CN110483291B - Synthesis method of (E) -beta-aryl-beta, gamma-unsaturated ester compound - Google Patents

Abstract

The invention belongs to the technical field of organic synthesis chemistry, and discloses a method for one-step synthesis of important (A) by using ethyl diazoacetate and arylboronic acid as coupling reagents and using copper to catalyze 1, 1-arylation alkylation reaction of alkyneE)‑βAryl-β,γ-unsaturated esters, in particular: mixing alkyne compound, solvent, ethyl diazoacetate, arylboronic acid compound, phenanthroline, CuI and K₃PO₄Mixing, then carrying out closed reaction for 1.2-3 hours at 90-110 ℃ in an inert gas atmosphere, and carrying out post-treatment after the reaction is finished. The invention has the characteristics of simple catalytic system, cheap and easily obtained raw materials, excellent functional group compatibility, high regional and chemical selectivity, wide substrate application range and the like, and is suitable for synthesizing various compounds (A, B, C, D, E, PE)‑βAryl-β,γ-unsaturated ester compounds.

Description

Synthesis method of (E) -beta-aryl-beta, gamma-unsaturated ester compound

Technical Field

The invention belongs to the technical field of organic synthesis chemistry, and particularly relates to a one-step synthesis method for catalyzing reaction of alkyne, ethyl diazoacetate and arylboronic acid by copperE)-βAryl-β,γA process for producing an unsaturated ester compound.

Background

β,γUnsaturated ester compounds are widely present in natural products with important biological activities and are also important organic synthesis intermediates ((a) Millar, j. g.; Oehlschlager, a. c.; Wong, j. W.) in organic synthesis.J. Org. Chem.1983, 48, 4404. (b) Oehlschlager, A. C.; Wong, J. W.; Verigin, V. G.; Pierced, H. D. J. Org. Chem.1983, 48, 5009. (c) Liang, J. L.; Javed, U.; Lee, S. H.; Park, J. G.; Jahng, Y. Arch. Pharm. Res. 2014, 37, 862. (d) Eissler, S.; Nahrwold, M.; Neumann, B.; Stammler, H. G.; Sewald, N. Org. Lett. 2007, 9817.), the synthetic methods for preparing such compounds have therefore attracted considerable attention from organic chemists.

At present, the methods reported in the literature mainly include: (1) carbonylation of leaving group-containing allylic substrates with CO ((a) Tsuji, J.; Sato, K.; Okumoto, H).J. Org. Chem. 1984, 49, 1341. (b) Murahashi, S.; Imada, Y.; Taniguchi, Y.; Higashiura, S. J. Org. Chem.1993, 58, 1538. (c) Liu, Q.; Wu, L.; Jiao, H.; Fang, X.; Jackstell, R.; Beller, M. Angew. Chem., Int. Ed. 2013, 528064.); (2) cross-coupling of the alkenyltrifluoroborate with ethyl 2-chloroacetate ((a) Molander, G.A.; Barcellos, T.; Trister, K.M.).Org. Lett. 2013, 15, 3342. (b) Brown, H. C.; Cho, B. T.; Park, W. S. J. Org. Chem. 1986, 513398.); (3) decarboxylated alkylcarboxylation of alpha, beta-unsaturated acids (Gao, B.; Xie, Y.; Shen, Z.; Yang, L.; Huang, H).Org. Lett.2015, 17, 4968.). Although there are many methods for synthesizing such compounds, there are some disadvantages such as difficulty in handling using a gaseous raw material, necessity of an expensive metal catalyst, low atom utilization, difficulty in controlling stereoselectivity, and the like. More importantly, for the synthesis of (E)-βAryl-β,γUnsaturated ester compounds are lacking an effective process. Therefore, an inexpensive catalytic system was developed to realizeE)-βAryl-β,γGreen, efficient synthesis of unsaturated ester compoundsIs extremely important.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides (A)E)-βAryl-β,γThe method for synthesizing the unsaturated ester compound is obtained by one-step synthesis reaction of alkyne, ethyl diazoacetate and arylboronic acid under the catalysis of cuprous iodide, and has the characteristics of simple reaction steps, cheap and easily-obtained raw materials, wide substrate application range, high stereoselectivity and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a composition ofE)-βAryl-β,γ-a method for the synthesis of unsaturated ester compounds, comprising in particular the steps of:

mixing alkyne compound, solvent, ethyl diazoacetate, arylboronic acid compound, phenanthroline (Phen), CuI and K₃PO₄Mixing, then carrying out closed reaction for 1.2-3 hours at 90-110 ℃ in an inert gas atmosphere, and carrying out post-treatment after the reaction is finished.

Specifically, the acetylene hydrocarbon compound is preferably phenylacetylene, 4-methylphenylacetylene, 4-ethylphenylacetylene, 4-propylphenylacetylene, 4-butylphenylacetylene, 4-tert-butylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 3-fluorophenylacetylene, 3-chlorophenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, methylpropargylether, glycidylpropargylether or cyclopropylacetylene.

Specifically, the aromatic boronic acid compound is preferably phenylboronic acid, 4-methylphenylboronic acid, 4-ethylphenylboronic acid, 4-isopropylphenylboronic acid, 4-tert-butylbenzene boronic acid, 4-vinylphenylboronic acid, 4-chlorophenylboronic acid, 4-bromobenzene boronic acid, 3-methylphenylboronic acid, 3-methoxyphenylboronic acid, 3-fluorobenzene boronic acid, 3-chlorobenzene boronic acid, 3-bromobenzene boronic acid or the like.

Further, the above (E)-βAryl-β,γIn the method for synthesizing the unsaturated ester compound, the molar ratio of the alkyne compound, ethyl diazoacetate and the arylboronic acid compound is preferably 1.2-1.5: 1: 2-3.

Further, the above (E)-βAryl-β,γ-is notIn the synthesis method of the saturated ester compound, the mole ratio of the ligand phenanthroline to the ethyl diazoacetate is preferably 5-15: 100.

further, the above (E)-βAryl-β,γIn the method for synthesizing the unsaturated ester compound, the molar ratio of the catalyst CuI to ethyl diazoacetate is preferably 5-15: 100.

further, the above (E)-βAryl-β,γ-in the process for the synthesis of unsaturated ester compounds, the base K₃PO₄The molar ratio to ethyl diazoacetate is preferably from 1.5 to 2.5: 1.

further, the above (E)-βAryl-β,γIn the method for synthesizing the unsaturated ester compound, the solvent is preferably 1, 4-dioxane, and 1 to 2ml of 1, 4-dioxane is preferably added per 0.3mmol of ethyl diazoacetate; the inert gas is nitrogen or argon.

In the invention, CuI is used as a catalyst, phenanthroline is used as a ligand, and K₃PO₄Is prepared through reaction of alkyne, ethyl diazoacetate and arylboronic acid compound in 1, 4-dioxane solvent and the stereo and regioselective reaction of alkyne and ethyl diazoacetateE)-βAryl-β,γ-unsaturated ester compounds. In the figure, the compound 1 is a phenylacetylene compound, an alkyl propargyl ether compound and the like with various substituents on aromatic rings. The compound 2 is ethyl diazoacetate, and the compound 3 is phenylboronic acid compound with various substituents on aromatic ring. The chemical reaction equation is as follows:

。

in the present invention, the bifunctional reaction of alkynes has been rapidly developed in recent years because it can synthesize a polysubstituted olefin in one step with high efficiency and atom economy. Currently, studies on the bifunctional reaction of alkynes mainly focus on the introduction of two new groups onto two carbon atoms of an alkyne, i.e. the 1, 2-bifunctional reaction of alkynes, whereas the 1, 1-bifunctional (geminal bifunctional) reaction of alkynes, i.e. the two carbon atoms of an alkyne are introduced into a single reaction vesselA new group introduced on the same carbon atom of an alkyne is rarely studied. Therefore, the present inventors studied and developed an inexpensive transition metal-catalyzed geminal bifunctional reaction of alkynes for efficient synthesis of: (E)-βAryl-β,γThe unsaturated ester compound has important theoretical research significance and application value. Compared with the prior art, the invention has the innovativeness that:

the raw materials used in the synthesis method are easily obtained from industrial products, the reagent is cheap, the catalytic system is simple, the substrate range is wide, the reaction operation is simple, the yield is high, and the synthesis method is high-area and chemoselectivity synthesis (E)-βAryl-β,γUnsaturated ester compounds provide a simple and practical process suitable for the synthesis of various (A), (B), (C), (D) and (D) in a) anE)-βAryl-β,γ-unsaturated ester compounds.

Drawings

FIG. 1 shows the product of example 1: (E)-βAryl-β,γOf unsaturated esters 4a¹H NMR spectrum;

FIG. 2 shows the product of example 1: (E)-βAryl-β,γOf unsaturated esters 4a¹³C NMR spectrum;

FIG. 3 shows the product of example 2: (E)-βAryl-β,γOf unsaturated esters 4b¹H NMR spectrum;

FIG. 4 shows the product of example 2: (E)-βAryl-β,γOf unsaturated esters 4b¹³C NMR spectrum;

FIG. 5 shows the product of example 4: (E)-βAryl-β,γOf unsaturated esters 4d¹H NMR spectrum;

FIG. 6 shows the product of example 4: (E)-βAryl-β,γOf unsaturated esters 4d¹³C NMR spectrum;

FIG. 7 shows the product of example 5: (E)-βAryl-β,γOf unsaturated esters 4e¹H NMR spectrum;

FIG. 8 shows the product of example 5: (E)-βAryl-β,γOf unsaturated esters 4e¹³C NMR spectrum.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

First, 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (1 mL), 41. mu.L of phenylacetylene (0.36 mmol) and 124.9 mg of p-methylphenylboronic acid (0.9 mmol) were put into a 35 mL sealed tube and mixed uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the drugs were added, nitrogen gas was introduced into the sealed tube for about 3 minutes, the air in the sealed tube was removed, the tube opening was sealed with a cock, and the reaction was stirred at 100 ℃ for 1.5 hours. After the reaction, the system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extracted with ethyl acetate, the organic phases were combined, the organic phase solvent was removed by distillation under reduced pressure, and the mixture was subjected to silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=50: 1) to yield 71.0 mg of colorless liquid product 4a in 85% yield. The reaction is shown in the following formula:

spectrogram analysis data

¹H NMR (400 MHz, CDCl₃): δ= 1.17 (t, J = 7.2 Hz, 3H), 2.36 (s, 3H), 3.69 (s, 2H), 4.11 (q, J = 7.2 Hz, 2H), 7.00 (s, 1H), 7.18 (d, J = 7.6 Hz, 2H), 7.28-7.41 (m, 7H); ¹³C NMR (100 MHz, CDCl₃): δ= 14.1, 21.1, 36.6, 60.8, 126.1, 127.1, 128.4, 128.8, 129.2, 130.4, 134.5, 137.4, 137.6, 138.8, 171.6. HRMS(ESI-TOF).Calcd for C₁₉H₂₁O₂, [M+H]⁺ m/z 281.1542, Found 281.1537。

The above-mentioned 4a compounds can be used for the synthesis of the known substances 3-arylnaphthols:

84 mg of 4a (0.3 mmol) are dissolved in 300 mg of concentrated H₂SO₄In, stirring at room temperature 2And (4) hours. After the reaction was completed, 2mL of cold water was carefully added, extraction was performed with ethyl acetate (3X 5 mL), the organic phases were combined, the solvent of the organic phase was removed by distillation under the reduced pressure, and the mixture was subjected to silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=10: 1) to obtain 52.0 mg of the product 5a as a white solid in 74% yield, according to the following reaction equation:

。

example 2

First, 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (1 mL), 47. mu.L of p-methylphenylacetylene (0.36 mmol) and 124.9 mg of p-methylphenylboronic acid (0.9 mmol) were put into a 35 mL sealed tube and mixed uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the drugs were added, nitrogen gas was introduced into the sealed tube for about 3 minutes, the air in the sealed tube was purged, the tube mouth was sealed with a cock, and the mixture was stirred at 100 ℃ for 1.5 hours. After the reaction, the reaction system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extraction was performed with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=50: 1) to give 72.0 mg of the colorless liquid product 4b (CAS number 130240-35-6) in 82% yield. The reaction is shown in the following formula:

spectrogram analysis data

Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ= 1.19 (t, J = 7.2 Hz, 3H), 2.37 (s, 3H), 2.38 (s, 3H), 3.71 (s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 6.99 (s, 1H), 7.18 (d, J = 5.2 Hz, 2H), 7.20 (d, J = 5.2 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ= 14.1, 21.1, 21.2, 36.6, 60.7, 126.0, 128.6, 129.1, 129.1, 130.4, 133.8, 134.6, 136.8, 137.2, 138.9, 171.7. HRMS(ESI-TOF).Calcd for C₂₀H₂₃O₂, [M+H]⁺ m/z 295.1698, Found 295.1688。

Example 3:

first, a 35 mL sealed tube was charged with a stirrer, and 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (1 mL), 42. mu.L of p-fluoroacetylene (0.36 mmol), and 124.9 mg of p-methylphenylboronic acid (0.9 mmol) were added thereto and mixed uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the drugs were added, nitrogen gas was introduced into the sealed tube for about 3 minutes, the air in the sealed tube was purged, the tube mouth was sealed with a cock, and the mixture was stirred at 100 ℃ for 1.5 hours. After the reaction, the reaction system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extraction was performed with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=50: 1) to give 63.0 mg of the colorless liquid product 4c in 70% yield. The reaction is shown in the following formula:

spectrogram analysis data

Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ= 1.18 (t, J = 7.2 Hz, 3H), 2.37 (s, 3H), 3.65 (s, 2H), 4.11 (q, J = 7.2 Hz, 2H), 6.95 (s, 1H), 7.06 (t, J = 7.2 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 7.34-7.40 (m, 4H); ¹³C NMR (100 MHz, CDCl₃): δ= 14.1, 21.1, 36.5, 60.8, 115.3 (d, J = 21.0 Hz), 126.0, 129.2, 129.3, 130.4 (d, J = 8.0 Hz), 133.6 (d, J = 4.0 Hz), 134.6, 137.5, 138.5, 161.9 (d, J = 245.0 Hz), 171.5. HRMS(ESI-TOF).Calcd for C₁₉H₂₀FO₂, [M+H]⁺ m/z 299.1447, Found 299.1438。

Example 4

First, 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (2 mL), 41. mu.L of phenylacetylene (0.36 mmol) and 145.0 mg of m-chlorobenzeneboronic acid (0.9 mmol) were put into a 35 mL sealed tube and mixed uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the drugs were added, nitrogen gas was introduced into the sealed tube for about 3 minutes, the air in the sealed tube was purged, the tube mouth was sealed with a cock, and the mixture was stirred at 100 ℃ for 1.5 hours. After the reaction, the reaction system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extraction was performed with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=50: 1) yield 65.0 mg colorless liquid product 4d, 72% yield. The reaction is shown in the following formula:

spectrogram analysis data

Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ= 1.18 (t, J = 7.2 Hz, 3H), 3.68 (s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 7.02 (s, 1H), 7.26-7.39 (m, 8H), 7.50 (s, 1H); ¹³C NMR (100 MHz, CDCl₃): δ= 14.1, 36.6, 60.9, 124.5, 126.5, 127.5, 127.6, 128.5, 128.7, 129.6, 132.3, 133.6, 134.4, 137.0, 143.7, 171.1. HRMS(ESI-TOF).Calcd for C₁₈H₁₈ClO₂, [M+H]⁺ m/z 301.0995, Found 301.0992。

Example 5

First, a 35 mL sealed tube was charged with a stirrer, and 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (1 mL), 31. mu.L of methyl propinyl ether (0.36 mmol), and 124.9 mg of p-methylphenylboronic acid (0.9 mg)mmol) and mixing uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the drugs were added, nitrogen gas was introduced into the sealed tube for about 3 minutes, the air in the sealed tube was purged, the tube mouth was sealed with a cock, and the mixture was stirred at 100 ℃ for 1.5 hours. After the reaction, the reaction system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extraction was performed with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=70: 1) to give 68.5 mg of the colorless liquid product 4e in 92% yield. The reaction is shown in the following formula:

spectrogram analysis data

Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ= 1.19 (t, J = 7.2 Hz, 3H), 2.34 (s, 3H), 3.39 (s, 3H), 3.53 (s, 2H), 4.10-4.17 (m, 4H), 6.07 (t, J = 6.4 Hz, 1H), 7.13 (d, J = 7.6 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ= 14.1, 21.0, 36.4, 58.2, 60.8, 69.4, 125.9, 127.5, 129.0, 135.4, 137.2, 138.5, 170.9. HRMS(ESI-TOF).Calcd for C₁₅H₂₀NaO₃, [M+Na]⁺ m/z 271.1310, Found 271.1303。

Example 6

First, 33. mu.L of ethyl diazoacetate (0.3 mmol), 1, 4-dioxane (1 mL), 31. mu.L of cyclopropylacetylene (0.36 mmol) and 124.9 mg of p-methylphenylboronic acid (0.9 mmol) were put into a 35 mL sealed tube and mixed uniformly. Then, 5.4 mg of Phen (0.03 mmol), 5.7 mg of CuI (0.03 mmol) and 130.0 mg of K were added to the above well-mixed solution in this order₃PO₄(0.6 mmol). After all the medicine is added, nitrogen is introduced into the sealed tube for about 3 minutes, air in the sealed tube is removed, the tube opening is sealed by a cock at 100 DEG CStirred under conditions for 1.5 hours. After the reaction, the reaction system was cooled to room temperature, 3 mL of distilled water was added to the reaction system, extraction was performed with ethyl acetate, the organic phases were combined, the solvent of the organic phase was removed by distillation under reduced pressure, and silica gel column chromatography (V)_{Petroleum ether}：V_{Ethyl acetate}=70: 1) yield 66.0 mg colorless liquid product 4f, yield 90%. The reaction is shown in the following formula:

spectrogram analysis data

Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ= 0.47-0.51 (m, 2H), 0.85-0.88 (m, 2H), 1.20 (t, J = 7.2 Hz, 3H), 1.58-1.66 (m, 1H), 2.31 (s, 3H), 3.61 (s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 5.31 (d, J = 9.2 Hz, 1H), 7.09 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ= 7.5, 11.3, 14.1, 21.0, 36.4, 60.6, 125.4, 128.9, 130.8, 135.7, 136.2, 139.2, 171.7. HRMS(ESI-TOF).Calcd for C₁₆H₂₁O₂, [M+H]⁺ m/z 245.1542, Found 245.1538。

Claims (6)

1. A composition ofE)-βAryl-β,γ-a method for the synthesis of an unsaturated ester compound, characterized in that it comprises the following steps:

mixing alkyne compound 1, solvent 1, 4-dioxane, ethyl diazoacetate 2, arylboronic acid compound 3, phenanthroline, CuI and K₃PO₄Mixing, then carrying out closed reaction for 1.2-3 hours at 90-110 ℃ in an inert gas atmosphere, and carrying out post-treatment after the reaction is finished to obtain a compound 4;

the chemical reaction equation is as follows:

the alkyne compound 1 is phenylacetylene, 4-methylphenylacetylene, 4-ethylphenylacetylene, 4-propylphenylacetylene, 4-butylphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 3-fluorophenylacetylene, 3-chlorophenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, methylpropargylether, glycidylpropargylether or cyclopropylacetylene;

the aromatic boric acid compound 3 is phenylboronic acid, 4-methylphenylboronic acid, 4-ethylphenylboronic acid, 4-isopropylphenylboronic acid, 4-tert-butylbenzene boronic acid, 4-vinylphenylboronic acid, 4-chlorobenzene boronic acid, 4-bromobenzene boronic acid, 3-methylphenylboronic acid, 3-methoxyphenylboronic acid, 3-fluorobenzene boronic acid, 3-chlorobenzene boronic acid or 3-bromobenzene boronic acid.

2. The composition of claim 1 (E)-βAryl-β,γThe synthesis method of the unsaturated ester compound is characterized in that the molar ratio of the alkyne compound to the ethyl diazoacetate to the arylboronic acid compound is 1.2-1.5: 1: 2-3.

3. The composition of claim 2 (E)-βAryl-β,γThe synthesis method of the unsaturated ester compound is characterized in that the molar ratio of the phenanthroline to the ethyl diazoacetate is 5-15: 100.

4. the composition of claim 2 (E)-βAryl-β,γ-a method for synthesizing an unsaturated ester compound, characterized in that the molar ratio of CuI to ethyl diazoacetate is 5-15: 100.

5. the composition of claim 2 (E)-βAryl-β,γ-a method for synthesizing an unsaturated ester compound, characterized in that K is₃PO₄The mol ratio of the diazoacetic acid ethyl ester is 1.5-2.5: 1.

6. the composition of claim 2 (E)-βAryl-β,γ-a method for the synthesis of an unsaturated ester compound, characterized in that the inert gas is nitrogen or argon.

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