Synthesis method of multifunctional 2-alkenyl furo cyclo-4-ketone and 5-alkenyl-3-furancarbonyl compound

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a multifunctional compound, a preparation method thereof, a derivative of the multifunctional compound and a preparation method of the derivative. According to the invention, gamma-hydroxy-alpha, beta-unsaturated olefine aldehyde and a compound 1 are used as reaction raw materials, and lewis acid is used as a catalyst to prepare the multifunctional compound under normal pressure. The preparation method is simple and easy to operate, raw materials are cheap and easy to obtain, reaction conditions are mild, and industrial production is easy. The polyfunctionalized compound prepared by the preparation method provided by the invention has high yield and purity, and has good economic benefits.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a polyfunctionalized compound, a preparation method thereof, derivatives of the polyfunctionalized compound, and a preparation method thereof. Background Art

[0002] 5-Vinyl-3-furancarbonyl compounds and furocyclic molecules are important structural units widely present in drugs or other bioactive molecules. The methods reported so far face problems such as relying on expensive metal catalysts, using dangerous diazo compounds, and limited substrate scope. Therefore, developing an economical, universal, and efficient synthesis method for polyfunctionalized furocycles and polyfunctionalized 5-vinyl-3-furancarbonyl compounds is of great significance for organic chemistry and medicinal chemistry. Summary of the Invention

[0003] In view of this, the present invention provides a polyfunctionalized compound, a preparation method thereof, derivatives of the polyfunctionalized compound, and a preparation method thereof. The preparation method of the polyfunctionalized compound provided by the present invention is simple and easy to operate, and the yield of the prepared polyfunctionalized compound is relatively high.

[0004] The present invention provides a preparation method of a polyfunctionalized compound, comprising the following steps:

[0005] Mix γ-hydroxy-α,β-unsaturated enal, compound 1, a Lewis acid catalyst, and an organic solvent, and carry out a cyclization reaction to obtain the polyfunctional compound;

[0006] The γ-hydroxy-α,β-unsaturated enal has the structure shown in Formula 1 or is Compound 1 has any one of the structures shown in Formulas 2 to 5:

[0007]

[0008] When the γ-hydroxy-α,β-unsaturated enal is Compound 1 is The polyfunctional compound is

[0009] When the γ-hydroxy-α,β-unsaturated enal is Compound 1 is any one of the structures shown in Formulas 2 to 5; when compound 1 is The polyfunctional compound has the structure shown in Formula I, when compound 1 is The polyfunctional compound has the structure shown in Formula II, when compound 1 is The polyfunctional compound has the structure shown in Formula III, when compound 1 is When, the polyfunctional compound has the structure shown in Formula IV:

[0010]

[0011] Wherein, R 1 and R 2 are independently aryl, phenyl, halogen-substituted phenyl, alkyl-substituted phenyl or alkyl;

[0012] R 3 and R 4 are independently hydrogen, carboxyl, alkyl or aryl;

[0013] X is -CH2- or -NH-, and n is 1 or 2;

[0014] R 5 and R 6 are independently aryl, alkyl or alkoxy;

[0015] Y is -O- or -S-;

[0016] R 7 and R 8 are independently methyl or ethyl.

[0017] Preferably, the includes γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, (E)-4,4-bis(4-bromophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-chlorophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-methylphenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(3-chlorophenyl)-4-hydroxy-2-butenal, (E)-4-hydroxy-4,4-di(naphthalen-2-yl)-2-butenal, (E)-4-hydroxy-4-phenyl-2-pentenal, (E)-4,4-bis(4-fluorophenyl)-4-hydroxy-2-butenal.

[0018] Preferably, the Lewis acid catalyst includes aluminum trifluoromethanesulfonate, scandium trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, indium trifluoromethanesulfonate, tin trifluoromethanesulfonate, iron trifluoromethanesulfonate or tris(pentafluorophenyl)borane;

[0019] The molar ratio of the γ-hydroxy-α,β-unsaturated enal to the Lewis acid catalyst is 1:0.01 to 0.2.

[0020] Preferably, the including 1,3 - cyclohexanedione, 5 - methylcyclohexane - 1,3 - dione, 5,5 - dimethylcyclohexane - 1,3 - dione, 5 - phenylcyclohexane - 1,3 - dione, 5 - (methoxyphenyl)cyclohexane - 1,3 - dione, 5 - (2 - furyl)-1,3 - cyclohexanedione, 3,5 - dioxocyclohexanecarboxylic acid, 1,3 - cycloheptanedione or 2,4 - piperidinedione;

[0021] The including 2,4 - pentanedione, 2,6 - dimethyl - 3,5 - heptanedione, 1,3 - diphenylpropanedione, ethyl acetoacetate, 2 - cyanoethyl 3 - oxobutyrate, allyl acetoacetate, methoxyethyl acetoacetate, 3 - bromopropyl 3 - oxobutyrate, (1R,2S,5R)-2 - isopropyl - 5 - methylcyclohexyl 3 - oxobutyrate, 1,7,7 - trimethylbicyclo[2.2.1]heptan - 2 - yl 3 - oxobutyrate, (3S,8R,9S,10R,13S,14S)-10,13 - dimethyl - 17 - oxo - 2,3,4,7,8,9,10,11,12,13,14,15,16,17 - tetradecahydro - 1H - cyclopenta[a]phenanthren - 3 - yl 3 - oxobutyrate, (5R,5aS,8aS,8bR)-2,2,7,7 - tetramethyltetrahydro - 5H - bis(1,3)dioxolane[4,5 - b:4',5'-d]pyran - 5 - methyl - 3 - oxobutyrate, 3,7 - dimethyloct - 6 - en - 1 - yl 3 - oxobutyrate or (3S,5S,8R,9S,10S,13R,14S,17R)-10,13 - dimethyl - 17 - ((R)-6 - methylhept - 2 - yl)hexadecahydro - 1H - cyclopenta[a]phenanthren - 3 - yl 3 - oxobutyrate;

[0022] The is 1,3 - dimethylbarbituric acid or 1,3 - diethyl - 2 - thiobarbituric acid.

[0023] Preferably, the molar ratio of the γ - hydroxy - α,β - unsaturated enal to Compound 1 is 1:1.8 - 2.2.

[0024] Preferably, the temperature of the cyclization reaction is 0 - 80 °C and the time is 2 - 34 h.

[0025] The present invention also provides a polyfunctionalized compound prepared by the preparation method according to the above technical solution, having any one of the structures shown in Formulas I - IV:

[0026]

[0027] wherein, R 1 and R 2 independently are aryl, phenyl, halogen - substituted phenyl, alkyl - substituted phenyl or alkyl;

[0028] R 3 and R 4 are independently hydrogen, carboxyl, alkyl or aryl;

[0029] X is -CH2- or -NH-, and n is 1 or 2;

[0030] R 5 and R 6 are independently aryl, alkyl or alkoxy;

[0031] Y is -O- or -S-;

[0032] R 7 and R 8 are independently methyl or ethyl.

[0033] Preferably, it has any one of the structures shown in Formula I-1 to I-17, Formula II-1 to II-14, and Formula III-1 to III-2:

[0034]

[0035]

[0036] The present invention also provides derivatives prepared from the polyfunctionalized compounds having the structure shown in Formula I in the above technical solution, having any one of the structures shown in Formula a to f:

[0037]

[0038] The present invention also provides a preparation method of the derivatives described in the above technical solution, including the following steps:

[0039] The preparation method includes the following steps: Mix N-bromosuccinimide and a first organic solvent and then carry out an electrophilic substitution reaction to obtain the

[0040] The preparation method includes the following steps: Mix methyltriphenylphosphonium bromide, potassium tert-butoxide and a second organic solvent and then carry out a Wittig reaction to obtain the

[0041] The preparation method includes the following steps: Mix sodium borohydride and a third organic solvent and then carry out a reduction reaction to obtain the

[0042] The preparation method includes the following steps: Mix After triethylsilane, trifluoroacetic acid and the fourth organic solvent are mixed, a silane reduction reaction is performed to obtain the

[0043] Said The preparation method comprises the following steps: After being dissolved in a fifth organic solvent and mixed, an electrocyclization / oxidation rearomatization reaction is performed to obtain the

[0044] Said The preparation method comprises the following steps: The ethanol solution of methylamine and the sixth organic solvent are mixed and subjected to an aminolysis reaction of furan to obtain the

[0045] The present invention uses γ-hydroxy-α,β-unsaturated olefinic aldehyde and compound 1 as reaction raw materials and Lewis acid as catalyst to prepare a multifunctional compound under normal pressure. The preparation method provided by the present invention is simple and easy to operate, the raw materials are cheap and easy to obtain, the reaction conditions are mild, and it is easy to industrialize production. The multifunctional compound prepared according to the preparation method provided by the present invention has a high yield and purity and has good economic benefits. DETAILED DESCRIPTION

[0046] The present invention provides a method for preparing a multifunctional compound, comprising the following steps:

[0047] Mixing γ-hydroxy-α,β-unsaturated olefinic aldehyde, compound 1, a Lewis acid catalyst and an organic solvent, and performing a ring-forming reaction to obtain the multifunctional compound;

[0048] The γ-hydroxy-α,β-unsaturated olefinic aldehyde has a structure shown in Formula 1 or is The compound 1 has a structure shown in any one of Formulas 2 to 5:

[0049]

[0050] As a specific embodiment of the present invention, when the γ-hydroxy-α, β-unsaturated olefinic aldehyde is When the compound 1 is The multifunctional compound is

[0051] When the γ-hydroxy-α,β-unsaturated olefinic aldehyde is When the compound 1 is any one of the structures shown in Formulas 2 to 5; when the compound 1 is When the multifunctional compound has the structure shown in formula I, when the compound 1 is When, the polyfunctional compound has the structure shown in Formula II, when the compound 1 is When, the polyfunctional compound has the structure shown in Formula III, when the compound 1 is When, the polyfunctional compound has the structure shown in Formula IV:

[0052]

[0053] In the present invention, R 1 is an aryl group, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group or an alkyl group, the aryl group of the R 1 can be a naphthyl group, the halogen-substituted phenyl group of the R 1 can be a 4-fluorophenyl group, a 4-chlorophenyl group, a 4-bromophenyl group, a 3-chlorophenyl group, the alkyl-substituted phenyl group of the R 1 can be a 4-methylphenyl group, the alkyl group of the R 1 can be a methyl group; R 2 is an aryl group, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group or an alkyl group, the aryl group of the R 2 can be a naphthyl group, the halogen-substituted phenyl group of the R 2 can be a 4-fluorophenyl group, a 4-chlorophenyl group, a 4-bromophenyl group or a 3-chlorophenyl group, the alkyl-substituted phenyl group of the R 2 can be a 4-methylphenyl group, the alkyl group of the R 2 can be a methyl group.

[0054] As a specific embodiment of the present invention, R 1 and R 2 can be simultaneously a naphthyl group, a phenyl group, a 4-fluorophenyl group, a 4-bromophenyl group, a 4-chlorophenyl group, a 4-methylphenyl group or a 3-chlorophenyl group; when R 1 is a phenyl group, R 2 can also be a methyl group.

[0055] As a specific embodiment of the present invention, the can include γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, (E)-4,4-bis(4-bromophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-chlorophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-methylphenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(3-chlorophenyl)-4-hydroxy-2-butenal, (E)-4-hydroxy-4,4-di(naphthalen-2-yl)-2-butenal, (E)-4-hydroxy-4-phenyl-2-pentenal or (E)-4,4-bis(4-fluorophenyl)-4-hydroxy-2-butenal.

[0056] In the present invention, R 3 is hydrogen, a carboxyl group, an alkyl group or an aryl group, the R3 The alkyl group of R includes methyl, and R 3 The aryl group of R includes phenyl, substituted phenyl, and 2-furyl, and R 3 The substituted phenyl of R includes p-methoxyphenyl; R 4 is hydrogen, carboxyl, alkyl or aryl, and the alkyl group of R 4 includes methyl, and R 4 The aryl group of R includes phenyl, substituted phenyl, and 2-furyl, and R 4 The substituted phenyl of R includes p-methoxyphenyl; X is -CH2- or -NH-, and n is 1 or 2.

[0057] As a specific embodiment of the present invention, R 3 and R 4 can both be hydrogen or methyl at the same time; when R 3 is methyl, R 4 can also be hydrogen, X is -CH2-, and n is 1; when R 4 is hydrogen, R 3 can also be phenyl, p-methoxyphenyl or 2-furyl, X is -CH2-, and n is 1.

[0058] As a specific embodiment of the present invention, the can include 1,3-cyclohexanedione, 5-methylcyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione, 5-phenylcyclohexane-1,3-dione, 5-(methoxyphenyl)cyclohexane-1,3-dione, 5-(2-furyl)-1,3-cyclohexanedione, 3,5-dioxocyclohexanecarboxylic acid, 1,3-cycloheptanedione or 2,4-piperidinedione.

[0059] In the present invention, R 5 is aryl, alkyl or alkoxy, the aryl group of R 5 includes phenyl, the alkyl group of R 5 includes methyl or isopropyl, and the alkoxy group of R 5 includes ethoxy, methoxyethoxy, bromopropoxy, DL-isobornyloxy, L-mentholoxy, dihydrocholesteroloxy, cyanoethoxy, dehydroepiandrosteroneoxy, fructose diacetoneoxy, citronelloloxy or allyloxy; R 6 is aryl, alkyl or alkoxy, the aryl group of R 6 includes phenyl, the alkyl group of R 6 includes methyl or isopropyl, and the alkoxy group of R 6 includes ethoxy, methoxyethoxy, bromopropoxy, DL-isobornyloxy, L-mentholoxy, dihydrocholesteroloxy, cyanoethoxy, dehydroepiandrosteroneoxy, fructose diacetoneoxy, citronelloloxy, allyloxy.

[0060] As a specific embodiment of the present invention, R 5 and R 6 can both be methyl, isopropyl, or phenyl; when R 6 is methyl, R 5 can also be ethoxy, cyanoethoxy hydrogen, allyloxy, methoxyethoxy, bromopropoxy, L-mentholoxy, DL-isobornyloxy, dehydroepiandrosterone oxy, fructose diacetone oxy, citronellol oxy, or dihydrocholesterol oxy.

[0061] As a specific embodiment of the present invention, the can include 2,4-pentanedione, 2,6-dimethyl-3,5-heptanedione, 1,3-diphenylpropanedione, ethyl acetoacetate, 2-cyanoethyl 3-oxobutyrate, allyl acetoacetate, methoxyethyl acetoacetate, 3-bromopropyl 3-oxobutyrate, (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 3-oxobutyrate, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 3-oxobutyrate, (3S,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 3-oxobutyrate, (5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis(1,3)dioxolane[4,5-b:4',5'-d]pyran-5-ylmethyl 3-oxobutyrate, 3,7-dimethyloct-6-en-1-yl 3-oxobutyrate, or (3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)hexadecahydro-1H-cyclopenta[a]phenanthren-3-yl 3-oxobutyrate;

[0062] In the present invention, R 7 is methyl or ethyl, and R 8 is methyl or ethyl; the can be 1,3-dimethylbarbituric acid or 1,3-diethyl-2-thiobarbituric acid

[0063] As a specific embodiment of the present invention, the Lewis acid catalyst may include aluminum trifluoromethanesulfonate (Al(OTf)3), scandium trifluoromethanesulfonate (Sc(OTf)3), bismuth trifluoromethanesulfonate (Bi(OTf)3), indium trifluoromethanesulfonate, tin trifluoromethanesulfonate, iron trifluoromethanesulfonate, or tris(pentafluorophenyl)borane. In the present invention, the Lewis catalyst has multiple activation functions that can promote the efficient and highly selective synthesis of products, and can achieve the synthesis of polyfunctional compounds under atmospheric pressure. During the reaction process, it is not necessary to activate the reactants in advance. During the preparation process, the Lewis acid catalyst can promote the rapid conversion of the 2H-pyran intermediate to the product.

[0064] As a specific embodiment of the present invention, the molar ratio of the γ-hydroxy-α,β-unsaturated enal to the Lewis acid catalyst can be 1:0.01 to 0.2. During the preparation process, the molar ratio of the γ-hydroxy-α,β-unsaturated enal to the Lewis acid catalyst can be 1:0.05 to 0.2. During the preparation process, the molar ratio of the γ-hydroxy-α,β-unsaturated enal to the Lewis acid catalyst can be 1:0.01 to 0.05. If the amount of the Lewis acid is reduced, the yield will not decrease significantly, but the reaction time will be prolonged. Increasing the amount of the Lewis acid will also lead to a decrease in the yield.

[0065] As a specific embodiment of the present invention, the organic solvent can be acetonitrile or ethyl acetate; the molar concentration of γ-hydroxy-α,β-unsaturated enal in the reaction solution system for the cyclization reaction can be 0.08 to 0.12 mol / L, specifically 0.1 mol / L. When the addition amount of the organic solvent is too high or too low, the molar concentration of γ-hydroxy-α,β-unsaturated enal in the reaction solution system for the cyclization reaction will decrease or increase accordingly, thereby resulting in a decrease in the yield of the polyfunctional compound.

[0066] As a specific embodiment of the present invention, the molar ratio of the γ-hydroxy-α,β-unsaturated enal to Compound 1 can be 1:1.8 to 2.2, specifically 1:2.

[0067] As a specific embodiment of the present invention, the temperature of the cyclization reaction can be 0 to 80 °C, can also be 20 to 70 °C, and can further be 30 to 45 °C; the time of the cyclization reaction can be 2 to 34 h, can also be 3 to 20 h, and can further be 4 to 7 h.

[0068] As a specific embodiment of the present invention, the preparation The reaction equation is: The preparation The reaction equation is as follows:

[0069] In the present invention, after the ring-forming reaction, it further includes: concentrating the system after the ring-forming reaction and then separating and purifying it by silica gel column chromatography to obtain the polyfunctionalized compound. The present invention has no special requirements for the concentration and silica gel column chromatography, and conventional methods in the art can be used.

[0070] The present invention also provides a polyfunctionalized compound prepared by the preparation method according to the above technical solution, having any one of the structures shown in Formulas I to IV:

[0071]

[0072] Wherein, R 1 and R 2 independently are aryl, phenyl, halogen-substituted phenyl, alkyl-substituted phenyl or alkyl;

[0073] R 3 and R 4 independently are hydrogen, carboxyl, alkyl or aryl;

[0074] X is -CH2- or -NH-, and n is 1 or 2;

[0075] R 5 and R 6 independently are aryl, alkyl or alkoxy;

[0076] R 7 and R 8 independently are methyl or ethyl.

[0077] As a specific embodiment of the present invention, the can be

[0078] As a specific embodiment of the present invention, the polyfunctionalized compound can have any one of the structures shown in Formulas I-1 to I-17, Formulas II-1 to II-14, and Formulas III-1 to III-2:

[0079]

[0080]

[0081] The present invention also provides a derivative prepared from the polyfunctionalized compound having the structure shown in Formula I in the above technical solution, having any one of the structures shown in Formulas a to f:

[0082]

[0083] As a specific embodiment of the present invention, the can be the can be the can be the can be the can be the can be

[0084] The present invention also provides a preparation method for the derivative described in the above technical solution, including the following steps:

[0085] the preparation method includes the following steps: Mix N-bromosuccinimide and a first organic solvent and then carry out an electrophilic substitution reaction to obtain the

[0086] the preparation method includes the following steps: Mix methyltriphenylphosphonium bromide, potassium tert-butoxide and a second organic solvent and then carry out a Wittig reaction to obtain the

[0087] the preparation method includes the following steps: Mix sodium borohydride and a third organic solvent and then carry out a reduction reaction to obtain the

[0088] the preparation method includes the following steps: Mix triethylsilane, trifluoroacetic acid and a fourth organic solvent and then carry out a silane reduction reaction to obtain the

[0089] the preparation method includes the following steps: Mix dissolve in a fifth organic solvent and then carry out an electrocyclization / oxidative dearomatization reaction to obtain the

[0090] the preparation method includes the following steps: Mix an ethanol solution of methylamine and a sixth organic solvent and then carry out an ammonolysis reaction of furan to obtain the

[0091] In the present invention, the preparation method includes the following steps: Mix After mixing N-bromosuccinimide with the first organic solvent, an electrophilic substitution reaction is carried out to obtain the As a specific embodiment of the present invention, the first organic solvent may be dichloromethane; the dichloromethane may be dry dichloromethane, and the water content of the dry dichloromethane is less than or equal to 50 ppm; the The molar ratio of to N-bromosuccinimide (NBS) can be 1:1.4 - 1.6, and can specifically be 1:1.5; there is no special limitation on the dosage of the first organic solvent in the present invention, as long as it can be completely dissolved. As a specific embodiment of the present invention, the temperature of the electrophilic substitution reaction can be room temperature, and the temperature of the room temperature is 20 - 35 °C; the time of the electrophilic substitution reaction can be 10 - 12 h. As a specific embodiment of the present invention, the electrophilic substitution reaction can be accompanied by stirring, and there is no special limitation on the stirring in the present invention, as long as the reaction can be sufficient.

[0092] In the present invention, the equation of the electrophilic substitution reaction is:

[0093] In the present invention, the The preparation method of includes the following steps: Mix Methyltriphenylphosphonium bromide, potassium tert-butoxide and a second organic solvent, and then carry out a Wittig reaction to obtain the As a specific embodiment of the present invention, the second organic solvent may be tetrahydrofuran; the The molar ratio of methyltriphenylphosphonium bromide (MePPh3Br) to potassium tert-butoxide (tBuOK) can be 1:2.8 - 3.2:2.8 - 3.2, and can specifically be 1:3:3; there is no special limitation on the dosage of the second organic solvent in the present invention, as long as it can be completely dissolved. As a specific embodiment of the present invention, the temperature of the Wittig reaction can be room temperature, and the temperature of the room temperature is 20 - 35 °C; the time of the Wittig reaction can be 11 - 13 h. As a specific embodiment of the present invention, the Wittig reaction can be accompanied by stirring, and there is no special limitation on the stirring in the present invention, as long as the reaction can be sufficient.

[0094] In the present invention, the equation of the Wittig reaction is:

[0095] In the present invention, the The preparation method of includes the following steps: Mix Sodium borohydride and a third organic solvent, and then carry out a reduction reaction to obtain the As a specific embodiment of the present invention, the third organic solvent may be methanol; the The molar ratio of [substance] to sodium borohydride can be 1:2.8 to 3.2, specifically 1:3. There is no special limitation on the dosage of the third organic solvent in the present invention, as long as it can completely dissolve. As a specific embodiment of the present invention, the temperature of the reduction reaction can be room temperature, and the temperature of room temperature is 20 to 35 °C; the time of the reduction reaction can be 6 to 8 h. As a specific embodiment of the present invention, the reduction reaction can be accompanied by stirring. There is no special limitation on the stirring in the present invention, as long as the reaction can be sufficient.

[0096] In the present invention, the equation of the reduction reaction is:

[0097] In the present invention, the The preparation method of [substance] includes the following steps: Mix triethylsilane, trifluoroacetic acid and a fourth organic solvent, and then carry out a silane reduction reaction to obtain the As a specific embodiment of the present invention, the fourth organic solvent can be dichloromethane, and the dichloromethane can be dry dichloromethane, and the moisture content of the dry dichloromethane is less than or equal to 50 ppm; the is prepared by the reduction reaction using as the raw material according to the above technical solution. The molar ratio of triethylsilane to trifluoroacetic acid can be 1:9.8 to 10.2:2.8 to 3.2, specifically 1:10:3. There is no special limitation on the dosage of the fourth organic solvent in the present invention, as long as it can completely dissolve. As a specific embodiment of the present invention, the temperature of the silane reduction reaction can be room temperature, and the temperature of room temperature is 20 to 35 °C; the time of the silane reduction reaction can be 2 to 4 h. As a specific embodiment of the present invention, the silane reduction reaction can be accompanied by stirring. There is no special limitation on the stirring in the present invention, as long as the reaction can be sufficient.

[0098] In the present invention, the equation of the silane reduction reaction is:

[0099] In the present invention, the The preparation method of [substance] includes the following steps: Dissolve in a fifth organic solvent and then carry out an electrocyclization / oxidative dearomatization reaction to obtain the As a specific embodiment of the present invention, the fifth organic solvent may be chloroform or toluene. The present invention has no special limitation on the amount of the fifth organic solvent, as long as it can be completely dissolved. As a specific embodiment of the present invention, the temperature of the electrocyclization / oxidation heavy aromatization reaction may be room temperature, and the room temperature is 20 to 35°C; the time of the electrocyclization / oxidation heavy aromatization may be 24 to 26 hours; the electrocyclization / oxidation heavy aromatization reaction may be carried out under the irradiation of an LED lamp, and the power of the LED lamp may be 2 to 4W, and may be specifically 3W; the wavelength of the LED light source may be 365nm. As a specific embodiment of the present invention, the electrocyclization / oxidation heavy aromatization reaction may be accompanied by stirring, and the present invention has no special limitation on the stirring, as long as the reaction can be sufficient.

[0100] In the present invention, the equation for the electrocyclization / oxidative heavy aromatization reaction is:

[0101] In the present invention, the The preparation method comprises the following steps: The ethanol solution of methylamine and the sixth organic solvent are mixed and subjected to an aminolysis reaction of furan to obtain the As a specific embodiment of the present invention, the sixth organic solvent may be an ethanol aqueous solution. The mass concentration of the ethanol aqueous solution may be 30%; the mass percentage of methylamine in the methylamine ethanol solution may be 25-35%, or may be 30%; The molar ratio of methylamine in the ethanol aqueous solution of methylamine can be 1:2.8-3.2, and can be specifically 1:3; the present invention has no special limitation on the amount of the sixth organic solvent, as long as it can be completely dissolved. As a specific embodiment of the present invention, the temperature of the aminolysis reaction of furan can be 140-160°C, and can be specifically 150°C; the time of the aminolysis reaction of furan can be 9-11h. As a specific embodiment of the present invention, the aminolysis reaction of furan can be accompanied by stirring, and the present invention has no special limitation on the stirring, as long as the reaction can be sufficient.

[0102] In the present invention, the equation for the aminolysis reaction of furan is:

[0103] The present invention The method for preparing derivatives using raw materials is simple, easy to operate, mild reaction conditions, and the prepared products have high purity.

[0104] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0105] After the preparation of each embodiment is completed, in order to further verify that the purified compound is indeed the target product to be prepared in this embodiment, the obtained solid product is analyzed. The analysis methods used are nuclear magnetic resonance and high-resolution mass spectrometry, and the detection results are listed in each embodiment.

[0106] Example 1

[0107] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 3 = R 4 being hydrogen, the X group being CH2, and n = 1 1,3-cyclohexanedione as the reaction raw material, and reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0108] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 45 °C for 5 h. The reaction equation is as follows:

[0109]

[0110] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 111.8 mg of solid product, and the calculated yield was 94%.

[0111] The analysis of the test is as follows:

[0112] 1. 1H NMR and 13C NMR analysis:

[0113] 1 HNMR(300MHz,CDCl3)δ7.47-7.37(m,3H),7.34-7.17(m,7H),6.89(s,1H),5.72(s,1H),2.75(t,J = 6.2Hz,2H),2.40(t,J = 6.4Hz,2H),2.08(p,J = 6.4Hz,2H)ppm.

[0114] 1313C NMR (75 MHz, CDCl3) δ 194.1, 165.8, 153.2, 142.1, 141.3, 139.5, 129.1, 129.0, 128.3, 128.0, 127.8, 126.9, 122.5, 114.9, 104.4, 37.6, 23.2, 22.3 ppm.

[0115] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 19 O2 [M + + H]: 315.1380, Found: 315.1389.

[0116] It can be seen from this result that its theoretical mass is 315.1380, while the observed value of the peak found in the actual mass spectrometry is 315.1389; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0117] This is the product of this example.

[0118] Example 2

[0119] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, R 3 being methyl, R 4 being hydrogen, X group being CH2, and 5-methylcyclohexane-1,3-dione with n = 1 as the reaction raw material, and reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0120] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 5-methylcyclohexane-1,3-dione (101.0 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL), and react at 45 °C for 5 h. The reaction equation is as follows:

[0121]

[0122] Concentrate the reaction solution and obtain 118.8 mg of solid product by silica gel column chromatography, and the calculated yield is 90%.

[0123] The analysis of the test is as follows:

[0124] 1. 1H NMR and 13C NMR analysis:

[0125] 11H NMR (300 MHz, CDCl3) δ 7.47 - 7.38 (m, 3H), 7.33 - 7.18 (m, 7H), 6.88 (s, 1H), 5.71 (s, 1H), 2.83 (dd, J1 = 16.4 Hz, J2 = 4.2 Hz, 1H), 2.51 - 2.28 (m, 3H), 2.20 - 2.09 (m, 1H), 1.12 (d, J = 6.1 Hz, 3H) ppm.

[0126] 13 13C NMR (75 MHz, CDCl3) δ 193.7, 165.5, 153.4, 142.1, 141.3, 139.5, 129.1, 129.0, 128.3, 128.0, 127.8, 126.9, 122.1, 115.0, 104.4, 46.0, 31.3, 30.5, 21.0 ppm.

[0127] 2. High - resolution mass spectrometry: HRMS (ESI) C 23 H 21 O2[M + + H]: 329.1536, Found: 329.1536.

[0128] It can be seen from this result that its theoretical mass is 329.1536, and the observed value of the peak found in the actual mass spectrum is 329.1536; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0129] This is the product of this example.

[0130] Example 3

[0131] Using γ - hydroxy - γ - diphenyl - α,β - unsaturated enal with R 1 = R 2 being phenyl, R 3 = R 4 being methyl, X group being CH2, and 5,5 - dimethylcyclohexane - 1,3 - dione with n = 1 as the reaction raw material, reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0132] Dissolve γ - hydroxy - γ - diphenyl - α,β - unsaturated enal (95.3 mg, 0.4 mmol), 5,5 - dimethylcyclohexane - 1,3 - dione (112.1 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL), and react at 45 °C for 5 h. The reaction equation is as follows:

[0133]

[0134] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 120.9 mg of solid product, and the yield was calculated to be 88%.

[0135] The analysis of the test is as follows:

[0136] 1. 1H NMR and 13C NMR analysis:

[0137] 1 H NMR (300 MHz, CDCl3) δ 7.47 - 7.36 (m, 3H), 7.33 - 7.18 (m, 7H), 6.89 (s, 1H), 5.72 (s, 1H), 2.62 (s, 2H), 2.28 (s, 2H), 1.08 (s, 6H) ppm.

[0138] 13 C NMR (75 MHz, CDCl3) δ 193.5, 164.9, 153.5, 141.9, 141.3, 139.5, 129.1, 129.0, 128.2, 128.0, 127.7, 126.9, 121.3, 115.0, 104.3, 51.9, 37.2, 34.9, 28.5 ppm.

[0139] 2. High-resolution mass spectrometry: HRMS (ESI) C 24 H 23 O2 [M + + H]: 343.1693, Found: 343.1691.

[0140] It can be seen from the results that the theoretical mass is 343.1693, while the observed value of the peak found in the actual mass spectrometry is 343.1691; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0141] is the product of this example.

[0142] Example 4

[0143] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, R 3 being phenyl, R 4 being hydrogen, X group being CH2, and 5-phenylcyclohexane-1,3-dione with n = 1 as the reaction raw material, and using aluminum trifluoromethanesulfonate as the catalyst for the reaction. The specific implementation process is as follows:

[0144] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 5-phenylcyclohexane-1,3-dione (150.6 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL), and react at 45 °C for 5 h. The reaction equation is as follows:

[0145]

[0146] Concentrate the reaction solution and obtain 123.1 mg of solid product by silica gel column chromatography, and the calculated yield is 79%.

[0147] The analysis of the test is as follows:

[0148] 1. 1H NMR and 13C NMR analysis:

[0149] 1 1H NMR (300 MHz, CDCl3) δ 7.48 - 7.38 (m, 3H), 7.37 - 7.19 (m, 12H), 6.90 (s, 1H), 5.77 (s, 1H), 3.53 - 3.39 (m, 1H), 3.12 - 2.88 (m, 2H), 2.67 (d, J = 8.3 Hz, 2H) ppm.

[0150] 13 13C NMR (75 MHz, CDCl3) δ 192.6, 164.9, 153.7, 142.4, 142.3, 141.2, 139.5, 129.1, 129.0, 128.8, 128.3, 128.1, 127.9, 127.2, 126.9, 126.7, 122.4, 114.9, 104.4, 44.9, 41.0, 31.1 ppm.

[0151] 2. High-resolution mass spectrometry: HRMS (ESI) C 28 H 23 O2 [M + + H]: 391.1693, Found: 391.1692.

[0152] It can be seen from this result that the theoretical mass is 391.1693, while the observed value of the peak found in the actual mass spectrum is 391.1692; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0153] Is the product of this example.

[0154] Example 5

[0155] Using R 1 = R 2γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal with phenyl as R 3 p-Methoxyphenyl as R 4 Using 5-(methoxyphenyl)cyclohexane-1,3-dione with hydrogen as R, X group as CH2, and n = 1 as the reaction raw material, the reaction was carried out with aluminum trifluoromethanesulfonate as the catalyst. The specific implementation process is as follows:

[0156] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 5-(methoxyphenyl)cyclohexane-1,3-dione (174.6 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL), and react at 45 °C for 4 h. The reaction equation is as follows:

[0157]

[0158] Concentrate the reaction solution and obtain 121.4 mg of solid product by silica gel column chromatography. The calculated yield is 72%.

[0159] The analysis of the test is as follows:

[0160] 1. 1H NMR and 13C NMR analysis:

[0161] 1 H NMR (300 MHz, CDCl3) δ 7.48 - 7.38 (m, 3H), 7.34 - 7.25 (m, 5H), 7.23 (dd, J1 = 7.4 Hz, J2 = 2.0 Hz, 2H), 7.19 - 7.12 (d, J = 4.3 Hz, 2H), 6.90 (s, 1H), 6.87 (d, J = 8.6 Hz, 2H), 5.77 (s, 1H), 3.79 (s, 3H), 3.51 - 3.34 (m, 1H), 3.10 - 2.83 (m, 2H), 2.68 - 2.61 (m, 2H) ppm.

[0162] 13 C NMR (75 MHz, CDCl3) δ 192.8, 165.1, 158.6, 153.7, 142.4, 141.2, 139.5, 134.5, 129.2, 129.0, 128.3, 128.1, 127.9, 127.7, 127.0, 122.4, 114.9, 114.1, 104.4, 55.3, 45.2, 40.3, 31.4 ppm.

[0163] 2. High-resolution mass spectrometry: HRMS (ESI) C 29 H 25 O3 [M ++H]: 421.1798, Found: 421.1795.

[0164] It can be seen from the results that the theoretical mass is 421.1798, while the observed value of the peak found in the actual mass spectrum is 421.1795; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0165] is the product of this example.

[0166] Example 6

[0167] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 3 being 2-furyl, R 4 being hydrogen, the X group being CH2, and n = 1 of 5-(2-furyl)-1,3-cyclohexanedione as the reaction raw material, reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0168] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 5-(2-furyl)-1,3-cyclohexanedione (142.5 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL) and react at 45 °C for 2.5 h. The reaction equation is as follows:

[0169]

[0170] Concentrate the reaction solution and obtain 76.2 mg of solid product by silica gel column chromatography, and the calculated yield is 50%.

[0171] The analysis of the test is as follows:

[0172] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0173] 1 H NMR (300 MHz, CDCl3) δ 7.48 - 7.39 (m, 3H), 7.35 - 7.25 (m, 6H), 7.25 - 7.18 (m, 2H), 6.89 (s, 1H), 6.28 (dd, J1 = 3.3 Hz, J2 = 1.9 Hz, 1H), 6.08 - 6.01 (m, 1H), 5.73 (s, 1H), 3.65 - 3.51 (m, 1H), 3.22 - 2.93 (m, 2H), 2.82 - 2.58 (m, 2H) ppm.

[0174] 1313C NMR (75 MHz, CDCl3) δ 192.0, 164.1, 155.4, 153.8, 142.5, 141.6, 141.2, 139.5, 129.1, 129.0, 128.3, 128.1, 127.9, 127.0, 122.4, 114.8, 110.2, 105.0, 104.3, 42.0, 34.2, 28.3 ppm.

[0175] 2. High-resolution mass spectrometry: HRMS (ESI) C 26 H 21 O3 [M + + H]: 381.1485, Found: 381.1491.

[0176] It can be seen from the results that the theoretical mass is 381.1485, while the observed value of the peak found in the actual mass spectrometry is 381.1491; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0177] is the product of this example.

[0178] Example 7

[0179] Using R 1 = R 2 is γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with benzene, R 3 is carboxyl group, R 4 is hydrogen, the X group is CH2, and 3,5-dioxocyclohexanecarboxylic acid with n = 1 is used as the reaction raw material, and the reaction is carried out with scandium trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0180] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 3,5-dioxocyclohexanecarboxylic acid (125.0 mg, 0.8 mmol) and scandium trifluoromethanesulfonate (39.5 mg, 0.08 mmol) in ethyl acetate (4 mL), and react at 25 °C for 30 h. The reaction equation is as follows:

[0181]

[0182] Concentrate the reaction solution and obtain 113.0 mg of solid product by silica gel column chromatography. The calculated yield is 79%.

[0183] The analysis of the test is as follows:

[0184] 1. 1H NMR and 13C NMR analysis:

[0185] 11H NMR (300 MHz, CDCl3) δ 9.64 (brs, 1H), 7.48 - 7.36 (m, 3H), 7.34 - 7.26 (m, 5H), 7.24 - 7.18 (m, 2H), 6.88 (s, 1H), 5.70 (s, 1H), 3.29 - 3.19 (m, 1H), 3.09 (d, J = 7.1 Hz, 2H), 2.82 - 2.60 (m, 2H) ppm.

[0186] 13 13C NMR (75 MHz, CDCl3) δ 190.9, 177.8, 163.2, 154.2, 143.0, 141.1, 139.4, 129.1, 129.0, 128.3, 128.2, 128.0, 127.0, 122.4, 114.6, 104.2, 39.5, 39.2, 25.6 ppm.

[0187] 2. High-resolution mass spectrometry: HRMS (ESI) C 23 H 17 O4 [M - - H]: 357.1132, Found: 357.1132.

[0188] It can be seen from this result that its theoretical mass is 357.1132, and the observed value of the peak found in the actual mass spectrometry is 357.1132; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0189] is the product of this example.

[0190] Example 8

[0191] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, R 3 = R 4 being hydrogen, X group being CH2, and 1,3-cycloheptanedione with n = 2 as the reaction raw material, reacting with scandium trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0192] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,3-cycloheptanedione (101.0 mg, 0.8 mmol) and scandium trifluoromethanesulfonate (39.5 mg, 0.08 mmol) in acetonitrile (4 mL), and react at 0 °C for 34 h. The reaction equation is as follows:

[0193]

[0194] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 85.9 mg of solid product, and the yield was calculated to be 65%.

[0195] The analysis of the test is as follows:

[0196] 1. 1H NMR and 13C NMR analysis:

[0197] 1 H NMR(300MHz,CDCl3)δ7.47-7.37(m,3H),7.34-7.19(m,7H),6.82(s,1H),5.86(s,1H),2.84(t,J=6.2Hz,2H),2.68-2.58(m,2H),1.99-1.79(m,4H)ppm.

[0198] 13 C NMR(75MHz,CDCl3)δ196.2,160.5,151.4,141.6,141.4,139.6,129.2,128.8,128.2,127.8,127.7,126.9,124.9,114.9,109.0,44.3,29.4,24.7,22.8ppm.

[0199] 2. High resolution mass spectrometry: HRMS(ESI)C 23 H 21 O2[M + +H]:329.1536,Found:329.1533.

[0200] It can be seen from the results that the theoretical mass is 329.1536, while the observed value of the peak found in the actual mass spectrometry is 329.1533; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0201] This is the product of this example.

[0202] Example 9

[0203] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with 1 R 2 = phenyl and (bicyclo[3.2.1]octane-2,4-dione) as reaction raw

[0204] materials, and aluminum trifluoromethanesulfonate was used as the catalyst for the reaction. The specific implementation process is as follows:

[0205] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), bicyclo[3.2.1]octane-2,4-dione (110.5 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL), and react at 45 °C for 3 h. The reaction equation is as follows:

[0206]

[0207] Concentrate the reaction solution and obtain 125.4 mg of solid product by silica gel column chromatography. The calculated yield is 92%.

[0208] The analysis of the test is as follows:

[0209] 1. 1H NMR and 13C NMR analysis:

[0210] 1 H NMR (300 MHz, CDCl3) δ 7.46 - 7.38 (m, 3H), 7.32 - 7.18 (m, 7H), 6.90 (s, 1H), 5.65 (s, 1H), 3.33 (t, J = 4.6 Hz, 1H), 2.95 (dd, J1 = 7.4 Hz, J2 = 4.8 Hz, 1H), 2.23 - 1.94 (m, 3H), 1.79 - 1.65 (m, 2H), 1.59 - 1.44 (m, 1H) ppm.

[0211] 13 C NMR (75 MHz, CDCl3) δ 197.3, 171.7, 152.9, 141.8, 141.2, 139.5, 129.1, 129.0, 128.2, 128.0, 127.7, 126.8, 119.5, 115.0, 104.6, 49.8, 40.9, 36.9, 29.6, 25.2 ppm.

[0212] 2. High-resolution mass spectrometry: HRMS (ESI) C 24 H 21 O2 [M + + H]: 341.1536, Found: 341.1538.

[0213] It can be seen from this result that the theoretical mass is 341.1536, while the observed value of the peak found in the actual mass spectrum is 341.1538; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0214] It is the product of this example.

[0215] Example 10

[0216] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 3 = R 4 being hydrogen, the X group being NH, and n = 1 2,4-piperidinedione as the reaction raw material, reacting with an aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0217] Dissolve γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 2,4-piperidinedione (90.5 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) in acetonitrile (4 mL) and react at 45 °C for 2 h. The reaction equation is as follows:

[0218]

[0219] Concentrate the reaction solution and obtain 69.2 mg of solid product by silica gel column chromatography. The calculated yield is 55%.

[0220] The analysis of the test is as follows:

[0221] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0222] 1 H NMR (300 MHz, CDCl3) δ 7.48 - 7.36 (m, 3H), 7.30 (d, J = 4.2 Hz, 4H), 7.26 - 7.19 (m, 3H), 6.89 (s, 1H), 5.81 (s, 1H), 5.66 (s, 1H), 3.55 (t, J = 7.1 Hz, 2H), 2.85 (t, J = 6.9 Hz, 2H) ppm.

[0223] 13 C NMR (75 MHz, CDCl3) δ 165.2, 158.1, 153.3, 141.6, 141.5, 139.6, 129.3, 129.0, 128.3, 128.0, 127.8, 127.0, 116.9, 115.1, 106.1, 40.1, 22.8 ppm.

[0224] 2. High-resolution mass spectrometry: HRMS (ESI) C 21 H 18 NO2[M + +H]: 316.1332, Found: 316.1341.

[0225] It can be seen from the results that the theoretical mass is 316.1332, while the observed value of the peak found in the actual mass spectrum is 316.1341; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0226] is the product of this example.

[0227] Example 11

[0228] Using R 1 = R 2 being (E)-4,4-bis(4-fluorophenyl)-4-hydroxy-2-butenal with 4-fluorophenyl, R 3 = R 4 being hydrogen, X group being CH2, and 1,3-cyclohexanedione with n = 1 as the reaction raw material, reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0229] (E)-4,4-bis(4-fluorophenyl)-4-hydroxy-2-butenal (109.7 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 45 °C for 5 h. The reaction equation is as follows:

[0230]

[0231] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 121.8 mg of solid product, and the calculated yield was 87%.

[0232] The analysis of the test is as follows:

[0233] 1. 1H NMR and 13C NMR analysis:

[0234] 1 H NMR (300 MHz, CDCl3) δ 7.28 - 7.16 (m, 4H), 7.15 - 7.07 (m, 2H), 7.03 - 6.93 (m, 2H), 6.79 (s, 1H), 5.86 (s, 1H), 2.76 (t, J = 6.3 Hz, 2H), 2.48 - 2.38 (m, 2H), 2.11 (p, J = 6.4 Hz, 2H) ppm.

[0235] 1313C NMR (75 MHz, CDCl3) δ 194.0, 166.0, 162.53 (d, J = 248.5 Hz), 162.46 (d, J = 247.7 Hz), 152.8, 139.9, 137.5 (d, J = 3.2 Hz), 135.2 (d, J = 3.6 Hz), 131.0 (d, J = 8.1 Hz), 128.6 (d, J = 8.1 Hz), 122.4, 116.0 (d, J = 21.4 Hz), 115.2 (d, J = 21.6 Hz), 115.2 (d, J = 1.8 Hz), 104.7, 37.5, 23.2, 22.3 ppm.

[0236] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 17 F2O2 [M + + H]: 351.1191, Found: 351.1194.

[0237] It can be seen from the results that its theoretical mass is 351.1191, while the observed value of the peak found in the actual mass spectrometry is 351.1194; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0238] is the product of this example.

[0239] Example 12

[0240] Using R 1 = R 2 is (E)-4,4-bis(4-bromophenyl)-4-hydroxy-2-butenal with 4-bromophenyl, R 3 = R 4 is hydrogen, the X group is CH2, and 1,3-cyclohexanedione with n = 1 is used as the reaction raw material, and the reaction is carried out with aluminum trifluoromethanesulfonate as the catalyst. The specific implementation process is as follows:

[0241] (E)-4,4-Bis(4-bromophenyl)-4-hydroxy-2-butenal (158.4 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL), and the reaction was carried out at 60 °C for 4 h. The reaction equation is as follows:

[0242]

[0243] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 153.4 mg of solid product, and the calculated yield was 81%.

[0244] The analysis of the test is as follows:

[0245] 1. 1H and 13C NMR spectra for nuclear magnetic resonance analysis:

[0246] 1 HNMR(300MHz,CDCl3)δ7.56(d,J=8.5Hz,2H),7.42(d,J=8.7Hz,2H),7.11(d,J=8.3Hz,2H),7.09(d,J=8.2Hz,2H),6.83(s,1H),5.98(s,1H),2.76(t,J=6.3Hz,2H),2.44(t,J=6.4Hz,2H),2.12(p,J=6.4Hz,2H)ppm.

[0247] 13 C NMR(75MHz,CDCl3)δ194.0,166.3,152.5,140.1,139.5,138.0,132.2,131.5,131.1,128.6,122.6,122.4,122.2,115.7,105.5,37.6,23.3,22.3ppm.

[0248] 2. High-resolution mass spectrometry: HRMS(ESI)Calcd for C 22 H 17 Br2O2[M + +H]:470.9590,Found:470.9581.

[0249] It can be seen from this result that its theoretical mass is 470.9590, while the observed value of the peak found in the actual mass spectrum is 470.9581; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0250] This is the product of this example.

[0251] Example 13

[0252] Using (E)-4,4-bis(4-chlorophenyl)-4-hydroxy-2-butenal with R 1 =R 2 being 4-chlorophenyl, R 3 =R 4 being hydrogen, X group being CH2, and 1,3-cyclohexanedione with n = 1 as the reaction raw materials, and using aluminum trifluoromethanesulfonate as the catalyst for the reaction. The specific implementation process is as follows:

[0253] (E)-4,4-Bis(4-chlorophenyl)-4-hydroxy-2-butenal (122.9 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL), and the reaction was carried out at 60 °C for 4 h. The reaction equation is as follows:

[0254]

[0255] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 124.5 mg of solid product, and the calculated yield was 81%.

[0256] The analysis of the test is as follows:

[0257] 1. 1H NMR and 13C NMR analysis:

[0258] 1 H NMR (300 MHz, CDCl3) δ 7.45 - 7.36 (m, 2H), 7.30 - 7.22 (m, 2H), 7.21 - 7.11 (m, 4H), 6.82 (s, 1H), 5.96 (s, 1H), 2.76 (t, J = 6.2 Hz, 2H), 2.43 (t, J = 6.4 Hz, 2H), 2.12 (p, J = 6.4 Hz, 2H) ppm.

[0259] 13 C NMR (75 MHz, CDCl3) δ 194.0, 166.3, 152.5, 139.7, 139.4, 137.6, 134.1, 133.9, 130.8, 129.3, 128.5, 128.2, 122.5, 115.7, 105.4, 37.6, 23.2, 22.3 ppm.

[0260] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 17 Cl2O2 [M + + H]: 383.0600, Found: 383.0601.

[0261] It can be seen from the results that the theoretical mass is 383.0600, and the observed value of the peak found in the actual mass spectrometry is 383.0601; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0262] This is the product of this example.

[0263] Example 14

[0264] Using R 1 = R2 (E)-4,4-bis(4-methylphenyl)-4-hydroxy-2-butenal, where R 3 = R 4 is hydrogen, the X group is CH2, and 1,3-cyclohexanedione with n = 1 is used as a reaction raw material, and the reaction is carried out using an aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0265] (E)-4,4-bis(4-methylphenyl)-4-hydroxy-2-butenal (106.5 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL), and the reaction was carried out at 45 °C for 2 h. The reaction equation is as follows:

[0266]

[0267] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 75.3 mg of a solid product, and the calculated yield was 55%.

[0268] The analysis of the test is as follows:

[0269] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0270] 1 H NMR (300 MHz, CDCl3) δ 7.25 - 7.15 (m, 4H), 7.13 - 7.04 (m, 4H), 6.82 (s, 1H), 5.75 (s, 1H), 2.76 (t, J = 6.2 Hz, 2H), 2.44 - 2.34 (m, 5H), 2.32 (s, 3H), 2.08 (p, J = 6.4 Hz, 2H) ppm.

[0271] 13 C NMR (75 MHz, CDCl3) δ 194.1, 165.6, 153.5, 142.3, 138.8, 137.7, 137.6, 136.5, 129.6, 129.0, 128.9, 126.9, 122.5, 114.0, 103.8, 37.6, 23.2, 22.3, 21.3, 21.0 ppm.

[0272] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 24 H 23 O2 [M + + H]: 343.1693, Found: 343.1696.

[0273] It can be seen from the results that the theoretical mass is 343.1693, while the observed value of the peak found in the actual mass spectrometry is 343.1696; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0274] is the product of this example.

[0275] Example 15

[0276] Using R 1 = R 2 being (E)-4,4-bis(3-chlorophenyl)-4-hydroxy-2-butenal with 3-chlorophenyl, R 3 = R 4 being hydrogen, X group being CH2, and 1,3-cyclohexanedione with n = 1 as the reaction raw material, and reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0277] (E)-4,4-bis(3-chlorophenyl)-4-hydroxy-2-butenal (122.9 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 80 °C for 2.5 h. The reaction equation is as follows:

[0278]

[0279] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 117.7 mg of solid product, and the calculated yield was 77%.

[0280] The analysis of the test is as follows:

[0281] 1. 1H NMR and 13C NMR analysis:

[0282] 1 H NMR(300 MHz, CDCl3) δ 7.46 - 7.33 (m, 2H), 7.30 - 7.19 (m, 4H), 7.18 - 7.08 (m, 2H), 6.86 (s, 1H), 5.93 (s, 1H), 2.75 (t, J = 6.3 Hz, 2H), 2.43 (t, J = 6.4 Hz, 2H), 2.11 (p, J = 6.4 Hz, 2H) ppm.

[0283] 1313C NMR (75 MHz, CDCl3) δ 193.9, 166.4, 152.2, 142.7, 140.7, 138.8, 134.8, 134.5, 130.3, 129.6, 129.3, 128.4, 127.9, 127.5, 126.8, 125.1, 122.5, 116.5, 105.9, 37.5, 23.2, 22.2 ppm.

[0284] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 17 Cl2O2 [M + + H]: 383.0600, Found: 383.0607.

[0285] It can be seen from this result that its theoretical mass is 383.0600, while the observed value of the peak found in the actual mass spectrometry is 383.0607; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0286] is the product of this example.

[0287] Example 16

[0288] Using (E)-4-hydroxy-4,4-bis(naphthalen-2-yl)but-2-enal with R 1 = R 2 being naphthyl, R 3 = R 4 being hydrogen, X group being CH2, and 1,3-cyclohexanedione with n = 1 as the reaction raw materials, reacting with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0289] (E)-4-Hydroxy-4,4-bis(naphthalen-2-yl)but-2-enal (135.4 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 45 °C for 5 h. The reaction equation is as follows:

[0290]

[0291] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 145.6 mg of solid product, and the calculated yield was 88%.

[0292] The analysis of the test is as follows:

[0293] 1. 1H NMR and 13C NMR analysis:

[0294] 11H NMR (300 MHz, CDCl3) δ 7.96 - 7.86 (m, 2H), 7.80 - 7.70 (m, 4H), 7.67 - 7.58 (m, 2H), 7.57 - 7.47 (m, 3H), 7.46 - 7.35 (m, 3H), 7.08 (s, 1H), 5.86 (s, 1H), 2.67 (t, J = 6.2 Hz, 2H), 2.35 (t, J = 6.4 Hz, 2H), 2.02 (p, J = 6.3 Hz, 2H) ppm.

[0295] 13 13C NMR (126 MHz, CDCl3) δ 194.1, 166.1, 153.2, 142.0, 139.0, 137.0, 133.7, 133.2, 133.0, 132.9, 128.6, 128.5, 128.3, 128.1, 127.9, 127.49, 127.47, 127.0, 126.3, 126.2, 124.6, 122.6, 115.7, 104.9, 37.6, 23.2, 22.3 ppm.

[0296] 2. High Resolution Mass Spectrometry: HRMS (ESI) Calcd for C 30 H 23 O2 [M + + H]: 415.1693, Found: 415.1690.

[0297] It can be seen from the results that the theoretical mass is 415.1693, while the observed value of the peak found in the actual mass spectrum is 415.169; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0298] is the product of this example.

[0299] Example 17

[0300] Using (E)-3-(9-hydroxy-9H-fluoren-9-yl)acrolein R 3 = R 4 is hydrogen, the X group is CH2, and 1,3-cyclohexanedione with n = 1 is used as the reaction raw material, and the reaction is carried out with aluminum trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0301] (E)-3-(9-hydroxy-9H-fluoren-9-yl)acrolein (94.5 mg, 0.4 mmol), 1,3-cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 45 °C for 7 h. The reaction equation is as follows:

[0302]

[0303] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 87.3 mg of a solid product, and the yield was calculated to be 70%.

[0304] The analysis of the test is as follows:

[0305] 1. 1H NMR and 13C NMR analysis:

[0306] 1 H NMR (300 MHz, CDCl3) δ 8.52 (d, J = 7.7 Hz, 1H), 7.77 - 7.60 (m, 3H), 7.43 - 7.21 (m, 4H), 7.14 (s, 1H), 6.94 (s, 1H), 3.00 (t, J = 6.2 Hz, 2H), 2.53 (t, J = 6.4 Hz, 2H), 2.22 (p, J = 6.4 Hz, 2H) ppm.

[0307] 13 C NMR (75 MHz, CDCl3) δ 193.9, 167.8, 151.9, 141.3, 139.8, 138.9, 135.7, 134.2, 128.8, 128.3, 127.1, 127.0, 125.4, 123.1, 120.0, 119.7, 119.6, 111.7, 110.3, 37.6, 23.6, 22.3 ppm.

[0308] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 17 O2 [M + + H]: 313.1223, Found: 313.1227.

[0309] It can be seen from the results that its theoretical mass is 313.1223, while the observed value of the peak found in the actual mass spectrometry is 313.1227; combined with nuclear magnetic resonance, the structure of the product can be determined as follows:

[0310] is the product of this example.

[0311] Example 18

[0312] Using R 1 is phenyl, R 2 is methyl (E)-4-hydroxy-4-phenyl-2-pentenal, R 3 = R 4Using 1,3 - cyclohexanedione with hydrogen as the hydrogen atom, X group as CH2, and n = 1 as the reaction raw material, the reaction is carried out with aluminum trifluoromethanesulfonate as the catalyst. The specific implementation process is as follows:

[0313] (E)-4 - Hydroxy - 4 - phenyl - 2 - pentenal (70.5 mg, 0.4 mmol), 1,3 - cyclohexanedione (89.7 mg, 0.8 mmol) and aluminum trifluoromethanesulfonate (19.0 mg, 0.04 mmol) were dissolved in acetonitrile (4 mL) and reacted at 45 °C for 7 h. The reaction equation is as follows:

[0314]

[0315] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 63.2 mg of solid product. The calculated yield was 63%, and the ratio of stereoisomers = 79 / 21.

[0316] The analysis of the test is as follows:

[0317] 1. 1H NMR and 13C NMR analysis:

[0318] 1 H NMR (300 MHz, CDCl3) δ 7.52 - 7.17 (m, 5H), 6.62 (s, 0.8H, major), 6.58 (s, 0.8H, major), 6.26 (s, 0.2H, minor), 5.78 (s, 0.2H, minor), 2.89 (t, J = 6.3 Hz, 1.6H, major), 2.73 (t, J = 6.3 Hz, 0.4H, minor), 2.50 (t, J = 6.5 Hz, 1.6H, major), 2.37 (s, 2.8H, major), 2.23 - 2.12 (m, 2.2H, major + minor), 2.08 (p, J = 6.4 Hz, 0.4H, minor) ppm.

[0319] 13 C NMR (75 MHz, CDCl3) δ 194.4, 194.2, 165.9, 165.1, 153.6, 152.7, 143.0, 141.6, 140.4, 137.9, 128.6, 128.3, 127.5, 127.4, 127.0, 125.7, 122.5, 122.1, 115.0, 114.8, 104.7, 102.7, 37.49, 37.46, 27.0, 23.3, 23.1, 22.4, 22.3, 18.2 ppm.

[0320] 2. High - resolution mass spectrometry: HRMS (ESI) Calcd for C 17 H17 O2[M + +H]: 253.1223, Found: 253.1222.

[0321] It can be seen from this result that the theoretical mass is 253.1223, while the observed value of the peak found in the actual mass spectrum is 253.1222; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0322] is the product of this example.

[0323] Example 19

[0324] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 7 = R 8 being methyl, and Y being oxygen atom 1,3-dimethylbarbituric acid as the reaction raw materials, reacting with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0325] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,3-dimethylbarbituric acid (125.0 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 4 h. The reaction equation is as follows:

[0326]

[0327] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 119.8 mg of solid product, and the calculated yield was 84%.

[0328] The analysis of the test is as follows:

[0329] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0330] 1 H NMR (300 MHz, CDCl3) δ 7.49 - 7.38 (m, 3H), 7.33 - 7.24 (m, 7H), 6.82 (s, 1H), 6.17 (s, 1H), 3.33 (s, 3H), 3.19 (s, 3H) ppm.

[0331] 1313C NMR (75 MHz, CDCl3) δ 157.9, 154.4, 150.3, 149.4, 141.6, 141.0, 139.8, 129.5, 128.7, 128.3, 127.93, 127.85, 126.9, 113.6, 106.3, 98.3, 29.1, 28.3 ppm.

[0332] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 19 N2O3 [M + + H]: 359.1390, Found: 359.1395.

[0333] It can be seen from the results that its theoretical mass is 359.1390, while the observed value of the peak found in the actual mass spectrometry is 359.13956; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0334] is the product of this example.

[0335] Example 20

[0336] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, 1,3-diethyl-2-thiobarbituric acid with R 7 = R 8 being ethyl and Y being a sulfur atom as reaction raw materials, and using bismuth trifluoromethanesulfonate as a catalyst for the reaction. The specific implementation process is as follows:

[0337] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,3-diethyl-2-thiobarbituric acid (160.0 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL), and the reaction was carried out at 25 °C for 3 h. The reaction equation is as follows:

[0338]

[0339] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 145.7 mg of a solid product, and the calculated yield was 90%.

[0340] The analysis of the test is as follows:

[0341] 1. 1H NMR and 13C NMR analysis:

[0342] 11H NMR (300 MHz, CDCl3) δ 7.51 - 7.35 (m, 3H), 7.35 - 7.21 (m, 7H), 6.85 (s, 1H), 6.27 (s, 1H), 4.57 (q, J = 6.9 Hz, 2H), 4.18 (q, J = 7.0 Hz, 2H), 1.27 (t, J = 7.0 Hz, 3H), 1.15 (t, J = 7.0 Hz, 3H) ppm.

[0343] 13 13C NMR (75 MHz, CDCl3) δ 172.8, 156.2, 153.8, 149.8, 142.5, 140.8, 139.7, 129.2, 128.6, 128.3, 128.1, 127.8, 126.9, 113.2, 106.3, 102.3, 44.5, 43.4, 12.4, 11.6 ppm.

[0344] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 24 H 23 N2O2S [M + + H]: 403.1475, Found: 403.1478.

[0345] It can be seen from this result that its theoretical mass is 403.1475, while the observed value of the peak found in the actual mass spectrometry is 403.1478; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0346] This is the product of this example.

[0347] Example 21

[0348] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, and 2,4-pentanedione with R 5 = R 6 being methyl as reaction raw materials, reacting with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0349] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 2,4-pentanedione (95.3 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0350]

[0351] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 117.0 mg of the solid product, and the yield was calculated to be 97%.

[0352] The analysis of the test is as follows:

[0353] 1. 1H NMR and 13C NMR analysis:

[0354] 1 H NMR(300MHz,CDCl3)δ7.49-7.39(m,3H),7.35-7.22(m,7H),6.87(s,1H),5.55(s,1H),2.46(s,3H),2.14(s,3H)ppm.

[0355] 13 C NMR(75MHz,CDCl3)δ194.0,157.1,150.7,141.0,139.9,129.3,128.9,128.3,127.72,127.65,126.7,122.7,115.0,109.1,28.6,14.2ppm.

[0356] 2. High resolution mass spectrometry: HRMS(ESI)Calcd for C 21 H 19 O2[M + +H]:303.1380,Found:303.1383.

[0357] It can be seen from the results that the theoretical mass is 303.1380, while the observed value of the peak found in the actual mass spectrometry is 303.1383; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0358] This is the product of this example.

[0359] Example 22

[0360] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 =R 2 being phenyl and 2,6-dimethyl-3,5-heptanedione with R 5 =R 6 being isopropyl as the reaction raw materials, and bismuth trifluoromethanesulfonate as the catalyst for the reaction. The specific implementation process is as follows:

[0361] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 2,6-dimethyl-3,5-heptanedione (125.0 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL), and the reaction was carried out at 25 °C for 9 h. The reaction equation is as follows:

[0362]

[0363] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 124.8 mg of an oily product, and the calculated yield was 87%.

[0364] The analysis of the test is as follows:

[0365] 1. 1H NMR and 13C NMR analysis:

[0366] 1 H NMR (300 MHz, CDCl3) δ 7.49 - 7.38 (m, 3H), 7.36 - 7.21 (m, 7H), 6.87 (s, 1H), 5.75 (s, 1H), 3.65 (hept, J = 6.9 Hz, 1H), 2.77 (hept, J = 6.9 Hz, 1H), 1.08 (d, J = 6.9 Hz, 6H), 1.04 (d, J = 6.9 Hz, 6H) ppm.

[0367] 13 C NMR (75 MHz, CDCl3) δ 200.5, 166.4, 150.3, 141.3, 140.6, 140.2, 129.5, 128.7, 128.2, 127.6, 127.5, 126.8, 119.3, 115.1, 109.5, 38.2, 27.4, 20.3, 18.5 ppm.

[0368] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 25 H 27 O2 [M + + H]: 359.2006, Found: 359.1999.

[0369] It can be seen from this result that the theoretical mass is 359.2006, while the observed value of the peak found in the actual mass spectrum is 359.1999; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0370] is the product of this example.

[0371] Example 23

[0372] Using R1 = R 2 γ-hydroxy-γ-diphenyl-α,β-unsaturated enal where R is phenyl, 5 = R 6 1,3-diphenylpropanedione where R is phenyl was used as the reaction raw material, and the reaction was carried out with bismuth trifluoromethanesulfonate as the catalyst. The specific implementation process is as follows:

[0373] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,3-diphenylpropanedione (179.4 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL), and the reaction was carried out at 25 °C for 9 h. The reaction equation is as follows:

[0374]

[0375] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 128.5 mg of solid product, and the calculated yield was 75%.

[0376] The analysis of the test is as follows:

[0377] 1. 1H NMR and 13C NMR analysis:

[0378] 1 H NMR (300 MHz, CDCl3) δ 7.75 (d, J = 7.6 Hz, 2H), 7.56 - 7.26 (m, 15H), 7.25 - 7.16 (m, 3H), 6.96 (s, 1H), 5.94 (s, 1H) ppm.

[0379] 13 C NMR (75 MHz, CDCl3) δ 191.4, 154.1, 151.3, 142.1, 141.3, 140.1, 137.7, 132.8, 129.6, 129.4, 129.3, 128.8, 128.3, 128.2, 128.1, 127.8, 127.6, 127.02, 127.00, 122.2, 114.6, 113.6 ppm.

[0380] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 31 H 22 NaO2 [M + + Na]: 449.1512, Found: 449.1504.

[0381] It can be seen from the results that the theoretical mass is 449.1512, while the observed value of the peak found in the actual mass spectrum is 449.1504; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0382] is the product of this example.

[0383] Example 24

[0384] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 5 being ethoxy, R 6 being methyl ethyl acetoacetate as the reaction raw material, and reacting with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0385] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), ethyl acetoacetate (104.1 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0386]

[0387] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 128.8 mg of an oily product, and the calculated yield was 97%.

[0388] The analysis of the test is as follows:

[0389] 1. 1H NMR and 13C NMR analysis:

[0390] 1 H NMR (300 MHz, CDCl3) δ 7.47 - 7.35 (m, 3H), 7.33 - 7.19 (m, 7H), 6.84 (s, 1H), 5.73 (s, 1H), 4.18 (q, J = 7.1 Hz, 2H), 2.43 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H) ppm.

[0391] 13 C NMR (75 MHz, CDCl3) δ 163.7, 157.7, 150.7, 141.4, 140.8, 139.8, 129.3, 128.8, 128.2, 127.7, 127.6, 126.8, 115.12, 115.09, 109.5, 59.9, 14.2, 13.6 ppm.

[0392] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 21 O3 [M ++H]: 333.1485, Found: 333.1484.

[0393] It can be seen from the results that the theoretical mass is 333.1485, while the observed value of the peak found in the actual mass spectrum is 333.1484; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0394] is the product of this example.

[0395] Example 25

[0396] Using R 1 = R 2 is phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 5 is cyanoethoxy, R 6 is methyl 2-cyanoethyl 3-oxobutyrate as the reaction raw material, and the reaction is carried out with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0397] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 2-cyanoethyl 3-oxobutyrate (104.1 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0398]

[0399] The reaction solution was concentrated and purified by silica gel column chromatography to obtain 135.8 mg of solid product, and the calculated yield was 95%.

[0400] The analysis of the test is as follows:

[0401] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0402] 1 H NMR (300 MHz, CDCl3) δ 7.49 - 7.39 (m, 3H), 7.34 - 7.19 (m, 7H), 6.84 (s, 1H), 5.68 (s, 1H), 4.30 (t, J = 6.2 Hz, 2H), 2.66 (t, J = 6.2 Hz, 2H), 2.46 (s, 3H) ppm.

[0403] 1313C NMR (75 MHz, CDCl3) δ 162.8, 158.6, 151.1, 141.4, 141.1, 139.6, 129.2, 128.8, 128.2, 127.8, 127.6, 126.8, 116.7, 114.8, 113.9, 109.0, 58.2, 17.9, 13.8 ppm.

[0404] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 23 H 20 NO3 [M + + H]: 358.1438, Found: 358.1439.

[0405] It can be seen from the results that the theoretical mass is 358.1438, while the observed value of the peak found in the actual mass spectrometry is 358.1439; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0406] This is the product of this example.

[0407] Example 26

[0408] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, allyloxy for R 5 and allyl acetoacetate with R 6 being methyl as the reaction raw materials, and using bismuth trifluoromethanesulfonate as the catalyst for the reaction. The specific implementation process is as follows:

[0409] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), allyl acetoacetate (113.7 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0410]

[0411] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 130.5 mg of an oily product, and the calculated yield was 95%.

[0412] The analysis of the test is as follows:

[0413] 1. 1H NMR and 13C NMR analysis:

[0414] 11H NMR (300 MHz, CDCl3) δ 7.49 - 7.35 (m, 3H), 7.34 - 7.19 (m, 7H), 6.85 (s, 1H), 5.98 - 5.83 (m, 1H), 5.72 (s, 1H), 5.32 - 5.14 (m, 2H), 4.63 (dt, J1 = 5.4 Hz, J2 = 1.6 Hz, 2H), 2.45 (s, 3H) ppm.

[0415] 13 13C NMR (75 MHz, CDCl3) δ 163.3, 158.0, 150.9, 141.3, 141.0, 139.8, 132.2, 129.3, 128.8, 128.2, 127.7, 127.6, 126.8, 117.4, 115.1, 114.8, 109.4, 64.4, 13.7 ppm.

[0416] 2. High - resolution mass spectrometry: HRMS (ESI) Calcd for C 23 H 21 O3 [M + + H]: 345.1485, Found: 345.1484.

[0417] It can be seen from this result that its theoretical mass is 345.1485, while the observed value of the peak found in the actual mass spectrometry is 345.1484; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0418] This is the product of this example.

[0419] Example 27

[0420] Using γ - hydroxy - γ - diphenyl - α,β - unsaturated enal with R 1 = R 2 being phenyl, R 5 being methoxyethoxy, and R 6 being methyl ethyl acetoacetate as the reaction raw material, and reacting with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0421] γ - hydroxy - γ - diphenyl - α,β - unsaturated enal (95.3 mg, 0.4 mmol), methyl ethyl acetoacetate (128.1 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0422]

[0423] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 138.5 mg of an oily product, and the calculated yield was 96%.

[0424] The analysis of the test is as follows:

[0425] 1. 1H NMR and 13C NMR analysis:

[0426] 1 H NMR(300MHz,CDCl3)δ7.48 - 7.36(m,3H),7.33 - 7.18(m,7H),6.84(s,1H),5.73(s,1H),4.27(t,J=4.7Hz,2H),3.58(t,J=4.7Hz,2H),3.35(s,3H),2.45(s,3H)ppm.

[0427] 13 C NMR(75MHz,CDCl3)δ163.5,158.1,150.8,141.3,140.9,139.8,129.3,128.8,128.2,127.62,127.56,126.8,115.0,114.8,109.4,70.4,63.2,59.0,13.6ppm.

[0428] 2. High - resolution mass spectrometry: HRMS(ESI)Calcd for C 23 H 22 NaO4[M + +Na]:385.1410,Found:385.1414.

[0429] It can be seen from the results that the theoretical mass is 385.1410, while the observed value of the peak found in the actual mass spectrometry is 385.1414; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0430] This is the product of this example.

[0431] Example 28

[0432] Using γ - hydroxy - γ - diphenyl - α,β - unsaturated enal with R 1 =R 2 being phenyl, R 5 being 3 - bromopropoxy, and R 6 being methyl 3 - oxobutyrate - 3 - bromopropyl ester as the reaction raw materials, and using bismuth trifluoromethanesulfonate as the catalyst for the reaction. The specific implementation process is as follows:

[0433] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 3-bromopropyl 3-oxobutyrate (177.6 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0434]

[0435] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 160.8 mg of an oily product, and the calculated yield was 94%.

[0436] The analysis of the test is as follows:

[0437] 1. 1H NMR and 13C NMR analysis:

[0438] 1 H NMR (300 MHz, CDCl3) δ 7.49 - 7.39 (m, 3H), 7.34 - 7.19 (m, 7H), 6.86 (s, 1H), 5.57 (s, 1H), 4.24 (t, J = 5.9 Hz, 2H), 3.39 (t, J = 6.7 Hz, 2H), 2.45 (s, 3H), 2.15 (p, J = 6.3 Hz, 2H) ppm.

[0439] 13 C NMR (75 MHz, CDCl3) δ 163.3, 158.0, 150.9, 141.1, 141.0, 139.8, 129.3, 128.9, 128.3, 127.7, 127.6, 126.7, 115.0, 114.6, 109.2, 61.5, 31.7, 29.2, 13.6 ppm.

[0440] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 23 H 22 BrO3 [M + + H]: 425.0747, Found: 425.0749.

[0441] It can be seen from this result that the theoretical mass is 425.0747, while the observed value of the peak found in the actual mass spectrum is 425.0749; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0442] This is the product of this example.

[0443] Example 29

[0444] Using R 1 = R2 γ-hydroxy-γ-diphenyl-α,β-unsaturated enal where R is phenyl 5 R is L-mentholoxy 6 (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 3-oxobutyrate where R is methyl is used as a reaction raw material, and the reaction is carried out with bismuth trifluoromethanesulfonate as a catalyst. The specific implementation process is as follows:

[0445] γ-hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 3-oxobutyrate (192.3 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) are dissolved in ethyl acetate (4 mL), and the reaction is carried out at 25 °C for 5 h. The reaction equation is as follows:

[0446]

[0447] The reaction solution is concentrated and then purified by silica gel column chromatography to obtain 171.6 mg of an oily product, and the calculated yield is 97%.

[0448] The analysis of the test is as follows:

[0449] 1. 1H NMR and 13C NMR analysis:

[0450] 1 H NMR (300 MHz, CDCl3) δ 7.46 - 7.36 (m, 3H), 7.34 - 7.19 (m, 7H), 6.86 (s, 1H), 5.66 (s, 1H), 4.70 (td, J1 = 10.8 Hz, J2 = 4.3 Hz, 1H), 2.44 (s, 3H), 2.11 - 2.01 (m, 1H), 1.88 - 1.75 (m, 1H), 1.72 - 1.62 (m, 2H), 1.56 - 1.44 (m, 1H), 1.41 - 1.31 (m, 1H), 1.16 - 0.96 (m, 2H), 0.93 - 0.85 (m, 7H), 0.73 (d, J = 6.9 Hz, 3H) ppm.

[0451] 13 C NMR (75 MHz, CDCl3) δ 163.4, 157.6, 150.7, 141.3, 140.8, 139.9, 129.4, 128.8, 128.3, 127.7, 127.6, 126.8, 115.4, 115.2, 109.6, 73.9, 47.1, 41.0, 34.3, 31.3, 26.4, 23.7, 22.0, 20.7, 16.6, 13.7 ppm.

[0452] 2. High-resolution mass spectrometry: HRMS(ESI) Calcd for C 30 H 35 O3[M + +H]: 443.2581, Found: 443.2559.

[0453] It can be seen from this result that its theoretical mass is 443.2581, while the observed value of the peak found in the actual mass spectrometry is 443.2559; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0454] is the product of this example.

[0455] Example 30

[0456] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 5 being DL-isoborneoxy, R 6 being methyl 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 3-oxobutyrate as the reaction raw material, reacting with bismuth trifluoromethanesulfonate catalyst, the specific implementation process is as follows:

[0457] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 3-oxobutyrate (190.6 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0458]

[0459] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 173.1 mg of an oily product, and the calculated yield was 98%.

[0460] The analysis of the test is as follows:

[0461] 1. 1H NMR and 13C NMR analysis:

[0462] 11H NMR (300 MHz, CDCl3) δ 7.47 - 7.36 (m, 3H), 7.34 - 7.19 (m, 7H), 6.89 (s, 1H), 5.51 (s, 1H), 4.68 (dd, J1 = 7.8 Hz, J2 = 3.1 Hz, 1H), 2.48 (s, 3H), 1.86 - 1.61 (m, 4H), 1.58 - 1.48 (m, 1H), 1.20 - 1.02 (m, 2H), 0.86 (d, J = 7.8 Hz, 6H), 0.78 (s, 3H) ppm.

[0463] 13 13C NMR (75 MHz, CDCl3) δ 163.2, 157.7, 150.7, 141.1, 140.8, 139.8, 129.2, 128.9, 128.3, 127.9, 127.6, 126.7, 115.3, 115.2, 109.2, 80.6, 48.6, 46.8, 45.0, 38.9, 33.7, 27.0, 20.2, 20.1, 13.5, 11.5 ppm.

[0464] 2. High Resolution Mass Spectrometry: HRMS (ESI) Calcd for C 30 H 32 NaO3 [M + + Na]:: 463.2244, Found:: 463.2246.

[0465] It can be seen from this result that its theoretical mass is 463.2244, while the observed value of the peak found in the actual mass spectrometry is 463.2246; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0466] This is the product of this example.

[0467] Example 31

[0468] Using γ - hydroxy - γ - diphenyl - α,β - unsaturated enal with R 1 = R 2 being phenyl, R 5 being dehydroepiandrosterone oxy group, and R 6 being methyl (3S,8R,9S,10R,13S,14S) - 10,13 - dimethyl - 17 - oxo - 2,3,4,7,8,9,10,11,12,13,14,15,16,17 - tetradecahydro - 1H - cyclopenta[a]phenanthren - 3 - yl - 3 - oxobutyrate as the reaction raw material, and using bismuth trifluoromethanesulfonate catalyst for the reaction. The specific implementation process is as follows:

[0469] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), (3S,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl-3-oxobutyrate (298.0 mg, 0.8 mmol) and bismuth(III) trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 3 h. The reaction equation is as follows:

[0470]

[0471] The reaction solution was concentrated and purified by silica gel column chromatography to obtain 194.5 mg of solid product, and the calculated yield was 85%.

[0472] The test analysis is as follows:

[0473] 1. 1H NMR and 13C NMR analysis:

[0474] 1 H NMR (300 MHz, CDCl3) δ 7.51 - 7.36 (m, 3H), 7.34 - 7.20 (m, 7H), 6.84 (s, 1H), 5.73 (s, 1H), 5.41 (d, J = 5.1 Hz, 1H), 4.73 - 4.59 (m, 1H), 2.51 - 2.24 (m, 6H), 2.17 - 2.00 (m, 2H), 1.99 - 1.82 (m, 4H), 1.74 - 1.41 (m, 6H), 1.35 - 1.03 (m, 7H), 0.88 (s, 3H) ppm.

[0475] 13 C NMR (75 MHz, CDCl3) δ 220.8, 163.1, 157.6, 150.7, 141.4, 140.8, 139.9, 139.8, 129.3, 128.7, 128.2, 127.64, 127.56, 126.8, 121.8, 115.3, 115.1, 109.7, 73.5, 51.6, 50.1, 47.4, 38.1, 36.9, 36.7, 35.7, 31.4, 31.3, 30.7, 27.8, 21.8, 20.3, 19.3, 13.7, 13.5 ppm.

[0476] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 39 H 42 NaO4 [M ++Na]: 597.2975, Found: 597.2966.

[0477] It can be seen from this result that the theoretical mass is 597.2975, while the observed value of the peak found in the actual mass spectrum is 597.2966; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0478] is the product of this example.

[0479] Example 32

[0480] Using R 1 = R 2 being phenyl γ-hydroxy-γ-diphenyl-α,β-unsaturated enal, R 5 being fructose diacetonoxy, R 6 being methyl (5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis(1,3)dioxolane[4,5-b:4',5'-d]pyran-5-ylmethyl-3-oxobutyrate as the reaction raw material, and using bismuth trifluoromethanesulfonate catalyst for the reaction. The specific implementation process is as follows:

[0481] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), (5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis(1,3)dioxolane[4,5-b:4',5'-d]pyran-5-ylmethyl-3-oxobutyrate (275.5 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL) and reacted at 25 °C for 5 h. The reaction equation is as follows:

[0482]

[0483] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 164.4 mg of an oily product, and the calculated yield was 75%.

[0484] The analysis of the test is as follows:

[0485] 1. Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0486] 11H NMR (300 MHz, CDCl3) δ 7.49 - 7.38 (m, 3H), 7.32 - 7.27 (m, 5H), 7.25 - 7.21 (m, 2H), 6.85 (s, 1H), 5.72 (s, 1H), 4.63 (dd, J1 = 7.9 Hz, J2 = 2.7 Hz, 1H), 4.55 (d, J = 11.8 Hz, 1H), 4.28 - 4.21 (m, 2H), 4.08 (d, J = 11.8 Hz, 1H), 3.92 (dd, J1 = 13.0 Hz, J2 = 1.9 Hz, 1H), 3.76 (dd, J1 = 13.0 Hz, J2 = 0.8 Hz, 1H), 2.49 (s, 3H), 1.52 (s, 3H), 1.46 (s, 3H), 1.36 (s, 3H), 1.18 (s, 3H) ppm.

[0487] 13 13C NMR (75 MHz, CDCl3) δ 162.9, 158.9, 150.9, 141.4, 141.1, 139.9, 129.4, 128.9, 128.3, 127.74, 127.70, 126.9, 115.1, 114.4, 109.2, 108.9, 108.7, 101.6, 70.9, 70.2, 70.1, 63.9, 61.3, 26.5, 25.9, 25.7, 24.1, 13.7 ppm.

[0488] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 32 H 35 O8[M + +H]: 547.2326, Found: 547.2318.

[0489] It can be seen from this result that its theoretical mass is 547.2326, while the observed value of the peak found in the actual mass spectrometry is 547.2318; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0490] is the product of this example.

[0491] Example 33

[0492] Using γ-hydroxy-γ-diphenyl-α,β-unsaturated enal with R 1 = R 2 being phenyl, R 5 being citronellyloxy, and R 6 being methyl 3,7-dimethyloct-6-en-1-yl 3-oxobutyrate as the reaction raw material, reacting with bismuth trifluoromethanesulfonate catalyst, the specific implementation process is as follows:

[0493] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), 3,7-dimethyloct-6-en-1-yl 3-oxobutyrate (192.3 mg, 0.8 mmol) and bismuth(III) trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL), and the reaction was carried out at 25 °C for 5 h. The reaction equation is as follows:

[0494]

[0495] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 155.6 mg of solid product, and the calculated yield was 88%.

[0496] The analysis of the test is as follows:

[0497] 1. 1H NMR and 13C NMR analysis:

[0498] 1 H NMR (300 MHz, CDCl3) δ 7.48 - 7.35 (m, 3H), 7.33 - 7.19 (m, 7H), 6.85 (s, 1H), 5.68 (s, 1H), 5.14 - 5.04 (m, 1H), 4.25 - 4.08 (m, 2H), 2.44 (s, 3H), 2.10 - 1.86 (m, 2H), 1.73 - 1.63 (m, 4H), 1.60 (s, 3H), 1.58 - 1.41 (m, 2H), 1.40 - 1.28 (m, 1H), 1.27 - 1.12 (m, 1H), 0.90 (d, J = 6.4 Hz, 3H) ppm.

[0499] 13 C NMR (75 MHz, CDCl3) δ 163.8, 157.7, 150.8, 141.3, 140.8, 139.8, 131.2, 129.3, 128.8, 128.2, 127.7, 127.6, 126.8, 124.6, 115.14, 115.12, 109.5, 62.4, 36.9, 35.4, 29.5, 25.6, 25.4, 19.4, 17.6, 13.6 ppm.

[0500] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 30 H 35 O3 [M + + H]: 443.2581, Found: 443.2574.

[0501] As can be seen from the results, its theoretical mass is 443.2581, while the observed value of the peak found in the actual mass spectrum is 443.2574; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0502] is the product of this example.

[0503] Example 34

[0504] Using R 1 = R 2 is γ-hydroxy-γ-diphenyl-α,β-unsaturated enal of benzene, R 5 is dihydrocholesteroloxy, R 6 is (3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)hexadecahydro-1H-cyclopenta[a]phenanthren-3-yl 3-oxobutyrate of methyl as the reaction raw material, and the reaction is carried out with bismuth trifluoromethanesulfonate catalyst. The specific implementation process is as follows:

[0505] γ-Hydroxy-γ-diphenyl-α,β-unsaturated enal (95.3 mg, 0.4 mmol), (3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)hexadecahydro-1H-cyclopenta[a]phenanthren-3-yl 3-oxobutyrate (378.2 mg, 0.8 mmol) and bismuth trifluoromethanesulfonate (13.1 mg, 0.02 mmol) were dissolved in ethyl acetate (4 mL), and the reaction was carried out at 25 °C for 5 h. The reaction equation is as follows:

[0506]

[0507] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 269.7 mg of solid product, and the calculated yield was 99%.

[0508] The analysis of the test is as follows:

[0509] 1. Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0510] 11H NMR (300 MHz, CDCl3) δ 7.46 - 7.35 (m, 3H), 7.32 - 7.19 (m, 7H), 6.83 (s, 1H), 5.74 (s, 1H), 4.82 - 4.66 (m, 1H), 2.41 (s, 3H), 1.96 (dt, J1 = 12.4 Hz, J2 = 3.2 Hz, 1H), 1.89 - 1.73 (m, 2H), 1.69 - 1.43 (m, 7H), 1.39 - 0.96 (m, 19H), 0.93 - 0.80 (m, 13H), 0.70 - 0.58 (m, 4H) ppm.

[0511] 13 13C NMR (75 MHz, CDCl3) δ 163.3, 157.5, 150.7, 141.5, 140.7, 139.9, 129.4, 128.8, 128.3, 127.7, 127.6, 126.9, 115.6, 115.2, 109.8, 73.5, 56.4, 56.3, 54.2, 44.6, 42.6, 40.0, 39.5, 36.7, 36.2, 35.8, 35.5, 35.4, 34.1, 32.0, 28.6, 28.2, 28.0, 27.6, 24.2, 23.8, 22.8, 22.5, 21.2, 18.6, 13.8, 12.2, 12.1 ppm.

[0512] 2. High - resolution mass spectrometry: HRMS (ESI) Calcd for C 47 H 62 NaO3[M + +Na]: 697.4591, Found: 697.4589.

[0513] It can be seen from this result that its theoretical mass is 697.4591, while the observed value of the peak found in the actual mass spectrum is 697.4589; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0514] is the product of this example.

[0515] Example 35

[0516] Using 2-(2,2 - diphenylethenyl)-6,7 - dihydrobenzofuran - 4(5H)-one of Example 1 and N - bromosuccinimide as reaction raw materials for reaction, the specific implementation process is as follows:

[0517] Under argon protection, 2-(2,2-diphenylethenyl)-6,7-dihydrobenzofuran-4(5H)-one (125.8 mg, 0.4 mmol) and N-bromosuccinimide (106.8 mg, 0.6 mmol) were dissolved in ultradry dichloromethane (4 mL) with a water content of ≤50 ppm, and the reaction was carried out at 25 °C for 11 h. The reaction equation is as follows:

[0518]

[0519] The reaction solution was concentrated and purified by silica gel column chromatography to obtain 101.1 mg of solid product, and the calculated yield was 64%.

[0520] The analysis of the test is as follows:

[0521] 1. 1H NMR and 13C NMR analysis:

[0522] 1 H NMR (300 MHz, CDCl3) δ 7.40 - 7.27 (m, 8H), 7.26 - 7.18 (m, 2H), 6.80 (s, 1H), 2.50 (t, J = 6.3 Hz, 2H), 2.49 - 2.38 (m, 2H), 2.03 (p, J = 6.4 Hz, 2H) ppm.

[0523] 13 C NMR (75 MHz, CDCl3) δ 192.6, 166.0, 149.6, 143.3, 141.9, 139.8, 129.8, 128.3, 128.1, 127.8, 127.6, 127.5, 119.5, 111.5, 97.7, 37.9, 23.3, 21.8 ppm.

[0524] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 18 BrO2 [M + +H]: 393.0485, Found: 393.0492.

[0525] It can be seen from this result that the theoretical mass is 393.0485, while the observed value of the peak found in the actual mass spectrum is 393.0492; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0526] This is the product of this example.

[0527] Example 36

[0528] Using 2-(2,2-diphenylethenyl)-6,7-dihydrobenzofuran-4(5H)-one of Example 1, methyltriphenylphosphonium bromide and potassium tert-butoxide as reaction raw materials for the reaction, the specific implementation process is as follows:

[0529] Under argon protection, methyltriphenylphosphonium bromide (428.7 mg, 1.2 mmol) and potassium tert-butoxide (134.7 mg, 1.2 mmol) were dissolved in ultradry tetrahydrofuran (4 mL) with a water content ≤ 50 ppm and reacted for 1.5 h. Then, 2-(2,2-diphenylethenyl)-6,7-dihydrobenzofuran-4(5H)-one (125.8 mg, 0.4 mmol) was added, and the reaction continued at 25 °C for 10.5 h. The reaction equation is as follows:

[0530]

[0531] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 101.1 mg of solid product, and the calculated yield was 64%.

[0532] The analysis of the test is as follows:

[0533] 1. 1H NMR and 13C NMR analysis:

[0534] 1 H NMR (300 MHz, CDCl3) δ 7.47 - 7.35 (m, 3H), 7.34 - 7.18 (m, 7H), 6.91 (s, 1H), 5.46 (s, 1H), 4.66 (dd, J1 = 9.3 Hz, J2 = 1.6 Hz, 2H), 2.58 (t, J = 6.2 Hz, 2H), 2.36 - 2.26 (m, 2H), 1.89 - 1.76 (m, 2H) ppm.

[0535] 13 C NMR (75 MHz, CDCl3) δ 152.6, 151.8, 141.6, 140.3, 139.5, 138.0, 129.5, 128.9, 128.2, 127.5, 127.3, 126.7, 121.1, 116.0, 105.3, 104.9, 31.1, 23.3, 23.1 ppm.

[0536] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 23 H 21 O [M + + H]: 313.1587, Found: 313.1590.

[0537] From the results, it can be seen that the theoretical mass is 313.1587, while the observed value of the peak found in the actual mass spectrum is 313.1590; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0538] is the product of this example.

[0539] Example 37

[0540] Using 2-(2,2-diphenylethynyl)-6,7-dihydrobenzofuran-4(5H)-one of Example 1 and sodium borohydride as reaction raw materials for the reaction, the specific implementation process is as follows:

[0541] 2-(2,2-Diphenylethynyl)-6,7-dihydrobenzofuran-4(5H)-one (157.1 mg, 0.5 mmol) and sodium borohydride (56.7 mg, 1.5 mmol) were dissolved in methanol (4 mL) and reacted at 25 °C for 7 h. The reaction equation is as follows:

[0542]

[0543] The reaction solution was concentrated and then purified by silica gel column chromatography to obtain 157.0 mg of solid product, and the calculated yield was 99%.

[0544] The analysis of the test is as follows:

[0545] 1. 1H NMR and 13C NMR analysis:

[0546] 1 H NMR (300 MHz, CDCl3) δ 7.49 - 7.36 (m, 3H), 7.33 - 7.21 (m, 7H), 6.92 (s, 1H), 5.43 (s, 1H), 4.52 (t, J = 4.3 Hz, 1H), 2.51 (m, 2H), 2.08 - 1.68 (m, 4H), 1.50 (s, 1H) ppm.

[0547] 13 C NMR (75 MHz, CDCl3) δ 151.9, 151.8, 141.7, 140.3, 139.2, 129.5, 129.0, 128.3, 127.6, 127.3, 126.7, 122.1, 116.1, 108.3, 63.8, 32.4, 23.0, 18.7 ppm.

[0548] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 21 O2 [M + + H]: 317.1536, Found: 317.1529.

[0549] It can be seen from this result that the theoretical mass is 317.1536, while the observed value of the peak found in the actual mass spectrum is 317.1529; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0550] is the product of this example.

[0551] Example 38

[0552] Using the product of Example 37, 2-(2,2-diphenylvinyl)-4,5,6,7-tetrahydrobenzofuran-4-ol, triethylsilane and trifluoroacetic acid as reaction raw materials for the reaction, the specific implementation process is as follows:

[0553] Under argon protection, 2-(2,2-diphenylvinyl)-4,5,6,7-tetrahydrobenzofuran-4-ol (126.6 mg, 0.4 mmol), triethylsilane (465.1 mg, 4.0 mmol) and trifluoroacetic acid (136.8 mg, 1.2 mmol) were dissolved in ultradry dichloromethane (4 mL) with a water content of ≤ 50 ppm and reacted at 25 °C for 3 h. The reaction equation is as follows:

[0554]

[0555] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 107.5 mg of a solid product, and the calculated yield was 88%.

[0556] The analysis of the test is as follows:

[0557] 1. 1H NMR and 13C NMR of nuclear magnetic resonance analysis:

[0558] 1 H NMR(300MHz,CDCl3)δ7.48-7.33(m,3H),7.33-7.16(m,7H),6.94(s,1H),5.20(s,1H),2.50(t,J=6.2Hz,2H),2.21(t,J=6.0Hz,2H),1.80-1.69(m,2H),1.67-1.56(m,2H)ppm.

[0559] 13 C NMR(75MHz,CDCl3)δ150.9,150.3,141.9,140.6,138.0,129.6,128.9,128.2,127.4,127.0,126.6,119.1,116.5,110.0,23.1,23.0,22.9,22.0ppm.

[0560] 2. High-resolution mass spectrometry: HRMS(ESI) Calcd for C 22 H 21 O[M + +H]: 301.1587, Found: 301.1582.

[0561] It can be seen from this result that its theoretical mass is 301.1587, while the observed value of the peak found in the actual mass spectrometry is 301.1582; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0562] is the product of this example.

[0563] Example 39

[0564] Using 2-(2,2-diphenylethynyl)-6,7-dihydrobenzofuran-4(5H)-one of Example 1 as the reaction raw material for the reaction, the specific implementation process is as follows:

[0565] 2-(2,2-Diphenylethynyl)-6,7-dihydrobenzofuran-4(5H)-one (62.8 mg, 0.2 mmol) was dissolved in chloroform (2 mL), and irradiated with a single 3W 365nm LED lamp at 25 °C for 25 h. The reaction equation is as follows:

[0566]

[0567] The reaction solution was concentrated and purified by silica gel column chromatography to obtain 34.5 mg of solid product, and the calculated yield was 55%.

[0568] The analysis of the test is as follows:

[0569] 1. 1H NMR and 13C NMR analysis:

[0570] 1 H NMR(300 MHz, CDCl3) δ 9.73(d, J = 8.5 Hz, 1H), 7.92(d, J = 8.5 Hz, 1H), 7.66(t, J = 7.8 Hz, 1H), 7.57(s, 1H), 7.54 - 7.41(m, 6H), 3.14(t, J = 6.4 Hz, 2H), 2.75(t, J = 6.6 Hz, 2H), 2.32(p, J = 6.5 Hz, 2H) ppm.

[0571] 1313C NMR (75 MHz, CDCl3) δ 194.1, 170.2, 151.8, 140.6, 139.4, 130.2, 129.8, 128.6, 128.4, 128.3, 127.5, 126.6, 126.5, 125.2, 119.1, 118.9, 112.5, 39.1, 24.5, 22.2 ppm.

[0572] 2. High-resolution mass spectrometry: HRMS (ESI) Calcd for C 22 H 17 O2 [M + + H]: 313.1223, Found: 313.1227.

[0573] It can be seen from the results that its theoretical mass is 313.1223, while the observed value of the peak found in the actual mass spectrometry is 313.1227; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0574] is the product of this example.

[0575] Example 40

[0576] Using 2-(2,2-diphenylethenyl)-6,7-dihydrobenzofuran-4(5H)-one and methylamine in Example 1 as reaction raw materials for reaction, the specific implementation process is as follows:

[0577] 2-(2,2-Diphenylethenyl)-6,7-dihydrobenzofuran-4(5H)-one (62.8 mg, 0.2 mmol) and an ethanol solution of methylamine (0.6 mL, 0.6 mmol) were dissolved in an aqueous ethanol solution with a mass concentration of 30% (2 mL), and the reaction was carried out in a sealed tube at 150 °C for 10 h. The reaction equation is as follows:

[0578]

[0579] The reaction solution was concentrated and then subjected to silica gel column chromatography to obtain 48.3 mg of a solid product, and the calculated yield was 74%.

[0580] The analysis of the test is as follows:

[0581] 1. 1H NMR and 13C NMR analysis:

[0582] 11H NMR (300 MHz, CDCl3) δ 7.43 - 7.33 (m, 3H), 7.32 - 7.24 (m, 5H), 7.22 - 7.16 (m, 2H), 6.76 (s, 1H), 5.79 (s, 1H), 3.51 (s, 3H), 2.71 (t, J = 6.2 Hz, 2H), 2.43 - 2.33 (t, J = 6.4 Hz, 2H), 2.10 (p, J = 6.3 Hz, 2H) ppm.

[0583] 13 13C NMR (75 MHz, CDCl3) δ 193.5, 143.9, 142.7, 141.9, 140.1, 132.3, 129.6, 129.0, 128.2, 127.8, 127.5, 127.2, 120.3, 115.1, 106.0, 37.8, 30.9, 23.3, 22.1 ppm.

[0584] 2. High Resolution Mass Spectrometry: HRMS (ESI) Calcd for C 23 H 22 NO [M + + H]: 328.1696, Found: 328.1703.

[0585] It can be seen from this result that its theoretical mass is 328.1696, while the observed value of the peak found in the actual mass spectrum is 328.1703; combined with nuclear magnetic resonance, the product structure can be determined as follows:

[0586] is the product of this example.

[0587] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. People can also obtain other embodiments based on this embodiment without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a multifunctional compound, characterized in that: The following steps are involved: Mixing γ-hydroxy-α,β-unsaturated olefinic aldehyde, compound 1, a Lewis acid catalyst and an organic solvent, and performing a ring-forming reaction to obtain the multifunctional compound; The γ-hydroxy-α,β-unsaturated olefinic aldehyde has a structure shown in Formula 1 or is The compound 1 has a structure shown in any one of Formulas 2 to 5: When the γ-hydroxy-α,β-unsaturated olefinic aldehyde is When the compound 1 is The multifunctional compound is When the γ-hydroxy-α,β-unsaturated olefinic aldehyde is When the compound 1 is any one of the structures shown in Formulas 2 to 5; when the compound 1 is When the multifunctional compound has the structure shown in formula I, when the compound 1 is When the multifunctional compound has the structure shown in Formula II, when the compound 1 is When the multifunctional compound has the structure shown in formula III, when the compound 1 is When the multifunctional compound has a structure shown in Formula IV: Among them, R 1 and R 2 are independently aryl, phenyl, halogen-substituted phenyl, alkyl-substituted phenyl or alkyl; R 3 and R 4 are independently hydrogen, carboxyl, alkyl or aryl; X is -CH2- or -NH-, n is 1 or 2; R 5 and R 6 are independently aryl, alkyl or alkoxy; Y is -O- or -S-; R 7 and R 8 is independently methyl or ethyl.

2. The preparation method according to claim 1, characterized in that: Said Including γ-hydroxy-γ-diphenyl-α, β-unsaturated aldehyde, (E)-4,4-bis(4-bromophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-chlorophenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(4-methylphenyl)-4-hydroxy-2-butenal, (E)-4,4-bis(3-chlorophenyl)-4-hydroxy-2-butenal, (E)-4-hydroxy-4,4-di(naphthalene-2-yl)-2-butenal, (E)-4-hydroxy-4-phenyl-2-pentenal, and (E)-4,4-bis(4-fluorophenyl)-4-hydroxy-2-butenal.

3. The preparation method according to claim 1 or 2, characterized in that: The Lewis acid catalyst includes aluminum trifluoromethanesulfonate, scandium trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, indium trifluoromethanesulfonate, tin trifluoromethanesulfonate, iron trifluoromethanesulfonate or tris(pentafluorophenyl)borane; The molar ratio of the γ-hydroxy-α, β-unsaturated olefinic aldehyde to the Lewis acid catalyst is 1:0.01-0.

2.

4. The preparation method according to claim 1, characterized in that: Said Including 1,3-cyclohexanedione, 5-methylcyclohexane-1,3-bicycloone, 5,5-dimethylcyclohexane-1,3-bicycloone, 5-phenylcyclohexane-1,3-bicycloone, 5-(methoxyphenyl)cyclohexane-1,3-bicycloone, 5-(2-furyl)-1,3-cyclohexanedione, 3,5-dioxocyclohexanecarboxylic acid, 1,3-cycloheptanedione or 2,4-piperidinedione; Said Including 2,4-pentanedione, 2,6-dimethyl-3,5-heptanedione, 1,3-diphenylpropanedione, ethyl acetoacetate, 2-cyanoethyl 3-oxobutyrate, allyl acetoacetate, methoxyethyl acetoacetate, 3-bromopropyl 3-oxobutyrate, (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl-3-oxobutyrate, 1,7,7-trimethylbicyclo[2.2.1]heptane-2-yl 3-oxobutyrate, (3S,8R,9S,10R,13S,14S)-10,13-dimethyl-17-oxo-2,3,4,7,8,9,10,11,12,13,14, 15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-3-yl-3-oxobutanoic acid, (5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5H-bis(1,3)dioxolane[4,5-b:4',5'-d]pyran-5-methyl-3-oxobutanoic acid, 3,7-dimethyloct-6-en-1-yl-3-oxobutanoate or (3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylhept-2-yl)hexadecanoic-1H-cyclopenta[a]phenanthrene-3-yl-3-oxobutanoate; Said It is 1,3-dimethylbarbituric acid or 1,3-diethyl-2-thiobarbituric acid.

5. The preparation method according to claim 1 or 4, characterized in that: The molar ratio of the γ-hydroxy-α,β-unsaturated olefinic aldehyde to compound 1 is 1:1.8-2.

2.

6. The preparation method according to claim 1, characterized in that: The temperature of the cyclization reaction is 0 to 80° C., and the time is 2 to 34 hours.

7. A multifunctional compound prepared by the preparation method according to any one of claims 1 to 6, characterized in that: Having a structure shown in any one of formulas Ⅰ to Ⅳ: Among them, R 1 and R 2 are independently aryl, phenyl, halogen-substituted phenyl, alkyl-substituted phenyl or alkyl; R 3 and R 4 are independently hydrogen, carboxyl, alkyl or aryl; X is -CH2- or -NH-, n is 1 or 2; R 5 and R 6 are independently aryl, alkyl or alkoxy; Y is -O- or -S-; R 7 and R 8 is independently methyl or ethyl.

8. The multifunctional compound according to claim 7, characterized in that: It has a structure shown in any one of formulas Ⅰ-1 to Ⅰ-17, formulas Ⅱ-1 to Ⅱ-14, and formulas Ⅲ-1 to Ⅲ-2:

9. A derivative prepared using the multifunctional compound having the structure shown in formula I in claim 7 as a raw material, characterized in that: Having any structure shown in formula a to f:

10. A method for preparing the derivative according to claim 9, comprising the following steps: Said The preparation method comprises the following steps: N-bromosuccinimide and the first organic solvent are mixed and subjected to an electrophilic substitution reaction to obtain the Said The preparation method comprises the following steps: Methyltriphenylphosphonium bromide, potassium tert-butoxide and a second organic solvent are mixed and subjected to Wittig reaction to obtain the Said The preparation method comprises the following steps: Sodium borohydride and the third organic solvent are mixed and then subjected to reduction reaction to obtain the Said The preparation method comprises the following steps: After triethylsilane, trifluoroacetic acid and the fourth organic solvent are mixed, a silane reduction reaction is performed to obtain the Said The preparation method comprises the following steps: After being dissolved in a fifth organic solvent and mixed, an electrocyclization / oxidation rearomatization reaction is performed to obtain the Said The preparation method comprises the following steps: The ethanol solution of methylamine and the sixth organic solvent are mixed and subjected to an aminolysis reaction of furan to obtain the

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