A method for preparing an α-hydroxy-β-dicarbonyl derivative

Abstract

The present invention is applicable to the technical field of organic synthesis, and provides a preparation method of α-hydroxy-β-dicarbonyl derivatives, comprising the following steps: under photo-initiation conditions, in the presence of an iodide and a phosphide or a nitride as a catalyst, water reacts with β-dicarbonyl to obtain α-hydroxy-β-dicarbonyl derivatives. In the present invention, an EDA system is formed by an iodide and a phosphide or a nitride and a β-dicarbonyl compound, free radicals are generated under light irradiation, and then a hydration reaction occurs to generate α-hydroxy-β-dicarbonyl derivatives. The catalytic system is simple, the conditions are mild, the solvent is green, no oxidant is required, the applicable range is wide, the production cost can be effectively reduced, the yield and chemical selectivity can be improved, and it can be conveniently applied to the preparation of various α-hydroxy-β-dicarbonyl derivatives.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing α-hydroxy-β-dicarbonyl derivatives. Background Art

[0002] α-Hydroxy-β-dicarbonyl building blocks are the core structures of many natural drugs. For example, they can be used to synthesize biologically important compounds such as cyclopentenone jellyfishin-like (1), biosynthetic precursors of valine and isoleucine (2) [α-acetolactate (2a) and α-acetylhydroxybutyrate (2b)], and tetracycline antibiotics such as doxycycline (3).

[0003]

[0004] Currently reported synthetic methods for quinazolinone compounds mainly include the following several:

[0005] In 2003, the Jens research group reported the metal-catalyzed α-hydroxylation of various cyclic and acyclic β-dicarbonyl compounds by molecular oxygen. In the reaction, cerium metal salt CeCl3·7H2O was used as the catalyst, which was not green enough. Moreover, the oxidation of acyclic dicarbonyl compounds was accompanied by side reactions and decomposition, and the substrate scope was relatively small.

[0006]

[0007] In 2004, the Togni research group reported the direct hydroxylation catalyzed by asymmetric transition metals titanium and ruthenium. This reaction used relatively expensive chiral transition metal catalysts to directly hydroxylate α-Hydroxy-β-oxoesters, but it had no reaction with weakly enolizable β-ketoesters.

[0008]

[0009] In 2010, the Hii research group reported the use of dimethyldioxirane (DMD) as an effective oxidant for the hydroxylation of 1,3-ketoesters. Under the conditions of chiral phosphine ligands and palladium catalysts, a series of chiral α-Hydroxy-β-oxoesters compounds were synthesized.

[0010]

[0011] In 2016, the Mario research group reported the asymmetric hydroxylation reaction of β-ketoesters with aziridine using chiral bifunctional urea ammonium salts as catalysts.

[0012]

[0013] Although the research on the metal-catalyzed reaction of 1,3-dicarbonyl compounds has gradually shifted to metal-free catalysis, the oxidant remains a major obstacle to making this reaction more environmentally friendly. Summary of the Invention

[0014] An object of an embodiment of the present invention is to provide a method for preparing an α-hydroxy-β-dicarbonyl derivative, aiming to solve the problems raised in the above-mentioned background technology.

[0015] An embodiment of the present invention is implemented as follows. A method for preparing an α-hydroxy-β-dicarbonyl derivative comprises the steps of: using β-dicarbonyl as a substrate, in a solvent, in an environment without an oxidant, under blue light initiation, and catalyzed by an iodide and a phosphide or a nitride, to obtain an α-hydroxy-β-dicarbonyl derivative. The reaction formula is as follows:

[0016]

[0017] Preferably, the β-dicarbonyl is one of 1,3-dicarbonyl and sulfone.

[0018] Preferably, R 1 , R 2 and R 3 groups in the β-dicarbonyl derivative are each independently selected from:

[0019] hydrogen, halogen, substituted or unsubstituted C 1～10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C 1～10 alkoxy, substituted or unsubstituted amino, carboxyl, ester group, acyl group, cyano group, nitro group, hydroxyl group, azide group.

[0020] Preferably, the molar ratio of the β-dicarbonyl derivative to the iodide is 1:0.1 - 2.0, the molar ratio of the β-dicarbonyl derivative to the phosphide is 1:0.1 - 2.0, and the molar ratio of the β-dicarbonyl derivative to the nitride is 1:0.1 - 2.0.

[0021] Preferably, the solvent is one or more of water, methanol, ethanol, dichloromethane, acetonitrile, benzene, toluene, acetone, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol, polyethylene glycol, etc.;

[0022] The iodide is one or more of sodium iodide, potassium iodide, lithium iodide, rubidium iodide, cesium iodide. In addition, there are sodium fluoride, sodium bromide, and sodium chloride that can replace the iodide;

[0023] The nitride is one or more of substituted or unsubstituted C 1～10 alkylamines (such as trimethylamine, triethylamine) and substituted or unsubstituted arylamines (such as triphenylamine);

[0024] The phosphide is one or more of a substituted or unsubstituted C 1～10 alkylphosphine (such as tripropylphosphine), a substituted or unsubstituted arylphosphine (such as triphenylphosphine);

[0025] The water is pure water or tap water.

[0026] Preferably, the reaction temperature is room temperature and the reaction time is 1 - 48 h.

[0027] Preferably, the reaction is carried out in air or an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0028] Preferably, the molar ratio of the solvent to the β-dicarbonyl derivative is 1:0.001 - 1.

[0029] Preferably, after the reaction is completed, the reaction solution is extracted with ethyl acetate, washed with water several times using the organic phase and dried using anhydrous magnesium sulfate, and finally the organic phase is concentrated to obtain the α-hydroxy-β-dicarbonyl derivative through flash chromatography and a C18 silica gel column.

[0030] Preferably, the concentration is carried out by one of atmospheric distillation, vacuum distillation, and rotary evaporation.

[0031] Preferably, post-treatment can also be carried out using column chromatography purification. The column chromatography uses silica gel of 200 - 300 mesh as the stationary phase, and the eluent is selected from at least one of petroleum ether, n-hexane, dichloromethane, water, acetonitrile, methanol, and ethyl acetate.

[0032] Preferably, the structural formula of the α-hydroxy-β-dicarbonyl derivative is as follows:

[0033]

[0034] The technical effect of the present invention lies in:

[0035] A preparation method of an α-hydroxy-β-dicarbonyl derivative provided by an embodiment of the present invention forms an EDA system through an iodide and a phosphide or a nitride and a β-dicarbonyl compound, generates free radicals under light, and then undergoes a hydration reaction to generate an α-hydroxy-β-dicarbonyl derivative. The catalytic system of the present invention is simple, the conditions are mild, the solvent is green, no oxidant is required, the scope of application is wide, the production cost can be effectively reduced, the yield and chemical selectivity can be improved, and it can be conveniently applied to the preparation of various α-hydroxy-β-dicarbonyl derivatives. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is the 1H NMR spectrum of compound 2a provided by Example 1 of the present invention;

[0037] Figure 213C NMR carbon spectrum of compound 2a prepared in Example 1 of the present invention. Detailed implementation mode

[0038] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the following further elaborates on the present invention in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0039] A preparation method of an α-hydroxy-β-dicarbonyl derivative, the steps are as follows:

[0040] Using β-dicarbonyl as a substrate, in a solvent, in an environment without an oxidant, under blue light initiation, catalyzed by an iodide and a phosphide or a nitride, to obtain an α-hydroxy-β-dicarbonyl derivative, and the reaction formula is as follows:

[0041]

[0042] Among them, β-dicarbonyl is one of 1,3-dicarbonyl and sulfone. R in the β-dicarbonyl derivative 1 , R 2 and R 3 groups are each independently selected from: hydrogen, halogen, substituted or unsubstituted C 1～10 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted C 1～10 alkoxy, substituted or unsubstituted amino, carboxyl, ester group, acyl group, cyano group, nitro group, hydroxyl group, azide group.

[0043] According to the present invention, the iodide is one or more of sodium iodide, potassium iodide, lithium iodide, rubidium iodide, cesium iodide. In addition, it can also be sodium fluoride, sodium bromide, sodium chloride that replace the iodide; the nitride is one or more of substituted or unsubstituted C 1～10 alkylamine, substituted or unsubstituted arylamine; the phosphide is one or more of substituted or unsubstituted C 1～10 alkylphosphine, substituted or unsubstituted arylphosphine. It should be understood that in the reaction of the present invention, the common point of the above catalysts is an iodide or a metal compound of a halogen element, the nitride is one or more of substituted or unsubstituted C 1～10 alkylamine, substituted or unsubstituted arylamine; the phosphide is one or more of substituted or unsubstituted C 1～10One or more of alkyl phosphines, substituted or unsubstituted aryl phosphines. Therefore, as long as the types of the above catalysts are selected, the above reactions of the present application can be achieved. Although only the embodiments of individual catalyst types are given in the specific embodiments of the present invention, those skilled in the art should understand that the embodiments are only used to explain the preferred implementation schemes given by the present invention and are not used to limit the present invention. Under the inspiration given by the embodiments, those skilled in the art can also obtain the present invention according to other catalysts given by the present invention.

[0044] According to the present invention, the solvent is one or more of water, methanol, ethanol, dichloromethane, acetonitrile, benzene, toluene, acetone, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol, polyethylene glycol, etc. Water is pure water or tap water; it should be understood that in the reaction of the present invention, the use of the above solvents is only for dissolving β-dicarbonyl derivatives, and the solvents themselves do not participate in the reaction. Therefore, as long as the solvents capable of dissolving β-dicarbonyl derivatives are selected, the above reactions of the present application can be achieved. Although only the embodiment of water as the solvent is given in the specific embodiments of the present invention, those skilled in the art should understand that the embodiments are only used to explain the preferred implementation schemes given by the present invention and are not used to limit the present invention. Under the inspiration given by the embodiments, those skilled in the art can also obtain the present invention according to other solvents given by the present invention.

[0045] According to the present invention, the molar ratio of β-dicarbonyl derivative to iodide is 1:0.1 - 2.0, the molar ratio of β-dicarbonyl derivative to phosphide is 1:0.1 - 2.0, and the molar ratio of β-dicarbonyl derivative to nitride is 1:0.1 - 2.0. It should be understood that in the reaction of the present invention, as long as the catalytic conditions of iodide and phosphide or nitride exist, the above reaction can occur. Although only the molar ratios of individual β-dicarbonyl derivatives to iodide, β-dicarbonyl derivatives to phosphide, and β-dicarbonyl derivatives to nitride are given in the specific embodiments of the present invention, those skilled in the art should understand that the embodiments are only used to explain the preferred implementation schemes given by the present invention and are not used to limit the present invention. Under the inspiration given by the embodiments, those skilled in the art can also obtain the present invention according to other parameters given by the present invention.

[0046] According to the present invention, the molar ratio of the solvent to the β-dicarbonyl derivative is 1:0.001 to 1. In the reaction of the present invention, as long as the β-dicarbonyl derivative can be dissolved in the solvent, although only individual molar ratios of the solvent to the β-dicarbonyl derivative are given in the specific examples of the present invention, those skilled in the art should understand that the examples are only used to explain the preferred implementation schemes given by the present invention and are not used to limit the present invention. Those skilled in the art can also obtain the present invention according to other parameters given by the present invention under the inspiration of the examples.

[0047] After the reaction of the present invention is completed, the reaction solution is extracted with ethyl acetate, the organic phase is washed with water multiple times and dried with anhydrous magnesium sulfate, and finally the organic phase is concentrated, and the α-hydroxy-β-dicarbonyl derivative is obtained through flash chromatography and a C18 silica gel column.

[0048] The structural formula of the α-hydroxy-β-dicarbonyl derivative prepared in the following examples of the present invention is as follows:

[0049]

[0050] In order to further understand the present invention, the preparation method of the α-hydroxy-β-dicarbonyl derivative provided by the present invention will be described in detail below in conjunction with examples. The protection scope of the present invention is not limited by the following examples.

[0051] Example 1

[0052] A preparation method of an α-hydroxy-β-dicarbonyl derivative (Compound 3a), the reaction formula and preparation method are as follows:

[0053] Method 1:

[0054]

[0055] The specific steps are as follows: Add β-dicarbonyl compound (0.2 mmol, 1.0 equiv.), PPh 3 (20% mmol), NaI (0.22 mmol, 1.1 equiv.) and H 2 O (2 mL) into a 25 mL quartz tube. The mixture is evacuated and purged with argon three times. Then, at room temperature, the mixture is stirred under irradiation of a 10 W blue LED for 36 hours. After completion, the mixture is quenched with water (5 mL) and extracted with ethyl acetate (10 mL × 3). The combined organic layers are dried over Na 2 SO 4 and concentrated under reduced pressure. The residue is purified by silica gel chromatography and eluted with an ethyl acetate / petroleum ether mixture to obtain the product, a colorless oily liquid, with a separation yield of 94%.

[0056] Method 2:

[0057]

[0058] The specific steps are as follows: Add β-dicarbonyl compound (0.2 mmol, 1.0 equiv.), PPh 3 (20% mmol), NaI (30% mmol) and EtOH:H2O = 1:2 (2 mL) into a 25 mL quartz tube. Then, at room temperature, under the irradiation of a 10 W white LED, stir the mixture for 36 hours. After completion, quench the mixture with water (5 mL) and extract with ethyl acetate (10 mL × 3). The combined organic layers are dried over Na 2 SO 4 and concentrated under reduced pressure. The residue is purified by silica gel chromatography, eluted with an ethyl acetate / petroleum ether mixture (20:1) to obtain the product, a colorless oily liquid, with a separation yield of 94%.

[0059] Structure identification of compound 2a:

[0060] Nuclear magnetic resonance data:

[0061] 1 1H NMR (400 MHz, Chloroform-d) δ 8.01–7.99 (m, 2H), 7.62–7.58 (m, 1H), 7.47 (t, J = 7.8 Hz, 2H), 4.51 (s, 1H), 4.24 (q, J = 7.2 Hz, 2H), 1.76 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H).

[0062] 13 13C NMR (101 MHz, Chloroform-d) δ 195.86, 172.22, 133.66, 133.01, 129.40, 128.57, 79.37, 62.45, 23.46, 13.76.

[0063] The 1 1H NMR 13 and Figure 1 13C NMR of compound 2a are as shown in Figure 2 . The analysis results indicate that the obtained target product is correct.

[0064] Example 2

[0065] A preparation method of an α-hydroxy-β-dicarbonyl derivative (3o), the structure and preparation method are as follows:

[0066]

[0067] The specific steps are as follows: Add 1 g (0.2 mmol, 1.0 equiv.) of β-dicarbonyl compound, NPh 3 (20% mmol), NaI (30% mmol), and EtOH:H2O = 9:1 (2 mL) into a 25 mL quartz tube. Then, at room temperature, irradiate the mixture with a 10 W white LED and stir for 36 hours. After completion, quench the mixture with water (5 mL) and extract with ethyl acetate (10 mL × 3). The combined organic layers are dried over Na 2 SO 4 and concentrated under reduced pressure. The residue is purified by silica gel chromatography, eluted with an ethyl acetate / petroleum ether mixture (20:1) to obtain the product, a colorless oily liquid, with a separation yield of 88%.

[0068] Structure identification of this compound:

[0069] Nuclear magnetic resonance data:

[0070] 1 H NMR (500 MHz, Chloroform-d) δ 8.74 (s, 1H), 7.57–7.55 (m, 2H), 7.35–7.31 (m, 2H), 7.15–7.11 (m, 1H), 4.32 (s, 1H), 3.89 (s, 3H), 1.76 (s, 3H).

[0071] 13 C NMR (125 MHz, DMSO-d 6 ) δ 162.02, 159.50, 152.09, 150.07, 134.28, 129.91, 127.85, 126.51, 123.87, 121.39, 116.80, 115.16, 55.37.

[0072] For compound 3o 1 H NMR, 13 The analysis results of 13C NMR data indicate that the obtained target product is correct.

[0073] Example 3

[0074] A preparation method of an α-hydroxy-β-carbonyl derivative (compound 5d), whose structure and preparation method are as follows:

[0075]

[0076] The specific steps are as follows: Add β-dicarbonyl compound (0.2 mmol, 1.0 equiv.), PPh 3 (20% mmol), NaI (0.22 mmol, 1.1 equiv.), and H2 O (2 mL). The mixture was evacuated and backfilled with argon three times. Then at room temperature, the mixture was stirred for 36 h under irradiation of a 10 W blue LED. After completion, the mixture was quenched with water (5 mL) and extracted with ethyl acetate (10 mL×3). The combined organic layers were dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluted with an ethyl acetate / petroleum ether mixture to give the product as a white solid in 86% isolated yield.

[0077] The specific procedure was as follows: In a 25 mL quartz tube, β-dicarbonyl compound (0.2 mmol, 1.0 equiv.), NPh 3 (20% mmol), NaI (30% mmol) and EtOH:H2O = 1:2 (2 mL) were added. Then at room temperature, the mixture was stirred for 36 h under irradiation of a 10 W white LED. After completion, the mixture was quenched with water (5 mL) and extracted with ethyl acetate (10 mL×3). The combined organic layers were dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluted with an ethyl acetate / petroleum ether mixture to give the product as a white solid in 81% isolated yield.

[0078] Structure identification of compound 5d:

[0079] NMR data:

[0080] 1 H NMR (500 MHz, Chloroform-d) δ 8.61–8.60 (m, 2H), 7.52–7.50 (m, 2H), 4.09 (s, 1H), 3.82 (s, 3H), 1.79 (s, 3H).

[0081] 13 C NMR (126 MHz, Chloroform-d) δ 174.91, 151.49, 149.85, 120.34, 75.14, 53.58, 26.78.

[0082] For compound 5d, 1 the 13 H NMR and

[0083] Example 4

[0084] This example illustrates a method for preparing the fungicide chlozolinate using the α-hydroxy-β-carbonyl derivative prepared by the present invention as an intermediate.

[0085] A preparation method of the fungicide drug Chlozolinate, whose structure and preparation method are as follows:

[0086]

[0087] The specific steps are as follows: Add 2,2,5-trimethyl-1,3-dioxane-4,6-dione (12.66 mmol, 1.0 equiv.) to EtOH:Toluene = 1:2 (0.1 M), evacuate and backfill with argon three times. The resulting mixture is stirred in an argon atmosphere at 95 °C for 18 hours. After the reaction is completed, add H 2 O and saturated NaHCO 3 (20 mL). Extract the mixture with EtOAc (5 mL x 2). Discard the organic layer. Acidify the aqueous layer with concentrated hydrochloric acid (until pH = 2). Extract the mixture with EtOAc (20 mL x 4). Wash the combined organic layers with brine (5 mL x 1). Dry the combined organic layers with Na 2 SO 4 and concentrate under reduced pressure to obtain the product 3-ethoxy-2-methyl-3-oxopropanoic acid (1.72 g, 93.0%), a colorless oily liquid.

[0088] Add 3-ethoxy-2-methyl-3-oxopropanoic acid (11.77 mmol, 1.0 equiv.) and thionyl chloride (10 mL) to a 50 mL round-bottom flask. The resulting mixture is stirred at 80 °C for 16 hours. The resulting mixture is concentrated in vacuo. Add dichloromethane (20 mL) and phenol (12.95 mmol, 1.1 equiv.) to the above mixture, stir the mixture at 0 °C, and slowly add triethylamine (23.54 mmol, 2.0 equiv.) dropwise within 5 minutes. The resulting mixture is stirred at 25 °C for 3 hours. Monitor the progress of the reaction by TLC. After the reaction is completed, quench the mixture with water and saturated Na 2 CO 3 (20 mL) and extract with dichloromethane (10 mL×3). The combined organic layers are dried with Na 2 SO 4 and concentrated under reduced pressure. The residue is purified by silica gel chromatography, eluted with an ethyl acetate / petroleum ether mixture to obtain the colorless oily liquid 1-ethyl-3-phenyl-2-methylmalonate (2.38 g, 90.8%).

[0089] In a 25 mL quartz tube, add 1-ethyl 3-phenyl-2-methylmalonate (0.2 mmol, 1.0 equiv.), NPh3 (20% mmol), NaI (30% mmol) and EtOH:H2O = 1:2 (2 mL). Then, at room temperature, irradiate the mixture with a 10 W white LED and stir for 36 h. After completion, quench the mixture with water (5 mL) and extract with ethyl acetate (10 mL × 3). The combined organic layers are dried over Na 2 SO 4 and concentrated under reduced pressure. The residue is purified by silica gel chromatography, eluted with a mixture of ethyl acetate / petroleum ether to give 1-ethyl 3-phenyl-2-hydroxy-2-methylmalonate (39.15 mg, 83%).

[0090] Under N 2 atmosphere, add triethylamine (25.3 mg, 0.25 mmol) and 3,5-dichlorophenyl isocyanate (70.7 mg, 0.375 mmol) to a solution of 1-ethyl 3-phenyl-2-hydroxy-2-methylmalonate (59.5 mg, 0.25 mmol) in dry n-hexane (10.0 mL). After stirring for 30 min under constant temperature conditions, reflux the reaction mixture overnight (16 h). After cooling, filter the suspension, evaporate the filtrate to dryness, and purify the residue by silica gel chromatography, eluted with a mixture of ethyl acetate / petroleum ether to give the white solid Chlozolinate (58.2 mg, 70.1%).

[0091] Structural identification of compound Chlozolinate:

[0092] Nuclear magnetic resonance data:

[0093] 1 H NMR (500 MHz, Chloroform-d) δ 7.46–7.44 (m, 3H), 4.34 (q, J = 7.0 Hz, 2H), 1.90 (s, 3H), 1.34 (t, J = 7.0 Hz, 3H).

[0094] 13 C NMR (126 MHz, Chloroform-d) δ 168.39, 164.05, 151.91, 135.72, 132.37, 129.33, 123.71, 83.89, 63.94, 18.80, 13.93.

[0095] For compound Chlozolinate 1 H NMR 13 and C NMR data analysis results indicate that the obtained target product is correct.

[0096] The present invention also synthesized compounds 3b - 5b shown in Table 1 by a method similar to that of the above Examples 1 - 3. The method for synthesizing compounds 3b - 5b is the same in principle as that of Examples 1 - 3, except for the raw materials. For the raw materials, structural formulas, and product yields of the synthesis reactions of compounds 3b - 5b, please refer to Table 1. The nuclear magnetic resonance data of compounds 3b - 5b are shown in detail in Table 2.

[0097] Table 1 Raw materials, structural formulas, and product yields of the synthesis reactions of compounds 3b - 5b

[0098]

[0099]

[0100] Table 2 Nuclear magnetic resonance data of compounds 3b - 5b

[0101]

[0102]

[0103]

[0104]

[0105] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing examples, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an α-hydroxy-β-dicarbonyl derivative, characterized in that, the steps are as follows: Using a β-dicarbonyl derivative as a substrate, in water, under an environment without an oxidant, under blue light irradiation, catalyzed by an iodide and a phosphide, to obtain an α-hydroxy-β-dicarbonyl derivative, The reaction formula is as follows: Among them, R 1 group, R 3 group is selected from: aryl, C 1～10 alkyl, C 1～10 alkoxy, R 2 group is selected from: hydrogen, C 1～10 alkyl, aryl; The iodide is one or more of sodium iodide, potassium iodide, lithium iodide, rubidium iodide, and cesium iodide; The phosphide is triphenylphosphine.

2. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, the molar ratio of the β-dicarbonyl derivative to the iodide is 1:0.1 - 2.0, and the molar ratio of the β-dicarbonyl derivative to the phosphide is 1:0.1 - 2.

0.

3. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, the water is pure water or tap water.

4. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, the reaction temperature is room temperature.

5. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, the reaction is carried out under an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

6. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, the molar ratio of the solvent to the β-dicarbonyl derivative is 1:0.001 - 1.

7. The method for preparing an α-hydroxy-β-dicarbonyl derivative according to claim 1, characterized in that, after the reaction is completed, the reaction solution is extracted with ethyl acetate, washed with water multiple times using the organic phase, dried with anhydrous magnesium sulfate, and finally the organic phase is concentrated, and the α-hydroxy-β-dicarbonyl derivative is obtained through flash chromatography and a C18 silica gel column.

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