CN109651209B - A method for preparing (E)-1-phenyl-4-sulfonylbut-1-ene compounds by activation of carbon-carbon σ-bonds - Google Patents

Abstract

The invention disclosesA composition ofE) The synthesis process of (E) -1-phenyl-4-sulfonyl butane-1-ene compound with methylene cyclopropane compound and organic sulfonate compound as material and in oxidant K₂S₂O₈And a certain amount of water to prepare a compound having various substituentsE) -1-phenyl-4-sulfonylbut-1-enes. The method does not need to use transition metal and/or alkali, is economic and environment-friendly, and has the advantages of easily available raw material sources, simple process route, mild reaction conditions, low process cost, wide substrate application range and high yield of target products.

Description

Preparation of (E)-1-phenyl-4-sulfonylbut-1-ene by activation of a carbon-carbon σ-bond method of compounding

technical field

The application belongs to the technical field of organic synthesis, and in particular relates to a method for preparing (E)-1-phenyl-4-sulfonylbut-1-ene compounds by activation of carbon-carbon σ-bonds.

Background technique

Carbon-carbon σ-bonds are a common class of chemical bonds with high stability. Recently, the activation of carbon-carbon σ-bonds has become a useful strategy for the simple construction of complex molecular frameworks, and many excellent carbon-carbon σ-bond activation transformations have been developed to construct new carbon-carbon bonds or carbon-heterobonds. Recently, various effective carbon-carbon sigma-bond activation strategies have been developed, including halogenation, oxidative cleavage, and cleavage of functional substrates bearing ester, carboxyl, carbonyl, hydroxyl, cyano, or oxime groups. Most of these reactions require the use of transition metals such as Ir, Pd, Ru, Rh, and Cu (see, for example, SYNLETT 2003, No. 13, pp2080–2082). However, it would be highly desirable if these transformations could be achieved without transition metals, which would provide simpler and more environmentally friendly options.

Sodium salt of organic sulfonic acid is widely used in organic synthesis and pharmaceutical synthesis as a kind of readily available and highly active salt. Therefore, a series of interesting transformations have been developed by using sodium salts of organic sulfonic acids as sulfonyl or hydrocarbyl sources. Recently, many chemists have proposed a number of sulfonylation methods for cross-coupling reactions and bifunctionalization reactions by using sodium salts of organosulfonates as a source of sulfonyl groups. In 2011, Maloney and colleagues reported a cross-coupling reaction between chloropyridine and sodium sulfonate for the construction of sulfonylated dipyrimidines (see, for example, K.-M. Maloney, J. Kuethe, K. Linn, Org. Lett. 2011, 13, 102). For coupling with C-H, various C-H bonds, including C(sp)-H bonds (see, e.g., J. Yang, Y.-Y. Liu, R.-J. Song, Z.-H. Peng, J. .-H. Li, Adv. Synth.Catal. 2016, 358, 2286), C(sp2)-H bonds (see e.g. F. Wang, X.-Z. Yu, Z.-S. Qi, X.- W.Li, Chem. Eur. J. 2016, 22, 511.) and C(sp3)-H bonds (see e.g. W.-H. Rao, B.-B. Zhan, K. Chen, P.-X . Ling, Z.-Z. Zhang, B.-F. Shi, Org. Lett. 2015, 17, 3552) can smoothly undergo cross-coupling sulfonylation. Kuhakarn's group proposed a cross-coupling sulfonylation of arylacetylenes (C(sp)-H bonds) with sodium sulfonates. Li and co-workers developed an Rh-catalyzed cross-coupling reaction between the C(sp2)-H bonds of arenes and sodium sulfonates. Shi's group described a palladium-catalyzed cross-coupling sulfonylation of C(sp3)-H bonds with sodium sulfonate. Interestingly, the sodium salt of organosulfonic acid can also be used for the sulfonylation and difunctionalization of unsaturated bonds, including carbon-carbon double bonds and carbon-carbon triple bonds. In 2016, his research group presented the 1,2-difunctionalization of alkynes with sodium sulfonate and water under transition metal-free and additive-free conditions. Li's research group reported the 1,2-difunctionalization of alkenes with tert-butyl nitrite and sodium sulfonate to synthesize α-sulfonylethane oximes. However, the reaction of saturated carbon-carbon σ-bonds with sodium salt of organic sulfonic acid has not been disclosed in the prior art.

Three-membered carbocyclic compounds, especially methylenecyclopropanes (MCPs), are highly reactive and belong to easily accessible structures, and are often used as important raw materials in organic synthesis. In this paper, we developed a novel bifunctionalization via carbon-carbon σ-bonds in methylenecyclopropane with organosulfonic acid sodium salt compounds and water under conditions that do not require the use of transition metals and bases A synthetic strategy for the selective synthesis of (E)-1-phenyl-4-sulfonylbut-1-ene compounds.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the deficiencies of the prior art, and provide a kind of starting material with methylene cyclopropane compounds, under the condition of not needing transition metals and alkalis, through carbon-carbon σ-bond activation bifunctionalization , a new method for the selective synthesis of ( E )-1-phenyl-4-sulfonylbut-1-enes.

The invention provides a method for synthesizing ( E )-1-phenyl-4-sulfonylbut-1-ene compounds, characterized in that the method comprises the following steps:

In the Schlenk sealed tube reactor, the methylene cyclopropane compounds shown in formula I and the organic sulfonate compounds shown in formula II are used as reaction raw materials, a certain amount of water, an oxidizing agent and an organic solvent are added, and heating The reaction is stirred, and after the completion of the reaction is monitored by TLC or GC-MS, the ( E )-1-phenyl-4-sulfonylbut-1-ene compound represented by formula III is obtained by post-treatment.

Wherein, in formula I, formula II and/or formula III, R ₁ represents one or more substituents on the connected benzene ring, selected from hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ Alkoxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₃ -C ₂₀ cycloalkyl, C _6~ C ₂₀ aryl -C _1~ C ₂₀ alkyl, C _6~ C ₂₀ aryl-C _1~ C ₂₀ alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR ₄ , -COR ₅ , -OCOR ₆ , -NR ₇ R ₈ ; wherein, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C Any one or more of ₃ -C ₂₀ cycloalkyl groups.

R ₂ is selected from hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, C _6～ C ₂₀ aryl-C _1～ C ₂₀ alkyl; Wherein, the substituent in the substituted or unsubstituted is selected from C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ acyl group, halogen, -NO ₂ , -CN , -OH, C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ .

R ₃ is selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₃ -C ₂₀ heteroaryl; wherein, the The substituents in the substituted or unsubstituted are selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, halogen, -NO ₂ , -CN, -OH , C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ .

For those skilled in the art, it can be understood that the number of substituents in the expression "substituted or unsubstituted" described in any of the above-mentioned parts of the present invention may be one or more, such as two, Three, four, five; when there are two or more substituents, each substituent can be independently selected from the above-mentioned definitions of substituents. The heteroaryl group has definitions well known in the art, and the heteroatom can be selected from heteroatom species such as O, S, N, and thus the heteroaryl group can be selected from, for example, furyl, pyridyl, thienyl, quinoline, etc. Lino, etc.

Preferably, in formula I, formula II and/or formula III, R ₁ represents one or more substituents on the connected benzene ring, selected from hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₆ -C ₁₄ aryl, C _6~ C ₁₄ aryl-C _1~ C ₆ alkyl, C _6~ C ₁₄ aryl-C _1~ C ₆ alkoxy, nitro, Halogen, -OH, -SH, -CN, -COOR ₄ , -COR ₅ , -OCOR ₆ , -NR ₇ R ₈ ; wherein, R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently selected from Any one of hydrogen, C ₁ -C ₆ alkyl, and C ₆ -C ₁₄ aryl.

R ₂ is selected from hydrogen, substituted or unsubstituted C ₁ -C ₆ alkyl, substituted or unsubstituted C ₆ -C ₁₄ aryl, C _6～ C ₁₄ aryl-C _1～ C ₆ alkyl; Wherein, the substituent in the substituted or unsubstituted is selected from C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ acyl group, halogen, -NO ₂ , -CN , -OH, C ₆ -C ₁₄ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ .

R ₃ is selected from substituted or unsubstituted C ₁ -C ₆ alkyl, substituted or unsubstituted C ₆ -C ₁₄ aryl, substituted or unsubstituted C ₃ -C ₁₄ heteroaryl; wherein, the The substituents in the substituted or unsubstituted are selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, halogen, -NO ₂ , -CN, -OH , C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ .

Most preferably, the compound of formula I is selected from the compounds shown in the structures of the following formulas I-1 to I-17:

The compound of formula II is selected from: sodium trifluoromethanesulfonate, sodium benzenesulfonate, sodium p-methoxybenzenesulfonate, sodium p-toluenesulfonate, sodium p-fluorobenzenesulfonate, sodium p-chlorobenzenesulfonate, Sodium bromobenzenesulfonate, sodium p-trifluoromethylbenzenesulfonate, sodium p-cyanobenzenesulfonate, sodium p-nitrobenzenesulfonate, sodium m-toluenesulfonate, 2,4,6-trimethylbenzene Sodium sulfonate, sodium 2-naphthalenesulfonate, sodium benzylsulfonate, sodium 2-thiophenesulfonate, sodium methanesulfonate.

According to the aforementioned method of the present invention, the oxidant is K ₂ S ₂ O ₈ .

According to the aforementioned method of the present invention, the reaction is carried out under an inert atmosphere or an air atmosphere, preferably under an inert atmosphere (argon). For the inert atmosphere, it can be understood that it refers to an atmosphere inert to the reaction, rather than mechanically considered an inert gas. For those skilled in the art, the inert atmosphere commonly used for organic reactions can be selected from an argon atmosphere or a nitrogen atmosphere. An argon atmosphere is preferred.

According to the aforementioned method of the present invention, wherein, the organic solvent is selected from any one of toluene, tetrahydrofuran, 1,4-dioxane, and acetonitrile. Preferably, the organic solvent is toluene. The amount of the organic solvent can be determined by those skilled in the art according to the actual situation of the reaction.

According to the aforementioned method of the present invention, the reaction temperature of the heating and stirring reaction is 40-120°C, preferably 60-100°C, and most preferably 80°C. The reaction time of the reaction is 12-72 hours, preferably 24-48 hours.

According to the aforementioned method of the present invention, the molar ratio of the compound of formula I, the compound of formula II, the oxidant (K ₂ S ₂ O ₈ ) and water is 1:(1~3):(1-3):(2-8) , preferably, the molar ratio of the compound of formula I, the compound of formula II, the oxidant (K ₂ S ₂ O ₈ ) and water is 1:2:2:4.

According to the aforementioned reaction of the present invention, wherein the post-processing operation is as follows: the mixed solution after the reaction is concentrated under reduced pressure to obtain a residue, and then the residue is separated by column chromatography to obtain the target product shown in formula III , wherein the eluent separated by silica gel column chromatography is a mixture of n-hexane and ethyl acetate.

The beneficial effects of the present invention are as follows:

(1) The present invention proposes for the first time that the methylene cyclopropane compound shown in formula I and the organic sulfonate compound shown in formula II are used as reaction raw materials to prepare ( E )-1- shown in formula III. The synthetic route of phenyl-4-sulfonyl but-1-ene compounds, which has not been reported in the prior art;

(2) The method of the present invention does not require the use of transition metals and/or alkalis, is economical and environmentally friendly, and has the advantages of easily available raw material sources, simple process routes, mild reaction conditions, low process costs, wide substrate adaptability and high target product yields. advantage.

Detailed ways

The present invention will be further described in detail below with reference to specific embodiments.

Embodiment 1-17 Reaction condition optimization test

Taking the compound shown in formula I-1 and the sodium trifluoromethanesulfonate shown in formula II-1 as reaction raw materials, the influence of different reaction conditions on the optimization results of the synthesis process was discussed, and a representative example 1 was selected. -17. The results are shown in Table 1.

Wherein the typical test operation of embodiment 1 is as follows:

The compound shown in formula I-1 (0.2 mmol), the sodium trifluoromethanesulfonate shown in formula II-1 (2 equivalents, 0.4 mmol), the oxidizing agent (K ₂ S ₂ O ₈ ) were added to the schlenk sealed tube reactor , 2 equiv, 0.4 mmol), H ₂ O (4 equiv, 0.6 mmol), and toluene (2 mL), then the reaction was stirred under argon protection at 80 °C for 48 hours, and the completion of the reaction was monitored by TLC or GC-MS Afterwards, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent was n-hexane/ethyl acetate) to obtain the target product of formula III-1 with a yield of 82%; ¹ H NMR (400 MHz, CDCl ₃ ) δ: 7.44-7.32 (m, 6H), 7.20 (t, J = 7.6 Hz, 1H), 6.96-6.87 (m, 3H), 6.20-6.12 (m, 1H), 5.10 (s, 2H) , 4.48-4.42(m, 1H), 4.25-4.19 (m, 1H), 2.70-2.65 (m, 2H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ: 155.6, 137.0, 128.6, 128.6, 128.6, 127.9, 127.3, 126.8, 126.2, 124.1, 122.9(d, J = 336.9 Hz), 121.0, 112.4, 70.3, 68.1, 33.8; ¹⁹ F NMR (282 MHz, CDCl ₃ ) δ:-78.3 (s, 1F);

Table I:

Among them, the specific operations and parameters of Examples 2-17 are the same as those of Example 1 except that the variables listed in Table 1 above are different from those of Example 1.

As can be seen from the above-mentioned Examples 1-17, the optimal reaction conditions are the reaction conditions of Example 1. Under the reaction conditions of Example 1, the inventors expanded the reaction substrate to further prepare various target compounds of formula III (Examples 18-34).

Formula I Formula II Formula III 18

CF₃SO₂Na Yield 88%; ¹H NMR (500 MHz, CDCl₃): 6.96 (s, 1H), 6.83-6.75 (m, 3H), 6.17-6.10 ( m, 1H), 4.49-4.45 (m, 1H), 4.26-4.23 (m, 1H), 3.80 (s, 3H), 3.79 (s, 3H), 2.72-2.66 (m, 2H). 19

CF₃SO₂Na Yield 82%; ¹H NMR (500 MHz, CDCl₃): 7.23 (t, <i>J</i> = 8.0 Hz, 1H), 6.95 (d, <i>J</i> = 7.6 Hz, 1H), 6.89 (s, 1H), 6.80 (t, <i>J</i> = 8.0 Hz, 1H), 6.49 (t, <i >J</i> = 16.0 Hz, 1H), 6.17-6.10 (m, 1H), 4.50-4.44(m, 1H), 4.27-4.21 (m, 1H), 3.82 (s, 3H), 2.70-2.64 (m,2H). 20

CF₃SO₂Na Yield 78%; ¹H NMR (500 MHz, CDCl₃): 7.41-7.39 (m, 1H), 7.17-7.15 (m, 3H), 6.73 ( d, <i>J</i> = 16.0 Hz, 1H), 6.04-5.97 (m, 1H), 4.51-4.46 (m, 1H), 4.28-4.23 (m, 1H), 2.72-2.67 (m, 2H), 2.33(s, 3H). twenty one

CF₃SO₂Na Yield 90%; ¹H NMR (500 MHz, CDCl₃): 7.61-7.55(m,4H), 7.46-7.41(m,4H), 7.36- 7.32 (m, 1H), 6.55 (d,<i>J</i> = 16.0 Hz, 1H), 6.22-6.14(m, 1H), 4.52-4.46(m, 1H), 4.28-4.22(m, 1H), 2.72-2.67 (m, 2H). twenty two

CF₃SO₂Na Yield 85%; ¹H NMR (500 MHz, CDCl₃): 7.28-7.26(m,4H), 6.49-6.45(m,1H), 6.16- 6.08 (m, 1H), 4.51-4.45 (m, 1H), 4.27-4.22 (m, 1H), 2.70-2.64 (m, 2H). twenty three

CF₃SO₂Na Yield 76%; ¹H NMR (500 MHz, CDCl₃): 7.11 (d, <i>J</i>=8.4Hz, 1H), 7.03 (d,<i>J</i>=8.4 Hz, 1H), 6.89(t,<i>J</i>=8.4Hz,1H), 6.41(d,<i>J</i>= 15.6 Hz, 1H), 6.04-5.96 (m, 1H), 4.48-4.44(m, 1H), 4.24-4.22(m, 1H), 3.89(s, 3H), 2.68-2.63 (m, 2H). twenty four

CF₃SO₂Na Yield 65%; ¹H NMR (500 MHz, CDCl₃): 7.36-7.30(m, 4H), 7.25-7.22(m, 1H), 6.52 ( d, <i>J</i> = 15.6 Hz, 1H), 6.18-6.10 (m, 1H), 4.50-4.44(m, 1H), 4.27-4.21(m, 1H), 2.70-2.65(m, 2H). 25

CF₃SO₂Na Yield 90%; ¹H NMR (500 MHz, CDCl₃): 7.41-7.33(m,3H), 7.28-7.21(m,5H), 7.16 ( d, <i>J</i> = 6.4 Hz, 2H), 6.05 (t, <i>J</i> = 7.6 Hz, 1H), 4.44-4.38(m, 1H), 4.20-4.15 (m , 1H),2.61-2.56 (m, 2H). 26

CF₃SO₂Na Yield 84%; ¹H NMR (500 MHz, CDCl₃): 7.12 (d,<i>J</i>=8.0Hz,2H), 7.05 -6.96(m,6H), 5.97(t, <i>J</i> = 7.2 Hz,1H), 4.42-4.37(m, 1H),4.19-4.14(m,1H),2.61-2.56(m , 2H), 2.39 (s, 3H), 2.32 (s, 3H). 27

CF₃SO₂Na Yield 90%; ¹H NMR (500 MHz, CDCl₃): 7.16-7.14(m,2H), 7.09-7.07(m,2H), 6.93- 6.90 (m, 2H), 6.83-6.79 (m, 2H), 5.89 (t,<i>J</i>=7.6Hz,1H),4.42-4.37(m,1H), 4.19-4.14(m, 1H), 3.83 (s, 3H), 3.78 (s, 3H), 2.61-2.56 (m, 2H). 28

CF₃SO₂Na Yield 81%; ¹H NMR (500 MHz, CDCl₃): 7.39-7.36(m, 2H), 7.28(s, 1H), 7.26-7.24 ( m, 1H), 7.14-7.08(m, 4H), 6.03 (d, <i>J</i>=7.6Hz,1H),4.46-4.40(m,1H),4.20-4.15 (m,1H) , 2.59-2.54 (m, 2H). 29

Sodium benzene sulfinate Yield 80%; ¹H NMR (500 MHz, CDCl₃): 7.70-7.68(m,2H), 7.54-7.48(m,3H), 7.14- 7.11 (m, 2H), 7.03-7.00 (m, 2H), 6.89-6.86(m, 2H), 6.81-6.78(m, 2H), 5.84 (t, <i>J</i> =7.6 Hz, 1H), 4.12-4.06 (m, 1H), 3.89(s, 3H), 3.83(s, 3H), 3.71-3.65(m, 1H), 2.47-2.42 (m, 2H). 30

Sodium p-methoxybenzene sulfinate Yield 87%; ¹H NMR (500 MHz, CDCl₃): 7.81 (d, <i>J</i>=8.8Hz, 2H), 7.07 (d,<i>J</i>=8.8 Hz, 2H), 7.00(d,<i>J</i>=8.4Hz,2H),6.95(d,<i>J</i>= 9.2 Hz, 2H), 6.87(d, <i>J</i> = 8.8 Hz, 2H), 6.78 (d,<i>J</i>=8.8Hz,2H),5.76(t,<i >J</i>=7.2 Hz, 1H), 4.06(t,<i>J</i>=6.8Hz,2H),3.86(s,3H),3.83(s, 3H), 3.79(s, 3H), 2.46-2.41 (m, 2H). 31

Sodium p-fluorobenzene sulfinate Yield 90%; ¹H NMR (500 MHz, CDCl₃): 7.84-7.80 (m, 2H), 7.17 (t, <i>J</i > =8.8 Hz, 2H), 7.07 (d, <i>J</i> = 8.8Hz, 2H), 6.95 (d, <i>J</i> = 8.4 Hz, 2H), 6.83 (d, <i>J</i> = 8.8 Hz, 2H), 6.78(d, <i>J</i> = 8.8 Hz, 2H), 5.81(t, <i>J</i> = 7.2 Hz, 1H), 3.84 (s, 3H), 3.78 (s, 3H), 3.17-3.13(m, 2H), 2.52-2.47 (m, 2H). 32

Sodium p-nitrobenzene sulfinate Yield 75%; ¹H NMR (500 MHz, CDCl₃): 8.32 (d, <i>J</i> = 8.4 Hz, 2H), 7.86 (d, <i>J</i> = 8.4 Hz, 2H), 7.11 (d, <i>J</i>= 8.4 Hz, 2H), 7.01 (d, <i>J</i> = 8.4Hz, 2H), 6.88 (d, <i>J</i> = 8.4 Hz, 2H), 6.80 (d, <i>J</i> = 8.4 Hz, 2H), 5.79 (t, <i> >J</i> = 7.6 Hz, 1H), 4.17-4.11 (m, 1H), 3.83 (s, 3H), 3.8-3.72 (m, 4H), 2.50-2.44 (m, 2H). 33

Sodium 2,4,6-Trimethylbenzenesulfinate Yield 80%; ¹H NMR (500 MHz, CDCl₃): 7.07 (d, <i>J</i> = 8.8 Hz, 2H), 7.00 (d, <i>J</i> = 8.8 Hz, 2H), 6.93 (s, 2H), 6.86 (d, <i>J</i> = 8.4 Hz, 2H), 7.78 (d, <i >J</i> = 8.8 Hz, 2H), 5.78(t, <i>J</i> = 7.6 Hz, 1H), 4.00 (t, <i>J</i>= 6.8 Hz, 2H) , 3.83 (s, 3H), 3.78 (s, 3H), 2.60 (s, 6H), 2.48-2.43 (m, 2H), 2.30 (s, 3H). 34

Sodium 2-naphthalene sulfinate Yield 85%; ¹H NMR (500 MHz, CDCl₃): 8.48 (s, 1H), 7.97-7.91 (m, 3H), 7.83 (d, <i>J</i> = 8.8 Hz, 1H), 7.69-7.63 (m, 2H), 7.01-6.94(m, 4H), 6.84-6.81 (m, 2H), 6.75-6.71 (m, 2H) , 5.73 (t, <i>J</i> =7.6 Hz, 1H), 4.13 (t, <i>J</i> = 6.4Hz, 2H), 3.81 (s, 3H), 3.78 (s, 3H), 2.48-2.43 (m, 2H).

The above-mentioned embodiments are only preferred embodiments of the present invention, rather than an exhaustive list of feasible implementations of the present invention. For those skilled in the art, without departing from the principle and spirit of the present invention, any obvious changes made to it should be considered to be included in the protection scope of the claims of the present invention.

Claims (13)

1. A synthetic method for preparing ( E )-1-phenyl-4-sulfonylbut-1-ene compound by activation of carbon-carbon σ bond, is characterized in that, described method comprises the steps: In the Schlenk sealed tube reactor, the methylene cyclopropane compounds shown in formula I and the sodium organosulfinate compounds shown in formula II are used as reaction raw materials, and a certain amount of water, an oxidant and an organic solvent are added, The reaction is heated and stirred, and after the completion of the reaction is monitored by TLC or GC-MS, the ( E )-1-phenyl-4-sulfonylbut-1-ene compound shown in formula III is obtained by post-treatment;

Wherein, in formula I, formula II and/or formula III, R ₁ represents one or more substituents on the connected benzene ring, selected from hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ Alkoxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₃ -C ₂₀ cycloalkyl, C _6~ C ₂₀ aryl -C _1~ C ₂₀ alkyl, C _6~ C ₂₀ aryl-C _1~ C ₂₀ alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR ₄ , -COR ₅ , -OCOR ₆ , -NR ₇ R ₈ ; wherein, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C Any one or more of ₃ -C ₂₀ cycloalkyl groups; R ₂ is selected from hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, C _6～ C ₂₀ aryl-C _1～ C ₂₀ alkyl; Wherein, the substituent in the substituted or unsubstituted is selected from C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ acyl group, halogen, -NO ₂ , -CN , -OH, C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ ; R ₃ is selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₃ -C ₂₀ heteroaryl; wherein, the The substituents in the substituted or unsubstituted are selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, halogen, -NO ₂ , -CN, -OH , C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ ; Wherein, the oxidant is K ₂ S ₂ O ₈ . 2. synthetic method according to claim 1 is characterized in that, in formula I, formula II and/or formula III, R ₁ represents one or more substituents on the connected benzene ring, selected from hydrogen, C ₁ - _C6 alkyl, _C1 - _C6 alkoxy, _C6 - _C14 aryl, C6 _{~ C14} aryl-C1 _{~ C6} alkyl, C6 _{~ C14} aryl -C _1~ C ₆ alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR ₄ , -COR ₅ , -OCOR ₆ , -NR ₇ R ₈ ; wherein, R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently selected from any one of hydrogen, C ₁ -C ₆ alkyl, and C ₆ -C ₁₄ aryl; R ₂ is selected from hydrogen, substituted or unsubstituted C ₁ -C ₆ alkyl, substituted or unsubstituted C ₆ -C ₁₄ aryl, C _6～ C ₁₄ aryl-C _1～ C ₆ alkyl; Wherein, the substituent in the substituted or unsubstituted is selected from C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ acyl group, halogen, -NO ₂ , -CN , -OH, C ₆ -C ₁₄ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ ; R ₃ is selected from substituted or unsubstituted C ₁ -C ₆ alkyl, substituted or unsubstituted C ₆ -C ₁₄ aryl, substituted or unsubstituted C ₃ -C ₁₄ heteroaryl; wherein, the The substituents in the substituted or unsubstituted are selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, halogen, -NO ₂ , -CN, -OH , C ₆ -C ₂₀ aryl, C ₃ -C ₆ cycloalkyl, -NMe ₂ . 3. according to the synthetic method described in any one of claim 1-2, it is characterized in that, formula I compound is selected from the compound shown in following formula I-1～I-22 structure:

. 4. according to the described synthetic method of any one of claim 1-2, it is characterised in that the compound of formula II is selected from sodium trifluoromethanesulfinate, sodium benzenesulfinate, p-methoxybenzenesulfinic acid Sodium, sodium p-toluene sulfinate, sodium p-fluorobenzene sulfinate, sodium p-chlorobenzene sulfinate, sodium p-bromobenzene sulfinate, sodium p-trifluoromethyl benzene sulfinate, p-cyanobenzene Sodium sulfinate, sodium p-nitrobenzene sulfinate, sodium m-toluene sulfinate, sodium 2,4,6-trimethylbenzene sulfinate, sodium 2-naphthalene sulfinate, benzyl sulfinate sodium, 2-thiophene sulfinate, sodium methanesulfinate. 5. The synthetic method according to any one of claims 1-2, wherein the reaction is carried out in an inert atmosphere or an air atmosphere. 6. The synthesis method according to claim 5, wherein the reaction is carried out under an argon atmosphere. 7. The synthetic method according to any one of claims 1-2, wherein the organic solvent is selected from any one of toluene, tetrahydrofuran, 1,4-dioxane, and acetonitrile. 8. synthetic method according to claim 7 is characterized in that, described organic solvent is toluene. 9 . The synthesis method according to claim 1 , wherein the reaction temperature of the heating and stirring reaction is 40-120° C.; the reaction time of the reaction is 12-72 hours. 10 . 10. synthetic method according to claim 9 is characterized in that, the reaction temperature of described heating and stirring reaction is 80 ℃; The reaction time of described reaction is 24～48 hours. 11. The synthetic method according to any one of claims 1-2, wherein the mol ratio of the compound of formula I, compound of formula II, oxidant K ₂ S ₂ O ₈ and water is 1:(1～3) :(1-3):(2-8). 12 . The synthesis method according to claim 11 , wherein the molar ratio of the compound of formula I, the compound of formula II, the oxidant K ₂ S ₂ O ₈ and water is 1:2:2:4. 13 . 13. according to the synthetic method described in any one of claim 1-2, it is characterized in that, described post-processing operation is as follows: the mixed solution after the reaction is concentrated under reduced pressure, obtains residue, then residue is passed through column The target product represented by formula III is obtained by separation by gel column chromatography, wherein the eluent separated by silica gel column chromatography is a mixture of n-hexane and ethyl acetate.