling.3 )-C(sp 3 ) bond is still one of the most challenging transformations in this field. Therefore, it is still of great value to develop a new efficient catalytic system to construct oxazinane compounds containing quaternary carbon center through reductive cross electrophilic coupling.

[0004] Heterocyclic nitrogen ligands play a crucial role in the development of transition metal catalysts. Compared with well-developed oxazoline ligands, oxazinane ligands with six-membered rings have special catalytic activity in transition metal catalysis. In addition, oxazoline compounds have many applications, such as pharmaceuticals, agricultural chemicals, polymers, and further as key components for the synthesis of complex chemical structures. It is worth noting that oxazinane compounds are very sensitive to acid. The current method for synthesizing oxazinane compounds still has the disadvantages of complex raw materials and complicated steps, so it is still of great significance to develop new, effective and practical methods to construct oxazinane compounds containing quaternary carbon centers. SUMMARY

[0005] The present application aims to provide a preparation method for synthesizing allyl-containing α-quaternary carbon secondary amine compounds, which has a wide range of substrates and good functional group compatibility.

[0006] Technical scheme: The present application adopts the following technical scheme.

[0007] The first object of the present application is to provide an allyl-containing α-quaternary carbon secondary amine compound, which has the following structural formula as shown in formula (3):

[0008]

[0009] In the formula, R represents any one of Ph, aryl, aryl derivative, heteroaryl and olefin, R 1 represents any one of H, aryl and aryl derivative, O represents an oxygen atom, N represents a nitrogen atom, H represents a hydrogen atom, Ph represents a phenyl group, and Ar represents any one of aryl, aryl derivative, heteroaryl and Ph.

[0010] Optionally, in the embodiments of the present application, the allyl-containing α-quaternary carbon secondary amine compound has any one of the following structures:

[0011]

[0012] A second object of the present application is to provide a method for preparing an allyl-containing alpha-quaternary secondary amine compound, comprising the following steps: dissolving an imine as shown in formula (1) and an allyl electrophile as shown in formula (2) in a solvent I, and adding a photocatalyst, a metal palladium catalyst, a diphosphine ligand, a non-metallic reducing agent and a base to perform a reaction, to obtain an imine reduction and selective allylation product as shown in formula (3), i.e. the allyl-containing alpha-quaternary secondary amine compound, and the reaction equation is as follows:

[0013]

[0014] In the formula, R represents any one of Ph, aryl, aryl derivative, heteroaryl and olefin, R 1 represents any one of H, aryl and aryl derivative, Y represents any one of Cl, Br, OTs, OBz, OAc and OCO2Ph, O represents an oxygen atom, N represents a nitrogen atom, H represents a hydrogen atom, Ph represents a phenyl group, and Ar represents any one of aryl, aryl derivative, heteroaryl and Ph.

[0015] Optionally, in the embodiment of the present application, the molar ratio of the imine to the allyl electrophile is 1:1-5, preferably 1:2.

[0016] Optionally, in the embodiment of the present application, the molar ratio of the imine to the photocatalyst is 1:0.001-0.05, preferably 1:0.02,

[0017] Optionally, in the embodiment of the present application, the molar ratio of the imine to the metal palladium catalyst is 1:0.001-0.05, preferably 1:0.025,

[0018] Optionally, in the embodiment of the present application, the molar ratio of the imine to the diphosphine ligand is 1:0.002-0.10, preferably 1:0.05,

[0019] Optionally, in the embodiment of the present application, the molar ratio of the imine to the non-metallic reducing agent is 1:1-5, preferably 1:2,

[0020] Optionally, in the embodiment of the present application, the molar ratio of the imine to the base is 1:1-5, preferably 1:2.

[0021] Optionally, in the embodiments of the present application, the allyl electrophile includes any one of allyl bromide, allyl acetate, allyl benzoate, allyl phenyl carbonate, allyl 4-methylbenzenesulfonate, 3-bromocyclohex-1-ene, allyl 2-phenylacetate, cinnamyl benzoate, 1-phenylallyl benzoate, (E)-3-(p-tolyl)allyl benzoate, (E)-3-(4-methoxyphenyl)allyl benzoate, (E)-3-(4-fluorophenyl)allyl benzoate.

[0022] Optionally, in the embodiments of the present application, the diphosphine ligand includes any one of triphenylphosphine, 1,4-bis(diphenylphosphino)butane and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos),

[0023] Optionally, in the embodiments of the present application, the solvent I includes any one of dichloroethane, toluene and dichloromethane,

[0024] Optionally, in the embodiments of the present application, the photocatalyst is any one of eosin Y disodium salt and metal iridium photosensitizer,

[0025] Optionally, in the embodiments of the present application, the metal palladium catalyst includes any one of palladium acetate, palladium tetraphenylphosphine and palladium acetylacetone,

[0026] Optionally, in the embodiments of the present application, the non-metallic reducing agent includes any one of diisopropylethylamine, triethylamine and dihydropyridine,

[0027] Optionally, in the embodiments of the present application, the base includes any one of cesium carbonate, potassium acetate, sodium bicarbonate and sodium carbonate.

[0028] Optionally, in the embodiments of the present application, the specific method of the reaction includes that the reactants are sealed and placed at a distance of 1-5 cm from a 30 W blue LED under nitrogen protection, and stirred at room temperature for 10-30 hours.

[0029] Further optionally, in the embodiments of the present application, the specific method of the reaction includes that the reactants are sealed and placed at a distance of 1-2 cm from a 30 W blue LED under nitrogen protection, and stirred at room temperature for 30 hours.

[0030] Optionally, in the embodiments of the present application, the wavelength of the blue LED is 450-500 nm, preferably 460 nm.

[0031] A third object of the present application is to provide an oxazine compound containing a quaternary carbon center, which has a structural formula as shown in the following formula (4):

[0032]

[0033] wherein R represents any one of aryl, heteroaryl and olefin, R 1 represents any one of aryl, alkyl, X represents any one of Cl, Br and I, O represents oxygen atom, N represents nitrogen atom, Ph represents phenyl, Ar represents Ph or aryl or aryl derivative, R 1 represents any one of H, aryl, aryl derivative.

[0034] Optionally, in the embodiments of the present application, the oxazine Ph or the compound has any one of the following structural formulae:

[0035]

[0036] A fourth object of the present application is to provide a method for preparing an oxazine compound containing a quaternary carbon center, which comprises subjecting an allyl-containing α-quaternary carbon secondary amine compound as shown in formula (3) to halogenation cyclization reaction with a halogenating agent to obtain an oxazine compound containing a quaternary carbon center as shown in formula (4), and the reaction equation is shown as follows:

[0037]

[0038] wherein R represents any one of aryl, heteroaryl and olefin, R 1 represents any one of aryl, alkyl, X represents any one of Cl, Br and I, O represents oxygen atom, N represents nitrogen atom, H represents hydrogen atom, Ph represents phenyl, Ar represents Ph or aryl or aryl derivative, R 1 represents any one of H, aryl, aryl derivative.

[0039] Optionally, in the embodiments of the present application,

[0040]

[0041] wherein R represents any one of aryl, heteroaryl and olefin, R 1 represents any one of aryl, alkyl, Y represents any one of Cl, Br, OTs, OBz, OAc, OCO2Ph, X represents any one of Cl, Br and I.

[0042] Optionally, in the embodiments of the present application, the halogenating agent comprises any one of N-bromosuccinimide, iodine, 1,3-dichloro-5,5-dimethylhydantoin.

[0043] Optionally, in the embodiments of the present application, the molar ratio of the allyl-containing α-quaternary carbon secondary amine compound to the halogenating agent is 1:1-3.

[0044] Optionally, in the embodiments of the present application, the halogenation cyclization reaction is carried out in solvent II, and the solvent II includes any one of dichloromethane, acetonitrile.

[0045] Optionally, in the embodiments of the present application, after the reaction is tracked by thin layer chromatography, extraction is carried out with a mixed solvent of ethyl acetate and petroleum ether, followed by concentration under reduced pressure, and the indole-containing polysubstituted tetrahydrofuran compound is obtained by silica gel column chromatography.

[0046] A fifth object of the present application is to provide the use of the above-mentioned oxazine compound containing a quaternary carbon center in pharmaceuticals and agrochemicals.

[0047] Optionally, in the embodiments of the present application, the above-mentioned oxazine compound containing a quaternary carbon center can be used as a pharmaceutical compound or a prepared pharmaceutical compound. For example, alitretinoin (anxiolytic, anticonvulsant drug) also has a similar parent nucleus structure (Arab. J. Chem. 2017, 10, S747-S756; Tetrahedron Lett. 2020, 61, 151965-151972; J. Org. Chem. 2023, 88, 8636-8642).

[0048]

[0049] Optionally, in the embodiments of the present application, the oxazine compound is also used as an important nitrogen ligand in transition metal catalysis, such as a six-membered ring oxazine compound as a metal bidentate nitrogen ligand, realizing the high selectivity of palladium-catalyzed allylation of 1,3-diphenyl-2-propenyl acetate (Tetrahedron: Asymmetry 1999, 10, 1795-1802; Tetrahedron: Asymmetry 2004, 15, 155-158; Angew. Chem., Int. Ed. 2004, 43, 5255-5260; Catal. Today 2007, 121, 140-150)

[0050]

[0051] Beneficial effects: The application discloses an imine reductive allylation compound and synthesis of oxazine compounds containing a quaternary carbon center, a new method for synthesizing oxazine compounds containing a quaternary carbon center through light / palladium synergistic catalysis of imine reductive allylation reaction and halogenation cyclization reaction with a halogenation reagent.

[0052] The application has the following advantages:

[0053] (1) The application has the characteristics of mild reaction conditions, high yield and wide substrate range. It is worth mentioning that in the light / palladium synergistic catalysis reaction system, the polarity of the imine can be reversed through two consecutive single electron reduction processes to generate an alpha-amino carbon anion intermediate; the carbon anion intermediate can further act as a nucleophile to obtain the product of imine reductive allylation. Under alkaline conditions, the synthesis of oxazine compounds is realized by utilizing the nucleophilicity of the oxygen atom on the amide.

[0054] (2) The target molecule of the application has important application value in the fields of medicine and medicinal chemistry.

[0055] (3) Oxazine compounds are also important nitrogen ligands in transition metal catalysis. Therefore, the oxazine compounds containing a quaternary carbon provided by the application provide a new synthesis method and lead compounds. BRIEF DESCRIPTION OF DRAWINGS

[0056] Figure 1 It is a reaction equation schematic diagram of the application.

[0057] Figure 2 It is the nuclear magnetic resonance H spectrum of compound 3-1, N-(1,1-diphenylbut-3-en-1-yl)benzamide prepared in Example 1.

[0058] Figure 3 It is the nuclear magnetic resonance C spectrum of compound 3-1, N-(1,1-diphenylbut-3-en-1-yl)benzamide prepared in Example 1.

[0059] Figure 4 It is the nuclear magnetic resonance H spectrum of compound 4-1, 6-(iodomethyl)-2,4,4-triphenyl-5,6-dihydro-4H-1,3-oxazine (4-1) prepared in Example 2.

[0060] Figure 5The image shows the C-NMR spectrum of compound 4-1,6-(iodomethyl)-2,4,4-triphenyl-5,6-dihydro-4H-1,3-oxazine (4-1) obtained in Example 2. Detailed Implementation

[0061] First, α-quaternary carbon secondary amine compounds containing allyl groups are synthesized. The method of this invention uses the imine shown in formula (1) and the allyl electrophilic reagent shown in formula (2) as reactants, and under photocatalysis and palladium synergistic catalysis, yields α-quaternary carbon secondary amine compounds containing allyl groups in a one-step reaction. This method utilizes the two single-electron reductions of the imine to form α-amino carbanions, which then act as nucleophiles to react with allyl palladium, efficiently and selectively synthesizing linear allylated products, namely the α-quaternary carbon secondary amine compounds containing allyl groups shown in formula (3). The raw materials used in this method are simple and readily available, the reaction conditions are mild, the functional group compatibility is good, and this method enables the efficient and selective synthesis of these compounds.

[0062]

[0063] In the formula, R represents any one of aryl, heteroaryl, and olefin. 1 Y represents any one of aryl or alkyl groups, and Y represents any one of Cl, Br, OTs, OBz, OAc, and OCO2Ph.

[0064] Then, based on this, we further realize a method for preparing oxazine compounds containing quaternary carbon centers by undergoing halogenation cyclization reactions with halogenating reagents. The method of this invention first synthesizes α-quaternary carbon secondary amine compounds containing allyl groups according to the method described above. In one example, specifically, using dichloromethane as a solvent, the imine shown in 1, the allyl bromide shown in 2, and disodium eosin Y, palladium acetate, 1,4-bis(diphenylphosphine)butane, diisopropylethylamine, and sodium carbonate are reacted in a certain molar ratio to obtain the imine-reduced allylated product shown in 3. The imine-reduced allylated product shown in 3 is further subjected to a halogenation cyclization reaction with a halogenating reagent in a certain molar ratio to obtain the oxazine compound containing a quaternary carbon center shown in formula 4. Figure 1 As shown, the general reaction formula of the present invention is:

[0065]

[0066] In the formula, R represents any one of aryl, heteroaryl, and olefin. 1 Y represents any one of aryl or alkyl, Y represents any one of Cl, Br, OTs, OBz, OAc, OCO2Ph, [X] represents any one of N-bromosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, and iodine, and X represents any one of Cl, Br, and I.

[0067] Example 1

[0068] For example, to prepare N-(1,1-diphenylbut-3-en-1-yl)benzamide as shown in the following structural formula (3-1):

[0069]

[0070] N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added to a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and nitrogen was filled 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (35 μL, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain compound 3-1, i.e. pure N-(1,1-diphenylbut-3-en-1-yl)benzamide, with an isolated yield of 94%, as shown in Figure 2 、 3 The structural characterization data are as follows:

[0071] 1 H NMR (400 MHz, CDCl3) δ 7.81 (m, 2H), 7.54-7.48 (m, 1H), 7.48-7.39 (m, 6H), 7.35 (t, J = 7.6 Hz, 4H), 7.27 (t, J = 6.9 Hz, 2H), 6.98 (s, 1H), 5.70-5.60 (m, 1H), 5.24 (dd, J = 17.1, 1.4 Hz, 1H), 5.14 (dd, J = 10.1, 1.0 Hz, 1H), 3.51 (d, J = 7.1 Hz, 2H);

[0072] 13 C NMR (101 MHz, CDCl3) δ 166.26, 144.38, 135.40, 133.80, 131.51, 128.67, 128.34, 127.04, 126.89, 126.81, 119.65, 64.51, 43.56;

[0073] Exact Mass ESI-MS: calculated m / z for[C 23 H 21 NONa] + :350.1515,found:350.1502.

[0074] Example 2 Compound 3-1 was subjected to halogenation cyclization reaction with iodine to prepare compound 4-1

[0075] For example, 6-iodomethyl-2,4,4-triphenyl-5,6-dihydro-4H-1,3-oxazine as shown in the following formula (4-1) was prepared:

[0076]

[0077] S1, Synthesis of compound 3-1: same as example 1.

[0078] S2, Synthesis of compound 4-1: a new dry Schlenk tube (10 mL) was connected to a vacuum tube, and nitrogen was filled 3 times, and then 1 mL of acetonitrile dissolved compound 3-1 was added under nitrogen atmosphere, and then 1 mL of acetonitrile dissolved iodine (50.8 mg, 0.2 mmol) and p-toluenesulfonyl chloride sodium (chloramine T) (55.5 mg, 0.2 mmol) were added, and chloramine T played the role of oxidant in the reaction, and the reaction was carried out at room temperature for 24 hours, and thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 4-1, which was 6-iodomethyl-2,4,4-triphenyl-5,6-dihydro-4H-1,3-oxazine, with an isolation yield of 82%, as shown in Figure 4 、 5 The structural characterization data are as follows:

[0079] 1 H NMR (400 MHz, CDC13) δ 8.29 - 8.14 (m, 2H), 7.64 (d, J = 7.4 Hz, 2H), 7.53 - 7.37 (m, 5H), 7.37 - 7.25 (m, 4H), 7.20 (dt, J = 14.4, 7.3 Hz, 2H), 4.04 - 3.97 (m, 1H), 3.44 - 3.35 (m, 2H), 3.09 (dd, J = 13.3, 2.3 Hz, 1H), 2.16 (dd, J = 13.1, 11.9 Hz, 1H);

[0080] 13C NMR (101 MHz, CDC13) δ 153.55, 148.18, 147.12, 133.41, 130.79, 128.51, 128.27, 128.13, 127.67, 126.64, 126.54, 126.45, 70.93, 61.80, 39.59, 8.12;

[0081] Exact Mass ESI-MS: calculateed m / z for [C 23 H 20 INOH] + : 454.0662, found: 454.0668.

[0082] Example 3: Compound 3-1 was subjected to bromo-cyclization reaction with N-bromosuccinimide to prepare compound 4-2

[0083] For example, 6-bromomethyl-2,4,4-triphenyl-5,6-dihydro-4H-l,3-oxazine as shown in the following formula (4-2) was prepared:

[0084]

[0085] S1, Synthesis of compound 3-1: same as example 1.

[0086] S2, Synthesis of compound 4-2: a new dry Schlenk tube (10 mL) was connected to a vacuum tube, and nitrogen was filled 3 times. Compound 3-1 dissolved in 3 mL of dichloromethane was added under nitrogen atmosphere, then 3 mL of N-bromosuccinimide (NBS) dissolved in dimethyl sulfoxide (0.1079 g, 0.6 mmol) was added, and the reaction was carried out at room temperature for 24 hours. Thin layer chromatography was used to track the reaction. After the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 4-2, i.e. 6-bromomethyl-2,4,4-triphenyl-5,6-dihydro-4H-l,3-oxazine, with an isolation yield of 85%, and the structure characterization data as follows:

[0087] 1 H NMR (400 MHz, CDC13) δ 8.24 - 8.12 (m, 2H), 7.68 - 7.60 (m, 2H), 7.52 - 7.36 (m, 5H), 7.30 (dt, J = 18.0, 7.7 Hz, 4H), 7.19 (d, J = 11.9 Hz, 2H), 4.26 - 4.19 (m, 1H), 3.57 (d, J = 5.3 Hz, 2H), 3.03 (dd, J = 13.4, 2.4 Hz, 1H), 2.22 (dd, J = 13.3, 11.9 Hz, 1H).

[0088] 13 C NMR (101 MHz, CDC13) δ 153.32, 148.20, 147.03, 133.43, 130.75, 128.49, 128.23, 128.09, 127.60, 126.61, 126.53, 126.43, 70.98, 61.53, 37.82, 34.45;

[0089] Exact Mass ESI-MS: calculateed m / z for [C 23 H 20 BrNOH] + : 406.0801, found: 406.0789.

[0090] Example 4 Compound 3-1 was subjected to chloro-cyclization reaction with 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) to prepare compound 4-3

[0091] For example, 6-iodomethyl-2,4,4-triphenyl-5,6-dihydro-4H-l,3-oxazine as shown in the following formula (4-1-3) was prepared:

[0092]

[0093] S1, Synthesis of compound 3-1: same as Example 1.

[0094] S2, Synthesis of compound 4-3: a new dry Schlenk tube (10 mL) was connected to a vacuum tube, and nitrogen was filled 3 times. Compound 3-1 dissolved in 2 mL of dichloromethane was added under nitrogen atmosphere, and then triphenyl phosphine oxide (0.6 mg, 0.002 mmol), dichlorosulfoxide (9 μL, 0.12 mmol), 1,3-dichloro-5,5-dimethylhydantoin (41.4 mg, 0.21 mmol) were further added. Dichlorosulfoxide and 1,3-dichloro-5,5-dimethylhydantoin were used as chlorine source in the reaction, and triphenyl phosphine oxide was used as catalyst. Then the reaction was stirred at room temperature for 24 hours in the reaction tube. Thin layer chromatography was used to track the reaction. After the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 4-3, i.e. 6-chloromethyl-2,4,4-triphenyl-5,6-dihydro-4H-l,3-oxazine, with an isolation yield of 82%, and the structure characterization data as follows:

[0095] 1H NMR (400 MHz, CDC13) δ 8.29 - 8.14 (m, 2H), 7.64 (d, J = 7.4 Hz, 2H), 7.53 - 7.37 (m, 5H), 7.37 - 7.25 (m, 4H), 7.20 (dt, J = 14.4, 7.3 Hz, 2H), 4.04 - 3.97 (m, 1H), 3.44 - 3.35 (m, 2H), 3.09 (dd, J = 13.3, 2.3 Hz, 1H), 2.16 (dd, J = 13.1, 11.9 Hz, 1H);

[0096] 13 C NMR (101 MHz, CDC13) δ 153.55, 148.18, 147.12, 133.41, 130.79, 128.51, 128.27, 128.13, 127.67, 126.64, 126.54, 126.45, 70.93, 61.80, 39.59, 8.12;

[0097] Exact Mass ESI-MS: calculateed m / z for [C 23 H 20 INOH] + : 454.0662, found: 454.0668.

[0098] Example 5

[0099] To prepare N-(1-phenyl-1-p-tolyl)but-3-en-1-yl)benzamide as shown in the following structural formula of formula (3-2):

[0100]

[0101] Synthesis of compound 3-2: N-phenyl(p-tolyl)methylene)benzamide (59.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (35 μL, 0.4 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain compound 3-2, i.e. pure N-(1-phenyl-1-p-tolyl)but-3-en-1-yl)benzamide, with an isolated yield of 81%, and the structure characterization data as follows:

[0102] 1 H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 7.3 Hz, 2H), 7.53-7.47 (m, 1H), 7.46-7.35 (m, 4H), 7.35-7.22 (m, 5H), 7.13 (d, J = 7.9 Hz, 2H), 6.93 (s, 1H), 5.69-5.59 (m, 1H), 5.20 (d, J = 17.0 Hz, 1H), 5.10 (d, J = 10.2 Hz, 1H), 3.47 (d, J = 7.0 Hz, 2H), 2.32 (s, 3H);

[0103] 13 C NMR (101 MHz, CDCl3) δ 166.25, 144.53, 141.51, 136.62, 135.43, 133.91, 131.48, 129.06, 128.65, 128.31, 126.95, 126.89, 126.73, 126.68, 119.55, 64.30, 43.49, 21.01;

[0104] Exact Mass ESI-MS: calculated m / z for [C 24 H 23 NONa] + : 364.1672, found: 364.1662.

[0105] Example 6

[0106] To prepare N-(l-(4-tert-butyl)phenyl-l-phenylbut-3-en-l-yl)benzamide as shown in the following formula (3-3):

[0107]

[0108] Synthesis of compound 3-3: N-((4-(tert-butyl)phenyl)(phenyl)methylene)benzamide (68.2 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added to a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and filled with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (35 μL, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-3, N-(l-(4-tert-butyl)phenyl-l-phenylbut-3-en-l-yl)benzamide, with an isolated yield of 85%, and the structure characterization data as follows:

[0109] 1 H NMR (400 MHz, CDC13) δ 7.79 (d, J = 7.2 Hz, 2H), 7.52 - 7.48 (m, 1H), 7.42 (dd, J = 16.2, 7.9 Hz, 4H), 7.32 (q, J = 8.5 Hz, 6H), 7.25 - 7.22 (m, 1H), 6.91 (s, 1H), 5.71 - 5.61 (m, 1H), 5.21 (d, J = 17.1 Hz, 1H), 5.11 (d, J = 10.2 Hz, 1H), 3.53 - 3.43 (m, 2H), 1.30 (s, 9H);

[0110] 13C NMR (101 MHz, CDC13) δ 166.27, 149.68, 144.67, 141.20, 135.47, 133.98, 131.43, 128.62, 128.24, 126.87, 126.73, 126.35, 125.26, 119.45, 64.30, 43.36, 34.39, 31.32;

[0111] Exact Mass ESI-MS: calculated m / z for [C 27 H 29 NONa] + : 406.2141, found: 406.2137.

[0112] Example 7

[0113] To prepare N-(1-(1,1'-biphenyl)-4-yl)-1-phenylbut-3-en-1-yl)benzamide as shown in the structural formula of formula (3-4):

[0114]

[0115] Synthesis of compound 3-4: N-(1,1'-biphenyl]-4-yl(phenyl)methylene)benzamide (72.2 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-4, N-(1-(1,1'-biphenyl)-4-yl)-1-phenylbut-3-en-1-yl)benzamide, with an isolated yield of 95%, and the structural characterization data as follows:

[0116] 1H NMR (400 MHz, CDC13) δ 7.81 (d, J = 7.3 Hz, 2H), 7.57 (t, J = 7.4 Hz, 4H), 7.50 (d, J = 7.1 Hz, 1H), 7.48 - 7.38 (m, 8H), 7.38 - 7.30 (m, 3H), 7.27 (d, J = 6.9 Hz, 1H), 6.97 (s, 1H), 5.68 (dt, J = 16.7, 9.5 Hz, 1H), 5.24 (d, J = 17.0 Hz, 1H), 5.14 (d, J = 10.0 Hz, 1H), 3.57 - 3.45 (m, 2H);

[0117] 13 C NMR (101 MHz, CDC13) δ 166.33, 144.23, 143.41, 140.57, 139.73, 135.33, 133.77, 131.58, 128.77, 128.70, 128.42, 127.30, 127.28, 127.13, 127.07, 127.02, 126.92, 126.81, 119.80, 64.37, 43.69;

[0118] Exact Mass ESI-MS: calcd m / z for [C 29 H 25 NONa] + : 426.1828, found: 426.1828.

[0119] Example 8

[0120] To prepare N-(l-phenyl-l-p-tolyl)but-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-5):

[0121]

[0122] Synthesis of compound 3-5: N-(4-methoxyphenyl)(phenyl)methylene)benzamide (63.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (35 μL, 0.4 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-5, i.e. N-(1-phenyl-1-p-tolyl)but-3-en-1-yl)benzamide, with an isolated yield of 83%, and the following structure characterization data:

[0123] 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 7.5 Hz, 2H), 7.53-7.48 (m, 1H), 7.43 (t, J = 7.4 Hz, 2H), 7.40-7.27 (m, 6H), 7.26-7.23 (m, 1H), 6.91 (s, 1H), 6.86 (d, J = 8.6 Hz, 2H), 5.63 (td, J = 16.9, 8.5 Hz, 1H), 5.21 (d, J = 16.9 Hz, 1H), 5.11 (d, J = 10.0 Hz, 1H), 3.78 (s, 3H), 3.45 (d, J = 6.4 Hz, 2H);

[0124] 13 C NMR (101 MHz, CDCl3) δ 166.24, 158.34, 144.56, 136.53, 135.40, 133.91, 131.47, 128.64, 128.28, 128.07, 126.95, 126.86, 126.74, 119.54, 113.57, 64.09, 55.21, 43.82;

[0125] Exact Mass ESI-MS: calculated m / z for [C 24 H 23 NO2Na] +: 380.1621, found: 380.1614.

[0126] Example 9

[0127] To prepare N-(l-phenyl-l-(4-trifluoromethyl)phenyl)but-3-en-l-yl)benzamide as shown in structural formula (3-6) for example:

[0128]

[0129] Synthesis of compound 3-6: N-phenyl(4-(trifluoromethyl)phenyl)methylene)benzamide (70.6 mg, 0.2 mmol), Eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum line and purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-6, N-(l-phenyl-l-(4-trifluoromethyl)phenyl)but-3-en-l-yl)benzamide, with an isolated yield of 84%, and the structural characterization data as follows:

[0130] 1 H NMR (400 MHz, CDC13) δ 7.79 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.56 - 7.50 (m, 3H), 7.45 (t, J = 7.6 Hz, 2H), 7.36 (d, J = 4.2 Hz, 4H), 7.29 (dd, J = 8.7, 4.2 Hz, 1H), 6.95 (s, 1H), 5.65 - 5.55 (m, 1H), 5.25 (d, J = 17.1 Hz, 1H), 5.16 (d, J = 10.1 Hz, 1H), 3.51 (dd, J = 14.0, 7.6 Hz, 1H), 3.41 (dd, J = 14.0, 6.6 Hz, 1H);

[0131] 13C NMR (101 MHz, CDC13) δ 166.33, 148.39 (d, J = 1.3 Hz), 143.12, 134.93, 133.13, 131.74, 129.04 (q, J = 32.4 Hz), 128.74, 128.60, 127.48, 127.30, 126.86, 126.86, 126.72, 125.21 (q, J = 3.7 Hz), 124.12 (q, J = 272.2 Hz), 122.82, 120.27, 64.30, 43.81;

[0132] 19 F NMR (564 MHz, CDC13) δ -62.45;

[0133] Exact Mass ESI-MS: calculated m / z for [C 24 H 20 F3NONa] + : 418.1389, found: 418.1388.

[0134] Example 10

[0135] To prepare N-(l-phenyl-l-(4-trifluoromethoxy)phenyl)but-3-en-l- yl)benzamide, as shown in structure (3-7):

[0136]

[0137] Synthesis of compound 3-7: N-(phenyl(4-(trifluoromethoxy)phenyl)methylene)benzamide (73.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-7, N-(1-phenyl-1-(4-trifluoromethoxy)phenyl)but-3-en-1-yl)benzamide, with an isolated yield of 95%, and the structure characterization data as follows:

[0138] 1 H NMR (400 MHz, CDCl3) δ 7.82-7.75 (m, 2H), 7.52 (t, J = 7.3 Hz, 1H), 7.48-7.41 (m, 4H), 7.36 (d, J = 4.2 Hz, 4H), 7.28 (dd, J = 8.4, 4.1 Hz, 1H), 7.16 (d, J = 8.3 Hz, 2H), 6.92 (s, 1H), 5.65-5.56 (m, 1H), 5.28-5.22 (m, 1H), 5.15 (d, J = 10.2 Hz, 1H), 3.49-3.37 (m, 2H);

[0139] 13 C NMR (101 MHz, CDCl3) δ 166.30, 147.97 (q, J = 1.8 Hz), 143.50, 142.94, 135.07, 133.34, 131.66, 128.71, 128.50, 127.34, 126.85, 126.75, 120.47 (q, J = 257.1 Hz), 120.41, 120.09, 120.06 (q, J = 2.3 Hz), 64.10, 44.13;

[0140] 19 F NMR (564 MHz, CDCl3) δ -57.66;

[0141] Exact Mass ESI-MS: calculated m / z for[C 24 H 20 F3NO2Na] + :434.1338, found:434.1342.

[0142] Example 11

[0143] To prepare N-(l-(4-cyanophenyl)-l-phenylbut-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-8):

[0144]

[0145] Synthesis of compound 3-8: N-((4-cyanophenyl)(phenyl)methylene)benzamide (62.0 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum line and purged with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-8, N-(l-(4-cyanophenyl)-l-phenylbut-3-en-l-yl)benzamide, with an isolation yield of 74%, and the structural characterization data as follows:

[0146] 1 H NMR (400 MHz, CDC13) δ 7.78 (d, J = 7.4 Hz, 2H), 7.61 (d, J = 8.3 Hz, 2H), 7.53 (d, J = 8.3 Hz, 3H), 7.46 (t, J = 7.4 Hz, 2H), 7.41 - 7.27 (m, 5H), 6.96 (s, 1H), 5.57 (dt, J = 16.8, 7.8 Hz, 1H), 5.26 (d, J = 16.9 Hz, 1H), 5.17 (d, J = 10.1 Hz, 1H), 3.47 (dd, J = 13.9, 8.0 Hz, 1H), 3.37 (dd, J = 13.8, 6.0 Hz, 1H);

[0147] 13 C NMR (101 MHz, CDC13) δ 166.42, 149.91, 142.38, 134.64, 132.84, 132.03, 131.89, 128.78, 128.75, 127.76, 127.69, 126.89, 126.70, 120.59, 118.83, 110.67, 64.32, 43.75;

[0148] Exact Mass ESI-MS: calculated m / z for [C 24 H 20 N2ONa] + : 375.1468, found: 375.1465.

[0149] Example 12

[0150] To prepare N-(1-(4-fluorophenyl)-1-phenylbut-3-en-1-yl)benzamide as shown in the following structural formula of formula (3-9):

[0151]

[0152] Synthesis of compound 3-9: N-(4-fluorophenyl)methylene)benzamide (60.6 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-9, N-(1-(4-fluorophenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolated yield of 98%, and the structural characterization data as follows:

[0153] 1H NMR (400 MHz, CDC13) δ 7.78 (d, J = 7.4 Hz, 2H), 7.54 - 7.49 (m, 1H), 7.47 - 7.40 (m, 2H), 7.40 - 7.30 (m, 6H), 7.29 - 7.25 (m, 1H), 7.01 (t, J = 8.6 Hz, 2H), 6.92 (s, 1H), 5.66 - 5.56 (m, 1H), 5.23 (d, J = 16.3 Hz, 1H), 5.14 (d, J = 10.2 Hz, 1H), 3.50 - 3.37 (m, 2H);

[0154] 13 C NMR (101 MHz, CDC13) δ 166.25, 161.60 (d, J = 246.2 Hz), 143.87, 140.15 (d, J = 3.3 Hz), 135.17, 133.54, 131.62, 128.71 (d, J = 7.9 Hz), 128.70, 128.43, 127.23, 126.86, 126.75, 119.95, 115.02 (d, J = 21.3 Hz), 64.06, 44.18;

[0155] 19 F NMR (564 MHz, CDC13) δ -115.85;

[0156] Exact Mass ESI-MS: calculated m / z for [C 23 H 20 FNONa] + : 368.1421, found: 368.1413.

[0157] Example 13

[0158] To prepare N-(l-(4-chlorophenyl)-l-phenylbut-3-en-l-yl)benzamide of the following structural formula shown as formula (3-10):

[0159]

[0160] Synthesis of compound 3-10: N-(4-chlorophenyl)(phenyl)methylene)benzamide (63.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-10, N-(1-(4-chlorophenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolated yield of 94%, and the structure characterization data as follows:

[0161] 1 H NMR (400 MHz, CDCl3) δ 7.77 (m, 2H), 7.59-7.48 (m, 1H), 7.48-7.41 (m, 2H), 7.38-7.32 (m, 6H), 7.31-7.25 (m, 3H), 6.91 (s, 1H), 5.66-5.55 (m, 1H), 5.25-5.20 (m, 1H), 5.16-5.11 (m, 1H), 3.49-3.35 (m, 2H);

[0162] 13 C NMR (101 MHz, CDCl3) δ 166.26, 143.54, 142.96, 135.06, 133.39, 132.78, 131.66, 128.71, 128.48, 128.42, 128.36, 127.31, 126.86, 126.72, 120.07, 64.08, 43.94;

[0163] Exact Mass ESI-MS: calculated m / z for [C 23 H 20 ClNONa] + : 384.1126, found: 384.1127.

[0164] Example 14

[0165] N-(1-phenyl-1-m-tolyl)but-3-en-1-yl)benzamide as shown in the following structural formula (3-11) is prepared as an example:

[0166]

[0167] Synthesis of compound 3-11: N-(phenyl-m-tolyl)methylene)benzamide (59.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and filled with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-11, N-(1-phenyl-1-m-tolyl)but-3-en-1-yl)benzamide, with an isolated yield of 83%, and the structural characterization data as follows:

[0168] 1 H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.9 Hz, 2H), 7.51 (t, J = 7.0 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.39 (d, J = 7.8 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.27-7.16 (m, 4H), 7.07 (s, 1H), 6.93 (s, 1H), 5.70-5.59 (m, 1H), 5.21 (d, J = 17.1 Hz, 1H), 5.10 (d, J = 10.1 Hz, 1H), 3.48 (d, J = 7.1 Hz, 2H), 2.32 (s, 3H);

[0169] 13C NMR (101 MHz, CDC13) δ 166.24, 144.51, 144.39, 137.85, 135.49, 133.90, 131.46, 128.65, 128.30, 128.22, 127.84, 127.38, 126.95, 126.89, 126.73, 123.85, 119.52, 64.45, 43.34, 21.82;

[0170] Exact Mass ESI-MS: calculateed m / z for [C 24 H 23 NONa] + :364.1672, found:364.1662.

[0171] Example 15

[0172] N-(1-(3-chlorophenyl)-1-phenylbut-3-en-1-yl)benzamide was prepared as follows:

[0173]

[0174] Synthesis of compound 3-12: N-(3-chlorophenyl)(phenyl)methylene)benzamide (63.8 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-12, N-(1-(3-chlorophenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolation yield of 83%, and the structure characterization data as follows:

[0175] 1H NMR (400 MHz, CDC13) δ 7.79 (d, J = 7.6 Hz, 2H), 7.55 - 7.49 (m, 1H), 7.45 (t, J = 7.5 Hz, 2H), 7.40 - 7.32 (m, 5H), 7.32 - 7.21 (m, 4H), 6.91 (s, 1H), 5.60 (dt, J = 17.0, 9.8 Hz, 1H), 5.23 (d, J = 17.1 Hz, 1H), 5.14 (d, J = 10.1 Hz, 1H), 3.53 - 3.34 (m, 2H);

[0176] 13 C NMR (101 MHz, CDC13) δ 166.26, 146.59, 143.38, 135.07, 134.24, 133.27, 131.66, 129.47, 128.71, 128.53, 127.35, 127.21, 127.12, 126.87, 126.67, 125.18, 120.10, 64.18, 43.67;

[0177] Exact Mass ESI-MS: calcd m / z for [C 23 H 20 ClNONa] + : 384.1126, found: 384.1120.

[0178] Example 16

[0179] To prepare N-(l-phenyl-l-o-tolyl)but-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-13):

[0180]

[0181] Synthesis of compound 3-13: N-(phenyl(o-tolyl)methylene)benzamide (59.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (140 μL, 0.8 mmol) and allyl bromide (70 μL, 0.8 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 48 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-13, N-(1-phenyl-1-o-tolyl)but-3-en-1-yl)benzamide, with an isolated yield of 73%, and the structure characterization data as follows:

[0182] 1 H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 7.7 Hz, 3H), 7.52-7.47 (m, 1H), 7.43 (t, J = 7.3 Hz, 2H), 7.34-7.28 (m, 3H), 7.27-7.24 (m, 1H), 7.20 (t, J = 8.5 Hz, 3H), 7.07 (d, J = 7.3 Hz, 1H), 7.00 (s, 1H), 5.57 (dt, J = 17.1, 8.5 Hz, 1H), 5.07-4.99 (m, 2H), 3.96 (dd, J = 13.2, 7.6 Hz, 1H), 3.15 (dd, J = 13.2, 6.6 Hz, 1H), 1.93 (s, 3H);

[0183] 13 C NMR (101 MHz, CDCl3) δ 165.65, 144.12, 142.28, 135.94, 135.32, 133.60, 132.79, 131.43, 128.71, 128.34, 127.73, 127.45, 127.06, 126.79, 125.82, 125.58, 119.22, 64.47, 43.25, 22.12;

[0184] Exact Mass ESI-MS: calculated m / z for [C 24 H23 NONa] + :364.1672, found:364.1663.

[0185] Example 17

[0186] To prepare N-(1-(2-methoxyphenyl)-1-phenylbut-3-en-1-yl)benzamide as shown in the following formula (3-14):

[0187]

[0188] Synthesis of compound 3-14: N-(2-methoxyphenyl)(phenyl)methylidene)benzamide (63.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). The Schlenk tube was connected to a vacuum tube and was purged with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (140 μL, 0.8 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm) and stirred at room temperature for 48 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-14, N-(1-(2-methoxyphenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolation yield of 76%, and the structural characterization data as follows:

[0189] 1 H NMR (400 MHz, CDCl3) δ 7.91-7.68 (m, 3H), 7.55-7.12 (m, 10H), 7.05-6.95 (m, 1H), 6.92-6.82 (m, 1H), 5.71-5.58 (m, 1H), 5.12-4.94 (m, 2H), 3.97-3.85 (m, 1H), 3.53 (s, 3H), 3.32 (dd, J = 12.8, 7.1 Hz, 1H);

[0190] 13C NMR (101 MHz, CDC13) δ 166.43, 157.09, 145.80, 136.06, 134.01, 132.75, 131.13, 128.85, 128.72, 128.52, 127.87, 126.85, 126.50, 125.91, 120.82, 118.28, 112.84, 64.40, 55.72, 42.30;

[0191] Exact Mass ESI-MS: calculated m / z for [C 24 H 23 NO2Na] + : 380.1621, found: 380.1616.

[0192] Example 18

[0193] To prepare N-(1-(2-fluorophenyl)-1-phenylbut-3-en-1-yl)benzamide as shown in the following formula (3-15):

[0194]

[0195] Synthesis of compound 3-15: N-(2-fluorophenyl)(phenyl)methylene)benzamide (60.6 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-15, N-(1-(2-fluorophenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolation yield of 93%, and the structure characterization data as follows:

[0196] 1H NMR (400 MHz, CDC13) δ 7.78 (d, J = 8.0 Hz, 2H), 7.57 - 7.47 (m, 2H), 7.43 (t, J = 7.6 Hz, 2H), 7.37 - 7.24 (m, 6H), 7.17 (t, J = 7.6 Hz, 1H), 7.12 (s, 1H), 6.98 (dd, J = 12.5, 8.1 Hz, 1H), 5.63 - 5.53 (m, 1H), 5.15 (d, J = 17.0 Hz, 1H), 5.08 (d, J = 10.1 Hz, 1H), 3.84 (dd, J = 13.8, 7.2 Hz, 1H), 3.26 (dd, J = 13.8, 6.9 Hz, 1H);

[0197] 13 C NMR (101 MHz, CDC13) δ 166.48, 160.43 (d, J = 247.1 Hz), 143.38, 135.35, 133.26, 131.48, 131.41 (d, J = 9.7 Hz), 129.32 (d, J = 1.3 Hz), 129.26 (d, J = 3.8 Hz), 128.64, 128.32, 127.30, 126.91, 126.16, 123.84 (d, J = 3.3 Hz), 119.53, 116.53 (d, J = 23.3 Hz), 63.07, 42.76 (d, J = 1.3 Hz);

[0198] 19 F NMR (564 MHz, CDC13) δ -109.71;

[0199] Exact Mass ESI-MS: calculated m / z for [C 24 H 20 FNONa] + : 368.1421, found: 368.1416.

[0200] Example 19

[0201] N-(1-(2-chlorophenyl)-1-phenylbut-3-en-1-yl)benzamide was prepared according to the following scheme (3-16):

[0202]

[0203] Synthesis of compound 3-16: N-(2-fluorophenyl)(phenyl)methylene)benzamide (63.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-16, N-(1-(2-chlorophenyl)-1-phenylbut-3-en-1-yl)benzamide, with an isolated yield of 98%, and the following structure characterization data:

[0204] 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 7.9 Hz, 1H), 7.81 (d, J = 7.5 Hz, 2H), 7.52-7.47 (m, 1H), 7.43 (t, J = 7.4 Hz, 2H), 7.40-7.31 (m, 4H), 7.30-7.23 (m, 3H), 7.17 (d, J = 7.6 Hz, 2H), 5.62-5.50 (m, 1H), 5.09-4.98 (m, 2H), 4.17 (dd, J = 13.2, 7.5 Hz, 1H), 3.08 (dd, J = 13.2, 6.7 Hz, 1H);

[0205] 13 C NMR (101 MHz, CDCl3) δ 166.22, 143.43, 141.30, 135.31, 133.23, 133.09, 131.81, 131.40, 129.87, 128.78, 128.62, 128.30, 127.09, 126.92, 126.43, 125.74, 119.25, 64.27, 42.99;

[0206] Exact Mass ESI-MS: calculated m / z for [C 23 H 20 ClNONa] +: 384.1126, found: 384.1121.

[0207] Example 20

[0208] N-(1-benzo[d][1,3]dioxol-5-yl)-1-phenylbut-3-en-1-yl)benzamide as shown in (3-17) is prepared as follows:

[0209]

[0210] S1, Synthesis of compound 3-17: N-(benzo[d][1,3]dioxol-5-yl(phenyl)methylene)benzamide (65.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-17, N-(1-benzo[d][1,3]dioxol-5-yl)-1-phenylbut-3-en-1-yl)benzamide, with an isolated yield of 86%, and the structure characterization data as follows:

[0211] 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 7.2 Hz, 2H), 7.53-7.48 (m, 1H), 7.43 (t, J = 7.3 Hz, 2H), 7.40-7.28 (m, 4H), 7.28-7.23 (m, 1H), 6.98-6.82 (m, 3H), 6.76 (d, J = 8.1 Hz, 1H), 5.92 (s, 2H), 5.64 (dq, J = 16.9, 7.1 Hz, 1H), 5.21 (d, J = 17.1 Hz, 1H), 5.11 (d, J = 10.1 Hz, 1H), 3.51-3.36 (m, 2H);

[0212] 13C NMR (101 MHz, CDC13) δ 166.23, 147.72, 146.40, 144.30, 138.65, 135.31, 133.75, 131.53, 128.66, 128.36, 127.08, 126.86, 126.63, 120.04, 119.65, 107.81, 107.77, 101.13, 64.33, 43.68;

[0213] Exact Mass ESI-MS: calculated m / z for [C 24 H 21 NO3Na] + : 394.1414, found: 394.1410.

[0214] S2, Synthesis of compound 4-4: A new dry Schlenk tube (10 mL) was connected to a vacuum line, purged with nitrogen 3 times, 1 mL of acetonitrile dissolved above crude product 3-1 was added under nitrogen atmosphere, then 1 mL of acetonitrile dissolved iodine (50.8 mg, 0.2 mmol) and p-toluenesulfonyl chloride sodium (chloramine T) (55.5 mg, 0.2 mmol) were added, chloramine T played the role of oxidant in the reaction, the reaction was carried out at room temperature for 24 hours, thin layer chromatography was used to track the reaction, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 4-4, i.e. 4-(benzo[d][l,3]dioxol-5-yl)-6-(iodomethyl)-2,4-diphenyl-5,6-dihydro-4H-l,3-oxazine, with an isolation yield of 71%, and the following structure characterization data:

[0215] 1 H NMR (600 MHz, CDC13) δ 8.17 (s, 2H), 7.62 (d, J = 4.4 Hz, 2H), 7.44 (d, J = 24.8 Hz, 3H), 7.33 (s, 2H), 7.20 (s, 1H), 6.91 - 6.81 (m, 2H), 6.72 (d, J = 6.3 Hz, 1H), 5.89 (d, J = 8.4 Hz, 2H), 4.05 (d, J = 5.3 Hz, 1H), 3.39 (s, 2H), 3.01 (d, J = 13.3 Hz, 1H), 2.11 (t, J = 12.0 Hz, 1H).

[0216] 13C NMR (151 MHz, CDC13) δ 153.5, 148.2, 147.8, 146.2, 141.3, 133.3, 130.8, 128.3, 128.1, 127.7, 126.6, 126.3, 119.4, 107.9, 107.6, 101.1, 71.0, 61.5, 39.7, 7.9.

[0217] HRMS (ESI-TOF) m / z: [M + H] + Calcd for C 24 H 21 INO3 498.0561; found 498.0557.

[0218] Example 21

[0219] To prepare N-(l-(naphthalen-2-yl)-l-phenylbut-3-en-l-yl)benzamide as shown in the following formula (3-18):

[0220]

[0221] Synthesis of compound 3-18: N-(naphthalen-2-yl(phenyl)methylene)benzamide (67.1 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-18, N-(l-(naphthalen-2-yl)-l-phenylbut-3-en-l-yl)benzamide, with an isolated yield of 88%, and the structure characterization data as follows:

[0222] 1H NMR (400 MHz, CDC13) δ 8.00 - 7.59 (m, 6 H), 7.58 - 7.12 (m, 11 H), 7.05 (s, 1 H), 5.66 (s, 1 H), 5.24 (d, J = 16.1 Hz, 1 H), 5.13 (s, 1 H), 3.60 (d, J = 33.0 Hz, 2 H);

[0223] 13 C NMR (101 MHz, CDC13) δ 166.37, 144.20, 141.76, 135.42, 133.78, 132.38, 131.58, 128.73, 128.42, 128.19, 127.49, 127.18, 126.95, 126.92, 126.20, 126.15, 125.41, 125.34, 119.76, 64.64, 43.45;

[0224] Exact Mass ESI-MS: calculated m / z for [C 27 H 20 NONa] + : 400.1672, found: 400.1669.

[0225] Example 22

[0226] To prepare N-(l-phenyl-l-thiophen-2-yl)but-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-19):

[0227]

[0228] Synthesis of compound 3-19: N-(phenyl(thiophen-2-yl)methylene)benzamide (58.2 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-19, N-(1-phenyl-1-thiophen-2-yl)but-3-en-1-yl)benzamide, with an isolated yield of 59%, and the structure characterization data as follows:

[0229] 1 H NMR (400 MHz, CDC13) δ 7.79 (d, J = 7.4 Hz, 2H), 7.54 - 7.48 (m, 1H), 7.43 (dd, J = 13.6, 7.4 Hz, 4H), 7.34 (t, J = 7.4 Hz, 2H), 7.28 (d, J = 6.9 Hz, 1H), 7.23 (d, J = 4.9 Hz, 1H), 7.06 (d, J = 2.8 Hz, 1H), 6.99 - 6.87 (m, 2H), 5.75 (dq, J = 17.0, 7.3 Hz, 1H), 5.26 (d, J = 17.1 Hz, 1H), 5.18 (d, J = 10.0 Hz, 1H), 3.45 (m, 2H);

[0230] 13 C NMR (101 MHz, CDC13) δ 166.16, 149.79, 143.94, 135.11, 133.34, 131.61, 128.67, 128.32, 127.33, 126.90, 126.41, 126.16, 125.56, 124.75, 120.15, 62.71, 45.55;

[0231] Exact Mass ESI-MS: calculated m / z for [C 21 H 19 NOSNa] +:356.1080, found: 356.1070.

[0232] Example 23

[0233] To prepare N-(l-(furan-2-yl)-l-phenylbut-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-20):

[0234]

[0235] Synthesis of compound 3-20: N-(furan-2-yl(phenyl)methylene)benzamide (55.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-20, N-(l-(furan-2-yl)-l-phenylbut-3-en-l-yl)benzamide, with an isolated yield of 53%, and the structural characterization data as follows:

[0236] 1 H NMR (400 MHz, CDC13) δ 7.79 (d, J = 7.3 Hz, 2H), 7.50 (d, J = 6.9 Hz, 1H), 7.47 - 7.30 (m, 7H), 7.27 (t, 1H), 6.95 (s, 1H), 6.32 (d, J = 31.0 Hz, 2H), 5.68 (dq, J = 16.5, 7.4 Hz, 1H), 5.24 (d, J = 17.1 Hz, 1H), 5.15 (d, J = 10.1 Hz, 1H), 3.43 (dd, J = 13.5, 6.7 Hz, 1H), 3.34 (dd, J = 13.6, 7.4 Hz, 1H);

[0237] 13C NMR (101 MHz, CDC13) δ 166.16, 155.91, 142.46, 141.67, 135.05, 133.34, 131.56, 128.62, 128.34, 127.35, 126.92, 126.10, 119.79, 110.42, 108.03, 61.28, 43.35;

[0238] Exact Mass ESI-MS: calculated m / z for [C 21 H 19 NO2Na] + : 340.1308, found: 340.1308.

[0239] Example 24

[0240] To prepare N-(l-phenyl-l-thiophen-3-yl)but-3-en-l-yl)benzamide as shown in the following structural formula of formula (3-21):

[0241]

[0242] Synthesis of compound 3-21: N-(phenyl(thiophen-3-yl)methylene)benzamide (58.2 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (140 μL, 0.8 mmol) and allyl bromide (70 μL, 0.8 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 48 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-21, N-(l-phenyl-l-thiophen-3-yl)but-3-en-l-yl)benzamide, with an isolated yield of 70%, and the structural characterization data as follows:

[0243] 1H NMR (400 MHz, CDC13) δ 7.78 (d, J = 5.0 Hz, 2H), 7.53 - 7.17 (m, 10H), 7.05 (s, 1H), 6.89 (s, 1H), 5.74 - 5.61 (m, 1H), 5.25 (d, J = 17.1 Hz, 1H), 5.16 (d, J = 9.4 Hz, 1H), 3.39 (d, J = 3.7 Hz, 2H);

[0244] 13 C NMR (101 MHz, CDC13) δ 166.11, 145.77, 143.98, 135.25, 133.73, 131.53, 128.65, 128.30, 127.23, 127.11, 126.86, 126.34, 125.67, 121.96, 119.80, 62.43, 44.76;

[0245] Exact Mass ESI-MS: calcd m / z for [C 21 H 19 NOSNa] + : 356.1080, found: 356.1084

[0246] Example 25

[0247] To prepare N-(l, l-diphenylbut-3-en-l-yl)-4-trifluoromethylbenzamide as shown in the following structural formula of formula (3-22):

[0248]

[0249] Synthesis of compound 3-22: N-diphenylmethylene-4-trifluoromethylbenzamide (69.8 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the pure compound 3-22, N-(1,1-diphenylbut-3-en-1-yl)-4-trifluoromethylbenzamide, with an isolated yield of 85%, and the structure characterization data as follows:

[0250] 1 H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.8 Hz, 2H), 7.70 (d, J = 7.9 Hz, 2H), 7.36 (q, J = 7.9 Hz, 8H), 7.29-7.25 (m, 2H), 6.95 (s, 1H), 5.63 (dq, J = 15.9, 7.7 Hz, 1H), 5.23 (d, J = 17.0 Hz, 1H), 5.13 (d, J = 10.1 Hz, 1H), 3.48 (d, J = 7.0 Hz, 2H);

[0251] 13 C NMR (101 MHz, CDCl3) δ 165.18, 144.10, 138.73, 133.68, 133.08 (q, J = 32.7 Hz), 128.39, 127.42, 127.20, 126.84, 125.66 (q, J = 3.6 Hz), 123.76 (q, J = 272.6 Hz), 119.75, 64.83, 43.46;

[0252] 19 F NMR (564 MHz, CDCl3) δ -62.89;

[0253] Exact Mass ESI-MS: calculated m / z for [C 24 H 20F3NONa] + : 418.1389, found: 418.1385.

[0254] Example 26

[0255] To prepare N-(1,1-diphenylbut-3-en-1-yl)-4-methoxybenzamide as shown in the following formula (3-23):

[0256]

[0257] Synthesis of compound 3-23: N-diphenylmethylene-4-methoxybenzamide (63.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added to a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and nitrogen was filled 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (35 μL, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 30 hours. Thin layer chromatography was used to track the reaction, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-23, N-(1,1-diphenylbut-3-en-1-yl)-4-methoxybenzamide, with an isolated yield of 79%, and the structural characterization data as follows:

[0258] 1 H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.8 Hz, 2H), 7.70 (d, J = 7.9 Hz, 2H), 7.36 (q, J = 7.9 Hz, 8H), 7.29-7.25 (m, 2H), 6.95 (s, 1H), 5.63 (dq, J = 15.9, 7.7 Hz, 1H), 5.23 (d, J = 17.0 Hz, 1H), 5.13 (d, J = 10.1 Hz, 1H), 3.48 (d, J = 7.0 Hz, 2H);

[0259] 13C NMR (101 MHz, CDC13) δ 165.18, 144.10, 138.73, 133.68, 133.08 (q, J = 32.7 Hz), 128.39, 127.42, 127.20, 126.84, 125.66 (q, J = 3.6 Hz), 123.76 (q, J = 272.6 Hz), 119.75, 64.83, 43.46;

[0260] 19 F NMR (564 MHz, CDC13) δ -62.89;

[0261] Exact Mass ESI-MS: calculated m / z for [C 24 H 20 F3NONa] + : 418.1389, found: 418.1385.

[0262] Example 27

[0263] To prepare N-(1,1-diphenylbut-3-en-1-yl)thiophene-2-carboxamide as shown in the following structural formula of formula (3-24):

[0264]

[0265] Synthesis of compound 3-24: N-(diphenylmethylene)thiophene-2-carboxamide (58.2 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (140 μL, 0.8 mmol) and allyl bromide (70 μL, 0.8 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30W blue LED (wavelength: 460 nm), and stirred at room temperature for 48 hours. Thin layer chromatography tracking reaction, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-24, N-(1,1-diphenylbut-3-en-1-yl)thiophene-2-carboxamide, with an isolated yield of 70%, and the structural characterization data as follows:

[0266] 1H NMR (400 MHz, CDC13) δ 7.52 (d, J = 3.2 Hz, 1H), 7.45 (d, J = 4.6 Hz, 1H), 7.43 - 7.29 (m, 8H), 7.26 (t, J = 7.1 Hz, 2H), 7.10 - 7.05 (m, 1H), 6.80 (s, 1H), 5.62 (dq, J = 17.2, 8.6 Hz, 1H), 5.23 (d, J = 17.1 Hz, 1H), 5.13 (d, J = 10.2 Hz, 1H), 3.44 (d, J = 7.1 Hz, 2H);

[0267] 13 C NMR (101 MHz, CDC13) δ 160.74, 144.11, 139.75, 133.68, 129.80, 128.31, 128.11, 127.64, 127.09, 126.87, 119.77, 64.64, 44.05;

[0268] Exact Mass ESI-MS: calcd m / z for [C 21 H 20 NOSNa] + : 356.1080, found: 356.1088.

[0269] Example 28

[0270] To prepare N-(l,l-diphenylbut-3-en-l-yl)-3-methylbut-2-enamide as shown in the following structural formula of formula (3-25):

[0271]

[0272] Synthesis of compound 3-25: N-diphenylmethylene-3-methylbut-2-enamide (52.6 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg, 0.004 mmol), palladium acetate (2.2 mg, 0.01 mmol), 1,4-bis(diphenylphosphino)butane (8.6 mg, 0.02 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl bromide (70 μL, 0.8 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-25, N-(1,1-diphenylbut-3-en-1-yl)-3-methylbut-2-enamide, with an isolated yield of 81%, and the structure characterization data as follows:

[0273] 1 H NMR (400 MHz, CDCl3) δ 7.36-7.26 (m, 8H), 7.25-7.18 (m, 2H), 6.09 (s, 1H), 5.68 (s, 1H), 5.65-5.55 (m, 1H), 5.11 (dd, J = 24.2, 13.7 Hz, 2H), 3.40 (d, J = 7.0 Hz, 2H), 2.07 (s, 3H), 1.83 (s, 3H);

[0274] 13 C NMR (101 MHz, CDCl3) δ 165.97, 150.98, 144.74, 133.94, 128.18, 126.78, 126.74, 119.12, 64.24, 43.22, 27.13, 19.79;

[0275] Exact Mass ESI-MS: calculated m / z for [C 21 H 23 NONa] + : 328.1672, found: 328.1672.

[0276] Example 29

[0277] For example, to prepare N-(1,1-diphenylbut-3-en-1-yl)benzamide shown in the following formula (3-26):

[0278]

[0279] Synthesis of compound 3-26: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl acetate (40 mg, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure N-(1,1-diphenylbut-3-en-1-yl)benzamide with an isolated yield of 64%, which had the same structural characterization as compound 1 prepared in Example 1.

[0280] Example 30

[0281] For example, to prepare N-(1,1-diphenylbut-3-en-1-yl)benzamide shown in the following formula (3-27):

[0282]

[0283] Synthesis of compound 3-27: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl benzoate (64.9 mg, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure N-(1,1-diphenylbut-3-en-1-yl)benzamide with an isolated yield of 78%, which had the same structural characterization data as compound 1 prepared in Example 1.

[0284] Example 31

[0285] To prepare N-(1,1-diphenylbut-3-en-1-yl)benzamide as shown in the following formula (3-28):

[0286]

[0287] Synthesis of compound 3-28: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl phenyl carbonate (71.3 mg, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure N-(1,1-diphenylbut-3-en-1-yl)benzamide with an isolated yield of 80%, which had the same structural characterization data as compound 1 prepared in Example 1.

[0288] Example 32

[0289] To prepare N-(1,1-diphenylbut-3-en-1-yl)benzamide as shown in the following formula (3-29):

[0290]

[0291] Synthesis of compound 3-29: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and allyl 4-methylbenzenesulfonate (84.9 mg, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure N-(1,1-diphenylbut-3-en-1-yl)benzamide with an isolated yield of 67%, which had the same structural characterization data as compound 1 prepared in Example 1.

[0292] Example 33

[0293] To prepare N-(cyclohex-2-en-1-yl diphenylmethyl)benzamide as shown in the following formula (3-30):

[0294]

[0295] Synthesis of compound 3-30: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and 3-bromocyclohex-1-ene (64.4 mg, 0.4 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-30, N-(cyclohex-2-en-1-ylphenylmethyl)benzamide, with an isolated yield of 93%, and the structure characterization data as follows:

[0296] 1 H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.2 Hz, 2H), 7.54-7.36 (m, 7H), 7.36-7.22 (m, 6H), 6.88 (s, 1H), 5.79-5.68 (m, 2H), 3.98 (s, 1H), 1.97-1.77 (m, 3H), 1.59-1.49 (m, 2H), 1.33-1.26 (m, 1H);

[0297] 13 C NMR (101 MHz, CDCl3) δ 166.21, 142.66, 142.05, 135.54, 131.42, 130.47, 128.63, 128.55, 128.43, 127.64, 127.60, 127.48, 127.02, 126.95, 126.85, 68.34, 42.28, 25.32, 25.13, 21.84;

[0298] Exact Mass ESI-MS: calculated m / z for [C 26 H 25 NONa] + : 390.1828, found: 390.1824.

[0299] Example 34

[0300] N-(1,1,3-triphenylbut-3-en-1-yl)benzamide as shown in the following structural formula (3-31):

[0301]

[0302] S1, Synthesis of compound 3-31: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and 2-phenylallyl acetate (70.5 mg, 0.4 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-31, N-(1,1-diphenylbut-3-en-1-yl)benzamide, with an isolated yield of 73%, and the structural characterization data as follows:

[0303] 1 H NMR (400 MHz, CDCl3) δ 7.39-7.30 (m, 5H), 7.30-7.21 (m, 10H), 7.21-7.15 (m, 4H), 7.14-7.11 (m, 1H), 6.83 (s, 1H), 5.09-5.04 (m, 1H), 4.64 (d, J = 2.2 Hz, 1H), 3.83 (d, J = 3.3 Hz, 2H);

[0304] 13 C NMR (101 MHz, CDCl3) δ 165.84, 144.40, 143.94, 142.74, 134.91, 131.19, 128.66, 128.24, 127.92, 127.28, 126.84, 126.66, 126.58, 119.60, 109.99, 65.58, 45.19;

[0305] Exact Mass ESI-MS: calculated m / z for [C 29 H 25 NONa]+ :426.1828, found:426.1824.

[0306] S2, Synthesis of compound 4-5: A new dry Schlenk tube (10 mL) was connected to vacuum line, purged with nitrogen 3 times, 1 mL acetonitrile solution of above crude product 3-1 was added under nitrogen atmosphere, then, 1 mL acetonitrile solution of iodine (50.8 mg, 0.2 mmol) and p-toluenesulfonyl chloride sodium (chloramine T) (55.5 mg, 0.2 mmol) were added, chloramine T played the role of oxidant in the reaction, the reaction was carried out at room temperature for 24 hours, thin layer chromatography was used to track the reaction, after the reaction was completed, the reaction mixture was quenched with 1 mL water, extracted with ethyl acetate for three times, concentrated under reduced pressure, the crude product was purified by column chromatography to obtain pure compound 4-5, 6-(iodomethyl)-2,4,6-tetraphenyl-5,6-dihydro-4H-1,3-oxazine, the isolated yield was 58%, and the structural characterization data were as follows:

[0307] 1 H NMR (600 MHz, CDC13) δ 8.39 (d, J = 5.9 Hz, 2H), 7.70 (d, J = 6.8 Hz, 2H), 7.51 (d, J = 7.5 Hz, 3H), 7.31 (d, J = 7.3 Hz, 2H), 7.19 - 7.13 (m, 3H), 7.11 - 7.04 (m, 5H), 6.95 - 6.90 (m, 2H), 6.87 (d, J = 6.9 Hz, 1H), 3.57 - 3.52 (m, 1H), 3.43 (d, J = 11.0 Hz, 1H), 3.27 (q, J = 14.0 Hz, 2H).

[0308] 13 C NMR (151 MHz, CDC13) δ 151.9, 148.5, 146.8, 141.3, 133.7, 131.0, 128.4, 128.3, 128.2, 127.9, 127.7, 127.4, 126.6, 126.3, 126.3, 125.7, 124.9, 77.6, 60.5, 42.9, 18.3.

[0309] HRMS (ESI-TOF) m / z: [M + H] Calcd for C + Calcd for C 29 H 25 INO 530.0975; found 530.0966.

[0310] Example 35

[0311] To prepare (E)-N-(1,1,4-triphenylbut-3-en-1-yl)benzamide as shown in the following formula (3-32):

[0312]

[0313] S1, Synthesis of compound 3-32: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and cinnamyl benzoate (95.3 mg, 0.4 mmol) or 1-phenylallyl benzoate (95.3 mg, 0.4 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-32, (E)-N-(1,1,4-triphenylbut-3-en-1-yl)benzamide, with an isolated yield of 80% and 84%, and the structural characterization data as follows:

[0314] 1 H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.9 Hz, 2H), 7.48 (t, J = 7.1 Hz, 1H), 7.44-7.30 (m, 10H), 7.29-7.17 (m, 7H), 6.96 (s, 1H), 6.50 (d, J = 15.8 Hz, 1H), 6.02 (dt, J = 15.0, 7.2 Hz, 1H), 3.67 (d, J = 7.3 Hz, 2H);

[0315] 13 C NMR (101 MHz, CDCl3) δ 166.58, 144.63, 137.32, 135.45, 134.49, 131.49, 128.68, 128.48, 128.41, 127.31, 127.13, 126.87, 126.75, 126.16, 125.29, 65.09, 42.06;

[0316] Exact Mass ESI-MS:calculated m / z for[C 29 H 25 NONa] + :426.1828,found:426.1829.

[0317] S2. Synthesis of Compounds 4-6: A new, dry Schlenk tube (10 mL) was connected to a vacuum tube and purged with nitrogen three times. Under a nitrogen atmosphere, 1 mL of the crude product 3-1 dissolved in acetonitrile was added. Then, 1 mL of iodine (50.8 mg, 0.2 mmol) dissolved in acetonitrile and sodium p-toluenesulfonyl chloramine (chloramine T) (55.5 mg, 0.2 mmol) were added. Chloramine T acts as an oxidizing agent in the reaction. The reaction was carried out at room temperature for 24 hours, and the reaction was monitored by thin-layer chromatography. After the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted three times with ethyl acetate, concentrated under reduced pressure, and purified by column chromatography to obtain pure 6-(iodo(phenyl)methyl)-2,4,4-triphenyl-5,6-dihydro-4H-1,3-oxazine with a separation yield of 85%. The structural characterization data are as follows:

[0318] 1 H NMR (600MHz, CDCl3) δ8.39(d,J=5.9Hz,2H),7.70(d,J=6.8Hz,2H),7.51(d,J=7.5Hz,3H),7.31(d,J=7.3Hz,2H),7.19–7.13(m,3H ),7.11–7.04(m,5H),6.95–6.90(m,2H),6.87(d,J=6.9Hz,1H),3.57–3.52(m,1H),3.43(d,J=11.0Hz,1H),3.27(q,J=14.0Hz,2H).

[0319] 13 C NMR (151MHz, CDCl3) δ151.9,148.5,146.8,141.3,133.7,131.0,128.4,128.3,128. 2,127.9,127.7,127.4,126.6,126.3,126.3,125.7,124.9,77.6,60.5,42.9,18.3.

[0320] HRMS(ESI-TOF)m / z:[M+H] + Calcd for C 29 H 25 INO 530.0975; found 530.0966.

[0321] Example 36

[0322] To prepare (E)-N-(1,1-diphenyl-4-(p-tolyl)but-3-en-1-yl)benzamide as shown in structural formula (3-33) for example:

[0323]

[0324] Synthesis of compound 3-33: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and (E)-3-(p-tolyl)allyl benzoate (100.9 mg, 0.4 mmol) were added by syringe under nitrogen protection. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was followed by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-33, (E)-N-(1,1-diphenyl-4-(p-tolyl)but-3-en-1-yl)benzamide, with an isolated yield of 79%, and the structural characterization data as follows:

[0325] 1 H NMR (400 MHz, CDCl3) δ 7.80-7.73 (m, 2H), 7.51-7.45 (m, 1H), 7.44-7.30 (m, 10H), 7.29-7.25 (m, 2H), 7.11 (d, J = 8.1 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 6.96 (s, 1H), 6.47 (d, J = 15.8 Hz, 1H), 6.00-5.92 (m, 1H), 3.68-3.61 (m, 2H), 2.30 (s, 3H);

[0326] 13C NMR (101 MHz, CDC13) δ 166.51, 144.60, 137.12, 135.47, 134.53, 134.42, 131.44, 129.16, 128.65, 128.36, 127.08, 126.85, 126.78, 126.06, 124.16, 65.07, 42.25, 21.17;

[0327] Exact Mass ESI-MS: calculated m / z for [C 30 H 27 NONa] + : 440.1985, found: 440.1986.

[0328] Example 37

[0329] To prepare (E)-N-(4-(4-methoxyphenyl)-l,l-diphenylbut-3-en-l-yl)benzamide as shown in the following formula (3-34):

[0330]

[0331] Synthesis of compound 3-34: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), Erioglaucine sodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and (E)-3-(4-methoxyphenyl) allyl benzoate (107.3 mg, 0.4 mmol) were added into the Schlenk tube under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain the purified compound 3-34, (E)-N-(4-(4-methoxyphenyl)-l,l-diphenylbut-3-en-l-yl)benzamide, with an isolated yield of 79%, and the structure characterization data as follows:

[0332] 1H NMR (400 MHz, CDC13) δ 7.76 (d, J = 6.7 Hz, 2H), 7.55 - 7.21 (m, 13H), 7.14 (d, J = 7.6 Hz, 2H), 6.96 (s, 1H), 6.77 (d, J = 7.5 Hz, 2H), 6.45 (d, J = 15.7 Hz, 1H), 5.90 - 5.79 (m, 1H), 3.76 (s, 3H), 3.61 (d, J = 6.4 Hz, 2H);

[0333] 13 C NMR (101 MHz, CDC13) δ 166.52, 159.02, 144.59, 135.49, 133.94, 131.45, 130.12, 128.65, 128.36, 127.29, 127.07, 126.85, 126.80, 122.92, 113.90, 65.08, 55.31, 42.33;

[0334] Exact Mass ESI-MS: calcd m / z for [C 30 H 27 NO2Na] + : 456.1934, found: 456.1932.

[0335] Example 38

[0336] To prepare (E)-N-(4-(4-fluorophenyl)-l,l-diphenylbut-3-en-l-yl)benzamide as shown in the following formula (3-35):

[0337]

[0338] Synthesis of compound 3-35: N-(diphenylmethylene)benzamide (57.0 mg, 0.2 mmol), eosin Y disodium salt (2.7 mg 0.004 mmol), palladium acetate (1.1 mg, 0.005 mmol), 1,4-bis(diphenylphosphino)butane (4.3 mg, 0.01 mmol), and sodium carbonate (42.4 mg, 0.4 mmol) were added into a dry Schlenk tube (10 mL). Then the Schlenk tube was connected to a vacuum tube and was purged with nitrogen for 3 times. Then dry dichloromethane (2 mL), diisopropylethylamine (70 μL, 0.4 mmol) and (E)-3-(4-fluorophenyl)allyl benzoate (102.5 mg, 0.4 mmol) were added under nitrogen protection by syringe. Finally, the reaction tube was sealed and placed at a distance of 1-2 cm from a 30 W blue LED (wavelength: 460 nm) and stirred at room temperature for 30 hours. The reaction was tracked by thin layer chromatography, and after the reaction was completed, the reaction mixture was quenched with 1 mL of water, extracted with ethyl acetate three times, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain pure compound 3-35, i.e. (E)-N-(4-(4-fluorophenyl)-1,1-diphenylbut-3-en-1-yl)benzamide, with an isolated yield of 72%, and the following structure characterization data:

[0339] 1 H NMR (400 MHz, CDC13) δ 7.80 - 7.72 (m, 2H), 7.48 (t, J = 7.3 Hz, 1H), 7.45 - 7.29 (m, 10H), 7.29 - 7.25 (m, 2H), 7.18 - 7.12 (m, 2H), 6.97 - 6.87 (m, 3H), 6.44 (d, J = 15.8 Hz, 1H), 5.94 (dt, J = 15.4, 7.3 Hz, 1H), 3.67 (d, J = 7.3 Hz, 2H);

[0340] 13 C NMR (101 MHz, CDC13) δ 166.56, 162.09 (d, J = 246.5 Hz), 144.66, 135.43, 133.47 (d, J = 3.2 Hz), 133.21, 131.49 (d, J = 2.1 Hz), 128.66, 128.41, 127.57 (d, J = 7.9 Hz), 127.13, 126.81, 126.66, 124.98, 115.31 (d, J = 21.6 Hz), 65.09, 41.71;

[0341] 19 F NMR (564 MHz, CDC13) δ -114.93;

[0342] Exact Mass ESI-MS: calculated m / z for[C 29 H 24 FNONa] + :444.1734, found:444.1736.

[0343] The examples provided above show that the present application provides a method for synthesizing oxazines containing quaternary carbon centers by photo-oxidation / reduction / palladium synergistic catalysis in two steps, which has the advantages of easy availability of raw materials, mild conditions, simple operation, good yield and large substrate expansion range.

[0344] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should also be considered within the scope of protection of the present application.

Claims

1. A process for preparing an allyl group-containing α-quaternary carbon secondary amine compound, characterized by, The method comprises the following steps: The imine shown as formula (1) and the allyl electrophile shown as formula (2) are dissolved in solvent I, and then reacted under the condition of adding a photocatalyst, a metal palladium catalyst, a diphosphine ligand, a non-metallic reducing agent and a base to obtain an imine reduction and selective allylation product shown as formula (3), i.e. the allyl-containing α-quaternary carbon secondary amine compound, and the reaction equation is as follows: wherein R represents any one of aryl, heteroaryl or olefin, R 1 represents any one of H, aryl, Y represents any one of Cl, Br, OTs, OBz, OAc, OCO2Ph, O represents an oxygen atom, N represents a nitrogen atom, H represents a hydrogen atom, Ph represents a phenyl group, and Ar represents any one of aryl, heteroaryl; The photocatalyst is eosin Y disodium salt, The metal palladium catalyst is any one selected from the group consisting of palladium acetate, tetrakis triphenylphosphine palladium and palladium acetylacetone, The diphosphine ligand is any one selected from the group consisting of triphenylphosphine, 1,4-bis(diphenylphosphino)butane and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, The non-metallic reducing agent is any one selected from the group consisting of diisopropylethylamine, triethylamine and dihydropyridine, The base is any one selected from the group consisting of cesium carbonate, potassium acetate, sodium bicarbonate and sodium carbonate. The specific method of the reaction comprises the following steps: under nitrogen protection, the reactants are sealed and placed at a distance of 1-5 cm from a 30W blue LED, and stirred at room temperature for 10-30 hours, wherein the wavelength of the blue LED is 450-500 nm.

2. The method of claim 1, wherein, The molar ratio of the imine to the allyl electrophile is 1:1-5.

3. The method of claim 2, wherein, The molar ratio of the imine to the allyl electrophile is 1:

2.

4. The method of claim 1, wherein, The molar ratio of the imine to the photocatalyst is 1:0.001-0.

05.

5. The method of claim 4, wherein, The molar ratio of the imine to the photocatalyst is 1:0.

02.

6. The method of claim 1, wherein, The molar ratio of the imine to the metal palladium catalyst is 1:0.001-0.

05.

7. The method of claim 6, wherein, The molar ratio of the imine to the metal palladium catalyst is 1:0.

025.

8. The method of claim 1, wherein, The molar ratio of the imine to the diphosphine ligand is 1:0.002-0.

10.

9. The method of claim 8, wherein, The molar ratio of the imine to the diphosphine ligand is 1:0.

05.

10. The method of claim 1, wherein, The molar ratio of the imine to the non-metallic reducing agent is 1:1-5.

11. The method of claim 10, wherein, The molar ratio of the imine to the non-metallic reducing agent is 1:

2.

12. The method of claim 1, wherein, The molar ratio of the imine to the base is 1:1-5.

13. The method of claim 12, wherein, The molar ratio of the imine to the base is 1:

2.

14. The method according to claim 1, characterized in that, The allyl electrophile is any one selected from the group consisting of allyl bromide, allyl acetate, allyl benzoate, allyl phenyl carbonate, allyl 4-methylbenzenesulfonate, 3-bromocyclohex-1-ene, allyl 2-phenylacetate, cinnamyl benzoate, 1-phenylallyl benzoate, (E)-3-(p-tolyl)allyl benzoate, (E)-3-(4-methoxyphenyl)allyl benzoate and (E)-3-(4-fluorophenyl)allyl benzoate.

15. The method of claim 1, wherein, Solvent I is any one selected from the group consisting of dichloroethane, toluene and dichloromethane.

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