A method for synthesizing 2-aryl-2-cyclohexanedione enol ester compounds

Abstract

The application belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of 2-aryl-2-cyclohexanedione enol ester compounds. The method uses a transition metal complex as a catalyst, and uses a phenyl boronic acid compound and an iodine onium compound as raw materials, first synthesizes a 3-hydroxy-2-aryl-2-cyclohexenone compound, and then synthesizes the 2-aryl-2-cyclohexanedione enol ester compound through acylation. The reaction condition is mild, no additional additives (such as alkali-sodium acetate, expensive silver salt-silver acetate, etc.) need to be added, the C-C bond can be efficiently and quickly constructed, the 2-aryl-2-cyclohexanedione cyclization derivative is obtained, the reaction operation is simple, the reaction time is short, the method has high efficiency and high safety, the substrate range is wide, the functional group tolerance is good, the method conforms to the concept of green chemistry and high atomic economy, and is very suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis technology. More specifically, it relates to a method for synthesizing 2-aryl-2-cyclohexanedione enol esters. Background Technology

[0002] Clethodim, a selective herbicide, is an acetyl-CoA carboxylase (ACC) inhibitor and belongs to the cyclohexanone class of herbicides. However, this type of herbicide is also toxic to non-target organisms that also contain acetyl-CoA carboxylase. Studies have shown that clethodim reduces fatty acid biosynthesis by inhibiting acetyl-CoA carboxylase, causing chlorosis in rapeseed and ultimately leading to reduced yield or even crop death. Therefore, there is an urgent need to develop new, safe herbicides that can control weeds without affecting crops, in order to expand their application.

[0003]

[0004] To address the aforementioned issues, Fu et al. (Fei Ye, Peng Ma, Yue Zhai, Fei Yang, Shuang Gao, Li-Xia Zhao, Ying Fu. Design, microwave-assisted synthesis, bioactivity and SAR of novel substituted 2-phenyl-2-cyclohexanedione enol ester derivatives RSC Adv., 2018, 8, 19883.) designed a class of novel substituted 2-aryl-2-cyclohexanedione enol ester derivatives based on structure-activity relationships and combinations of active substructures. These derivatives exhibit a certain degree of chlorophyll recovery. Among them, compound 3 (S24) shows the best repair activity against clethodim damage, even surpassing that of the commercially available safener cloquintocet-mexyl. Furthermore, greenhouse experiments indicate that compound 3 (S24) has the best safety activity, with various properties similar to the safener cloquintocet. Therefore, substituted 2-aryl-2-cyclohexanedione enol ester derivatives have become novel lead compounds for the development of new safeners.

[0005]

[0006] Furthermore, current research has demonstrated that cyclic diketones and their derivatives possess herbicidal and growth-inhibiting properties. For example, patent application WO 2010 / 089211 A1 discloses a series of herbicides containing a 3-hydroxy-2-aryl-2-cyclohexanone skeleton, which can be used to control weed growth, particularly on crops, inhibiting unwanted plant growth. Patent application WO 2014 / 084410 A1 also discloses a series of herbicides containing a similar skeleton with excellent weed control efficacy. All of the above demonstrates that compounds containing a 3-hydroxy-2-aryl-2-cyclohexanone skeleton can be potential novel and highly effective herbicides.

[0007]

[0008] To prepare 2-aryl-2-cyclohexanedione enol ester derivatives and expand the range of herbicide compounds available, Fu's research group established a microwave-assisted synthesis route for 2-aryl-2-cyclohexenedione enol ester derivatives via carbon-carbon coupling and acylation reactions catalyzed by a CuI / L-proline system.

[0009]

[0010] However, this synthesis method has some drawbacks: (1) The solvent used is high-boiling-point dimethyl sulfoxide (DMSO), which is generally removed by extraction in the post-reaction treatment and requires multiple water washes to completely remove; (2) Microwave assistance is required to achieve the goal of shortening the reaction time and increasing the product yield. Without microwave assistance, the reaction time is 48 hours, and microwave-assisted synthesis requires a microwave synthesis reactor, which undoubtedly limits the large-scale application of this reaction; (3) The catalytic system requires complex conditions and high-consumption reagents, such as the addition of excessive 1,3-cyclohexanedione compounds, sodium carbonate (base), L-proline and other additives, which does not meet the requirements of green chemistry. Summary of the Invention

[0011] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of existing methods for synthesizing 2-aryl-2-cyclohexanedione enol esters, such as requiring microwave assistance, long reaction time, and high reagent consumption. The present invention provides a method for synthesizing 2-aryl-2-cyclohexanedione enol esters with mild reaction conditions, short reaction time, and good functional group tolerance.

[0012] The purpose of this invention is to provide a 2-aryl-2-cyclohexanedione enol ester compound.

[0013] Another object of the present invention is to provide the use of the 2-aryl-2-cyclohexanedione enol ester compounds in the preparation of herbicides.

[0014] The above-mentioned objective of this invention is achieved through the following technical solution:

[0015] A synthetic method for 2-aryl-2-cyclohexanedione enol esters is provided, and the synthetic route is as follows:

[0016]

[0017] Wherein, R1 is hydrogen, C 1～4 Alkyl or phenyl;

[0018] R2 is an unsubstituted or substituted benzoyl group, C 1～4 Alkyl group, C 3～6 Cycloalkyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl;

[0019] X is an unsubstituted or substituted phenyl, naphthyl, thiophenyl, or furanyl group;

[0020] The substituted benzoyl group and substituted phenyl group are monosubstituted or polysubstituted, and the substituents are selected from halogen, phenyl, cyano, C 1～4 Alkoxy, C 1～4 Alkyl, C 1～4 Ester group, C 1～4 Alkyl group, hydroxyl group, halogenated C 1～4 One or more of the alkoxy groups;

[0021] Specifically, the following steps are included:

[0022] S1. Place the compound of formula I phenylboronic acid, the compound of formula II iodine ylide, and the transition metal complex catalyst in the reaction solvent, and react them completely at 30-80°C under closed conditions. After post-treatment, the compound of formula III 3-hydroxy-2-aryl-2-cyclohexenone is obtained.

[0023] S2. Place the compounds of formula III 3-hydroxy-2-aryl-2-cyclohexenone and the compounds of formula V acyl chloride obtained in step S1 in an organic solvent and react them completely at 0-50°C under sealed conditions. After post-treatment, the compounds of formula IV 2-aryl-2-cyclohexanedione enol ester are obtained.

[0024] This invention utilizes a transition metal complex catalyst to catalyze the reaction of phenylboronic acid compounds with iodine ylide compounds, achieving carbon-carbon coupling using phenylboronic acid and iodine ylide as substrates. Acylation then yields 2-aryl-2-cyclohexanedione enol esters. Notably, this invention allows for direct reaction in the reaction solvent without the need for alkali (unlike the classic Suzuki reaction which requires NaHCO3). It uses readily available and commercially viable phenylboronic acid as a substrate, which is widely sourced and inexpensive. Furthermore, the transition metal complex catalyst used in this invention is poorly soluble in diethyl ether. After the reaction, the product is extracted with diethyl ether, leaving the rhodium catalyst in the aqueous phase. This catalyst can be reused in the reaction solution, maintaining a high yield (over 70% yield after 5 cycles), thus maximizing catalyst recycling and significantly reducing costs. This aligns with the principles of green chemistry and high atom economy, making it highly suitable for large-scale industrial production.

[0025] Preferably, R1 is hydrogen or C. 1～4 Alkyl or phenyl;

[0026] R2 is benzoyl, o-bromobenzoyl, acetyl, propionyl, cyclopropionyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl;

[0027] X is an unsubstituted or substituted phenyl, naphthyl, thiophenyl, or furanyl group;

[0028] The substituted phenyl group may be monosubstituted or polysubstituted, and the substituent may be selected from halogen, phenyl, cyano, C 1～4 Alkoxy, C 1～4 Alkyl, C 1～4 Ester group, C 1～4 One or more of the alkyl ketone groups.

[0029] Further, in step S1, the transition metal complex catalyst is a pentamethylcyclopentadienyl transition metal complex or a dichlorobis(4-methylisopropylphenyl) transition metal complex.

[0030] Preferably, in step S1, the transition metal complex catalyst is selected from one or more of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, dichlorobis(4-methylisopropylphenyl)ruthenium(II), and dichloro(pentamethylcyclopentadienyl)iridium(III) dimer.

[0031] Furthermore, in step S1, the reaction solvent is selected from one or more of 1,4-dioxane, acetonitrile, and water.

[0032] Further, in step S1, the amount of the transition metal complex catalyst added is 1 to 4% of the molar amount of the phenylboronic acid compound of formula I.

[0033] Furthermore, in step S1, the amount of the iodine ylide compound of formula II added is 80 to 120% of the molar amount of the phenylboronic acid compound of formula I.

[0034] Furthermore, in step S1, the reaction time at 30–80°C under sealed conditions is 10–60 minutes. The actual reaction time can be tracked and detected using TLC.

[0035] Preferably, in step S1, the reaction temperature is 30–60°C; more preferably, the reaction temperature is 50°C.

[0036] Preferably, in step S1, the post-treatment can be extraction with an organic solvent, followed by drying to remove the organic solvent (the solvent can be evaporated by heating).

[0037] Furthermore, in step S2, the organic solvent is selected from one or more of dichloromethane, dichloroethane, and tetrahydrofuran.

[0038] Further, in step S2, the amount of the V-type acyl chloride compound added is 100 to 200% of the molar amount of the III-hydroxy-2-aryl-2-cyclohexenone compound.

[0039] Furthermore, in step S2, the reaction time at 0–50°C under sealed conditions is 2–8 hours.

[0040] Preferably, in step S2, the post-treatment involves removing the solvent from the reaction solution (by heating to evaporate the solvent), and the resulting product is purified and eluted with silica gel to obtain the product; wherein the eluent is obtained by mixing petroleum ether and ethyl acetate in a volume ratio of (1-8):1.

[0041] A 2-aryl-2-cyclohexanedione enol ester compound having the structure of formula IV:

[0042]

[0043] Wherein, R1 is hydrogen, C 1～4 Alkyl or phenyl;

[0044] R2 is an unsubstituted or substituted benzoyl group, C 1～4 Alkyl group, C 3～6 Cycloalkyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl;

[0045] X is an unsubstituted or substituted phenyl, naphthyl, thiophenyl, or furanyl group;

[0046] The substituted benzoyl group and substituted phenyl group are monosubstituted or polysubstituted, and the substituents are selected from halogen, phenyl, cyano, C1～4 Alkoxy, C 1～4 Alkyl, C 1～4 Ester group, C 1～4 Alkyl group, hydroxyl group, halogenated C 1～4 One or more of the alkoxy groups.

[0047] Preferably, R1 is hydrogen or C. 1～4 Alkyl or phenyl;

[0048] R2 is benzoyl, o-bromobenzoyl, acetyl, propionyl, cyclopropionyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl;

[0049] X is an unsubstituted or substituted phenyl, naphthyl, thiophenyl, or furanyl group;

[0050] The substituted phenyl group may be monosubstituted or polysubstituted, and the substituent may be selected from halogen, phenyl, cyano, C 1～4 Alkoxy, C 1～4 Alkyl, C 1～4 Ester group, C 1～4 One or more of the alkyl ketone groups.

[0051] Additionally, the present invention also claims protection for the use of the 2-aryl-2-cyclohexanedione enol ester compounds in the preparation of herbicides.

[0052] The present invention has the following beneficial effects:

[0053] This invention uses transition metal complexes as catalysts and phenylboronic acid compounds and iodine ylide compounds as raw materials to first synthesize 3-hydroxy-2-aryl-2-cyclohexenone compounds, and then synthesize 2-aryl-2-cyclohexanedione enol ester compounds via acylation. The reaction conditions are mild, requiring no additional additives (such as alkali-sodium acetate, expensive silver salt-silver acetate, etc.) to efficiently and rapidly construct C-C bonds to obtain 2-aryl-2-cyclohexanedione cyclized derivatives. Simultaneously, the reaction is simple to operate, has a short reaction time, and exhibits high efficiency and safety. Furthermore, it has a broad substrate range and good functional group tolerance, conforming to the principles of green chemistry and high atom economy, making it highly suitable for large-scale industrial production. Attached Figure Description

[0054] Figure 1 The image shows the hydrogen NMR spectrum of compound 3 obtained in Example 1 of this invention.

[0055] Figure 2 This is the carbon NMR spectrum of compound 3 obtained in Example 1 of the present invention.

[0056] Figure 3 This is a statistical chart showing the results of the catalyst cycling experiment in the experimental examples of this invention. Detailed Implementation

[0057] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0058] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0059] Example 1: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0060] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0061]

[0062] The specific synthesis steps are as follows:

[0063] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0064] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of benzoyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0065] S3. After the reaction is complete, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 3) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 65%.

[0066] See NMR data Figures 1-2 The details are as follows:

[0067] 1H NMR(400MHz, CDCl3) δ7.86(d,J=7.4Hz,2H),7.58(t,J=7.3Hz,1H),7.41(t,J=7.5Hz,2H),7.35–7.27( m,2H),7.23(dd,J=16.2,7.1Hz,3H),2.89(t,J=5.8Hz,2H),2.69(t,J=6.2Hz,2H),2.29–2.20(m,2H).

[0068] 13 C NMR (150MHz, CDCl3) δ198.0,165.5,163.7,133.9,131.4,130.6,130.2,129.7,128.7,128.7,128.0,127.8,37.8,29.3,21.0.

[0069] Example 2: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0070] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0071]

[0072] The specific synthesis steps are as described in Example 1, yielding product (compound 5) with a yield of 77%.

[0073] The specific NMR data are as follows:

[0074] 1 H NMR(600MHz, CDCl3) δ7.83(dd,J=8.3,1.1Hz,2H),7.75(dd,J=9.2,3.5Hz,3H),7.70(s,1H),7.49(dd,J=11.8, 4.3Hz,1H),7.44–7.38(m,2H),7.35–7.29(m,3H),2.92(t,J=6.2Hz,2H),2.75–2.67(m,2H),2.31–2.21(m,2H).

[0075] 13 C NMR (150MHz, CDCl3) δ 198.0, 165.7, 163.6, 133.9, 133.0, 132.8, 130.4, 130.1, 129.1, 128.8, 128.5, 128.5, 128.1, 127.6, 127.4, 126.0, 125.8, 37.7, 29.3, 21.0. Example 3: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0076] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0077]

[0078] The specific synthesis steps are as described in Example 1, yielding product (compound 7) with a yield of 76%.

[0079] The specific NMR data are as follows:

[0080] 1 H NMR(600MHz, CDCl3) δ7.86(dd,J=8.4,1.2Hz,2H),7.58–7.53(m,1H),7.42–7.36(m,2H),6.79(d,J=8.3Hz,1H),6.74(dd,J=8.3,1 .9Hz,1H),6.70(d,J=1.9Hz,1H),3.80(s,3H),3.73(s,3H),2.84(t,J=6.2Hz,3H),2.65(dd,J=8.8,4.7Hz,2H),2.23–2.18(m,2H).

[0081] 13 C NMR (150MHz, CDCl3) δ198.2,165.2,163.7,148.4,148.2,133.9,130.2,130 .0,128.6,128.6,123.7,122.3,112.8,110.7,55.7,55.7,37.7,29.3,20.8.

[0082] Example 4: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0083] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0084]

[0085] The specific synthesis steps are as described in Example 1, yielding product (compound 9) with a yield of 37%.

[0086] The specific NMR data are as follows:

[0087] 1H NMR (600MHz, CDCl3) δ7.85–7.82(m,2H),7.62–7.55(m,3H),7.44–7.40(m,2H), 7.32–7.28(m,2H),2.88(t,J=6.2Hz,2H),2.70–2.63(m,2H),2.27–2.20(m,2H).

[0088] 13 C NMR (150MHz, CDCl3) δ197.1,166.7,163.3,136.6,134.4,131.8,130.8,130.2,129.2,128.9,128.1,118.9,111.6,37.5,29.4,20.8.

[0089] Example 5: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0090] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0091]

[0092] The specific synthesis steps are as described in Example 1, yielding product (compound 11) with a yield of 73%.

[0093] The specific NMR data are as follows:

[0094] 1 H NMR (600MHz, CDCl3) δ7.87 (dd, J=8.3, 1.2Hz, 2H), 7.59–7.53 (m, 1H), 7.40 (t, J=7.9Hz, 2H), 7.14–7.0 9(m,2H),6.84–6.79(m,2H),3.73(s,3H),2.84(t,J=6.2Hz,2H),2.67–2.63(m,2H),2.23–2.17(m,2H).

[0095] 13 C NMR (150MHz, CDCl3) δ198.3,165.2,163.7,159.1,133.9,131.0,130.2,130.1,128.7,128.7,123.5,113.5,55.2,37.8,29.4,21.0.

[0096] Example 6: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0097] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0098]

[0099] The specific synthesis steps are as described in Example 1, yielding product (compound 13) in 70% yield.

[0100] The specific NMR data are as follows:

[0101] 1 H NMR(600MHz, CDCl3)δ7.88–7.85(m,2H),7.59–7.54(m,1H),7.42–7.37(m,2H),7.11–7.0 5(m,4H),2.85(dd,J=8.0,4.5Hz,2H),2.68–2.63(m,2H),2.27(s,3H),2.24–2.17(m,2H).

[0102] 13 C NMR (150MHz, CDCl3) δ198.2,165.2,163.7,137.4,133.9,130.5,130.2,129.6,128.7,128.6,128.3,37.8,29.3,21.3,21.0.

[0103] Example 7: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0104] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0105]

[0106] The specific synthesis steps are as described in Example 1, yielding product (compound 15) in 58% yield.

[0107] The specific NMR data are as follows:

[0108] 1 H NMR (600MHz, CDCl3) δ7.85 (dd, J=8.4, 1.2Hz, 2H), 7.60–7.54 (m, 1H), 7.42–7.38 (m, 2H), 7.17 –7.13(m,2H),6.99–6.94(m,2H),2.85(t,J=6.2Hz,2H),2.68–2.63(m,2H),2.25–2.19(m,2H).

[0109] 13C NMR (150MHz, CDCl3) δ197.9,165.8,163.6,162.35(d,J=246.5Hz),134.1,131.56(d,J=8.2Hz),1 30.2,129.7,128.8,128.5,127.25(d,J=3.5Hz),115.1,115.08(d,J=21.4Hz),37.7,29.3,21.0.

[0110] Example 8: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0111] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0112]

[0113] The specific synthesis steps are as described in Example 1, yielding product (compound 17) with a yield of 37%.

[0114] The specific NMR data are as follows:

[0115] 1 H NMR (600MHz, CDCl3) δ7.83–7.80(m,2H),7.57–7.53(m,1H),7.40–7.35(m,2H),7.30–7.27(m,2H),7. 12–7.09(m,2H),2.87(t,J=6.2Hz,2H),2.66(dd,J=8.7,4.7Hz,2H),2.24–2.18(m,2H),1.24(s,9H).

[0116] 13 C NMR (150MHz, CDCl3) δ198.2,165.5,163.8,150.5,133.9,130.4,130.2,129.4,128.9,128.6,128.3,125.0,37.8,34.6,31.4,29.4,21.0.

[0117] Example 9: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0118] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0119]

[0120] The specific synthesis steps are as described in Example 1, yielding product (compound 19) with a yield of 49%.

[0121] The specific NMR data are as follows:

[0122] 1 H NMR (600MHz, CDCl3) δ7.98–7.92(m,1H),7.83(dd,J=8.4,1.2Hz,1H),7.59–7.54(m,1H),7.39(dd,J=8.2,7.6H z,1H),7.29–7.23(m,1H),3.86(s,2H),2.88(t,J=6.2Hz,1H),2.67(dd,J=8.8,4.7Hz,1H),2.28–2.18(m,1H).

[0123] 13 C NMR (150MHz, CDCl3) δ197.5,167.0,166.1,163.5,136.5,134.2,130.2,130.0,129.9,129.4,129.3,128.8,128.3,52.2,37.7,29.37,20.97.

[0124] Example 10: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0125] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0126]

[0127] The specific synthesis steps are as described in Example 1, yielding product (compound 21) with a yield of 54%.

[0128] The specific NMR data are as follows:

[0129] 1 H NMR (600MHz, CDCl3) δ7.86 (dd, J=8.3, 1.1Hz, 1H), 7.58 (dd, J=10.7, 4.3Hz, 1H), 7.44–7.3 9(m,2H),7.10–7.04(m,1H),2.85(t,J=6.2Hz,1H),2.67–2.62(m,1H),2.24–2.18(m,1H).

[0130] 13 C NMR (150MHz, CDCl3) δ197.6,165.8,163.5,134.2,131.5,131.2,130.3,130.2,129.58(s),128.8,128.4,122.1,37.6,29.3,20.9.

[0131] Example 11: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0132] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0133]

[0134] The specific synthesis steps are as described in Example 1, yielding product (compound 23) with a yield of 72%.

[0135] The specific NMR data are as follows:

[0136] 1 H NMR (600MHz, CDCl3) δ7.76 (dd, J=8.3, 1.2Hz, 2H), 7.48–7.45 (m, 1H), 7.32–7.28 (m, 4H), 7.27–7.19 (m, 5H) ,7.18–7.14(m,3H),3.59(ddd,J=16.7,11.6,4.8Hz,1H),3.15(dd,J=17.8,11.3Hz,1H),2.94–2.83(m,3H).

[0137] 13 C NMR (150MHz, CDCl3) δ197.2,164.6,163.7,142.3,134.0,131.2,130.3,130. 2,129.8,129.0,128.7,128.5,128.1,128.0,127.4,126.8,44.8,39.2,37.1.

[0138] Example 12: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0139] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0140]

[0141] The specific synthesis steps are as described in Example 1, yielding product (compound 25) in 87% yield.

[0142] The specific NMR data are as follows:

[0143] 1H NMR (600MHz, CDCl3) δ7.84(d,J=8.0Hz,1H),7.55(t,J=7.4Hz,1H),7.39(t,J=7.8Hz, 1H),7.28(t,J=7.5Hz,1H),7.23–7.17(m,2H),2.75(s,1H),2.54(s,1H),1.24(s,3H).

[0144] 13 C NMR (150MHz, CDCl3) δ198.0,163.9,163.8,133.9,131.3,130.1,129.7,129.6,128.7,128.7,128.0,127.8,51.7,43.1,32.8,28.3.

[0145] Example 13: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0146] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0147]

[0148] The specific synthesis steps are as described in Example 1, yielding product (compound 27) in 78% yield.

[0149] The specific NMR data are as follows:

[0150] 1 H NMR (600MHz, CDCl3) δ7.85(dd,J=8.3,1.1Hz,2H),7.55(dd,J=10.6,4.3Hz,1H),7.39(t,J=7.8Hz,2H),7.28(d,J=7.3Hz ,2H),7.22(d,J=7.4Hz,1H),7.19–7.16(m,2H),2.83–2.69(m,3H),2.41(dd,J=16.0,13.5Hz,1H),1.00(d,J=6.8Hz,3H).

[0151] 13 C NMR (150MHz, CDCl3) δ198.4,165.5,163.7,134.0,131.4,130.2,130.1,129.7,128.7,128.7,128.0,127.8,41.9,39.8,33.3,32.1,19.7.

[0152] Example 14: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0153] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0154]

[0155] The specific synthesis steps are as described in Example 1, yielding product (compound 29) in 58% yield.

[0156] The specific NMR data are as follows:

[0157] 1 H NMR (600MHz, CDCl3) δ7.88 (dd, J=8.4, 1.2Hz, 2H), 7.57–7.50 (m, 2H), 7.39 (td, J=8.2, 1.5Hz, 4H), 7.32–7.29(m,1H),7.28–7.26(m,2H),2.89(t,J=6.2Hz,2H),2.71–2.67(m,2H),2.28–2.22(m,2H).

[0158] 13 C NMR (150MHz, CDCl3) δ198.0,165.6,163.6,140.8,140.4,133.9,130.3,130. 1,130.1,128.7,128.6,128.6,128.5,127.3,127.1,126.7,37.7,29.3,20.9.

[0159] Example 15: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0160] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0161]

[0162] The specific synthesis steps are as described in Example 1, yielding product (compound 31) with a yield of 46%.

[0163] The specific NMR data are as follows:

[0164] 1 H NMR (600MHz, CDCl3) δ7.89–7.86(m,2H),7.85–7.82(m,2H),7.59–7.55(m,1H),7.41–7.37(m,2H ),7.31–7.28(m,2H),2.88(t,J=6.2Hz,2H),2.71–2.65(m,2H),2.54(s,3H),2.27–2.21(m,2H).

[0165] 13 C NMR (150MHz, CDCl3) δ198.1,197.5,166.2,163.5,136.7,136.3,134.2,130.2,130.2,129.8,128.8,128.3,128.0,37.7,29.4,26.7,20.9.

[0166] Example 16: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0167] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0168]

[0169] The specific synthesis steps are as described in Example 1, yielding product (compound 33) in 55% yield.

[0170] The specific NMR data are as follows:

[0171] 1 H NMR (600MHz, CDCl3) δ7.87–7.84(m,1H),7.61–7.55(m,1H),7.45–7.39(m,1H),7.28–7.2 2(m,1H),7.15–7.10(m,1H),2.85(t,J=6.2Hz,1H),2.68–2.63(m,1H),2.25–2.18(m,1H).

[0172] 13 C NMR (150MHz, CDCl3) δ197.7,165.9,163.5,134.2,133.8,131.2,130.2,129.9,129.6,128.8,128.4,128.3,37.7,29.4,20.9.

[0173] Example 17: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0174] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0175]

[0176] The specific synthesis steps are as described in Example 1, yielding product (compound 35) with a yield of 27%.

[0177] The specific NMR data are as follows:

[0178] 1 H NMR(600MHz, CDCl3)δ8.00(dd,J=7.8,1.2Hz,1H),7.77(dd,J=8.3,1.2Hz,2H),7.54–7.50(m,1H), 7.40(td,J=7.5,1.4Hz,1H),7.35(dd,J=10.9,4.8Hz,2H),7.31(td,J=7.7,1.3Hz,1H),7.17(dd,J= 7.6,1.1Hz,1H),4.34–4.24(m,2H),2.93(dt,J=17.9,5.7Hz,1H),2.80(ddd,J=17.9,8.1,5.3Hz,1H ),2.74–2.67(m,1H),2.63(ddd,J=16.4,7.2,4.8Hz,1H),2.31–2.18(m,2H),1.36(t,J=7.1Hz,3H).

[0179] 13 C NMR (150MHz, CDCl3) δ 197.9, 166.6, 163.7, 163.1, 133.9, 133.4, 132.0, 131.1, 131.0, 130.5, 130.3, 130.1, 128.7, 128.6, 128.1, 61.0, 37.6, 29.0, 21.0, 14.4. Example 18: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound.

[0180] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0181]

[0182] The specific synthesis steps are as described in Example 1, yielding product (compound 37) in 55% yield.

[0183] The specific NMR data are as follows:

[0184] 1 H NMR (600MHz, CDCl3) δ7.86 (dd, J=8.2, 1.0Hz, 2H), 7.60 (dd, J=11.8, 5.1Hz, 3H), 7.42 (t, J= 7.8Hz,2H),6.95–6.91(m,2H),2.84(t,J=6.2Hz,2H),2.68–2.61(m,2H),2.25–2.17(m,2H).

[0185] 13C NMR (150MHz, CDCl3) δ197.5,165.7,163.4,137.1,134.1,131.6,130.9,130.1,129.6,128.7,128.3,93.8,37.5,29.2,20.8.

[0186] Example 19: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0187] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0188]

[0189] The specific synthesis steps are as described in Example 1, yielding product (compound 39) with a yield of 71%.

[0190] The specific NMR data are as follows:

[0191] 1 H NMR (600MHz, CDCl3) δ7.85(dd,J=8.4,1.2Hz,2H),7.56(s,1H),7.39(dd,J=8.2,7.6Hz,2H),7.18(t,J=7.9Hz,1H),6.76(ddd, J=4.9,3.7,2.1Hz,2H),6.72(dd,J=2.3,1.7Hz,1H),3.69(s,3H),2.86(t,J=6.2Hz,2H),2.69–2.62(m,2H),2.25–2.19(m,2H).

[0192] 13 C NMR (150MHz, CDCl3) δ198.0,165.6,163.7,159.2,134.0,132.7,130.6,130.2,129.0,128.7,122.2,115.0,114.0,55.2,37.8,29.3,21.0.

[0193] Example 20: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0194] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0195]

[0196] The specific synthesis steps are as described in Example 1, yielding product (compound 41) with a yield of 40%.

[0197] The specific NMR data are as follows:

[0198] 1 H NMR (600MHz, CDCl3) δ8.07(dd,J=8.3,1.2Hz,2H),7.64(dt,J=8.7,1.2Hz,1H),7.49(dd,J=10.9,4.8Hz,2H),7.34(dd,J=3.7,1.0Hz, 1H), 7.28 (dd, J=5.1, 1.1Hz, 1H), 6.96 (dd, J=5.1, 3.7Hz, 1H), 2.89 (t, J=6.2Hz, 2H), 2.68 (dd, J=8.8, 4.6Hz, 2H), 2.22–2.15 (m, 2H).

[0199] 13 C NMR (150MHz, CDCl3) δ197.0,164.8,163.3,134.2,130.8,130.6,129.0,128.9,128.7,126.7,126.4,123.5,38.0,29.9,20.7.

[0200] Example 21: A method for synthesizing 2-aryl-2-cyclohexanedione enol esters

[0201] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0202]

[0203] The specific synthesis steps are as described in Example 1, yielding product (compound 43) with a yield of 46%.

[0204] The specific NMR data are as follows:

[0205] 1 H NMR (600MHz, CDCl3) δ8.12–8.06(m,2H),7.67–7.60(m,1H),7.49(dd,J=10.8,4.9Hz,2H),7.19(d,J=1.2Hz,1H), 6.84(d,J=3.4Hz,1H), 6.36(dd,J=3.4,1.8Hz,1H), 2.85(t,J=6.2Hz,2H), 2.65–2.60(m,2H), 2.19–2.13(m,2H).

[0206] 13C NMR (150MHz, CDCl3) δ196.3,164.6,163.8,145.4,142.2,134.0,130.4,129.1,128.8,120.3,112.6,111.0,38.1,30.2,20.5.

[0207] Example 22: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0208] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0209]

[0210] The specific synthesis steps are as described in Example 1, yielding product (compound 45) in 55% yield.

[0211] The specific NMR data are as follows:

[0212] 1 H NMR(600MHz, CDCl3)δ7.79(dd,J=8.2,1.1Hz,2H),7.56–7.51(m,1H),7.36(t,J =7.8Hz,2H),7.22(td,J=8.3,1.7Hz,1H),7.05(dd,J=7.5,1.7Hz,1H),6.87(td, J=7.5,0.8Hz,1H),6.82(d,J=8.3Hz,1H),3.66(s,3H),2.99(ddd,J=18.0,8.0, 5.3Hz,1H),2.83(dt,J=18.1,5.7Hz,1H),2.74–2.59(m,2H),2.29–2.16(m,2H).

[0213] 13 C NMR (150MHz, CDCl3) δ197.9,165.9,163.6,157.0,133.8,131.2,130.1,129.5,129.0,128.6,127.3,120.8,120.4,110.9,55.7,37.7,29.3,21.3.

[0214] Example 23: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0215] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0216]

[0217] The specific synthesis steps are as follows:

[0218] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0219] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of benzenesulfonyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0220] S3. After the reaction is complete, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 46) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 81%.

[0221] The specific NMR data are as follows:

[0222] 1 H NMR (600MHz, CDCl3) δ7.55–7.51(m,1H),7.41(dd,J=8.5,1.2Hz,2H),7.33–7.28(m,2H),7.22 –7.15(m,3H),6.94–6.88(m,2H),3.01(t,J=6.2Hz,2H),2.60–2.54(m,2H),2.21–2.13(m,2H).

[0223] 13 C NMR (150MHz, CDCl3) δ197.7,163.1,135.9,134.1,131.4,130.5,130.2,129.1,127.9,127.8,127.8,37.6,30.1,21.0.

[0224] Example 24: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0225] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0226]

[0227] The specific synthesis steps are as follows:

[0228] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0229] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of acetyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0230] S3. After the reaction is complete, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 47) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 75%.

[0231] The specific NMR data are as follows:

[0232] 1 H NMR(600MHz, CDCl3)δ7.34(dd,J=10.2,4.6Hz,2H),7.31–7.27(m,1H),7.12–7.09 (m,2H),2.70(t,J=6.2Hz,2H),2.61–2.57(m,2H),2.18–2.12(m,2H),1.94(s,3H).

[0233] 13 C NMR (150MHz, CDCl3) δ197.9,167.8,165.1,131.6,130.5,129.6,128.0,127.8,37.6,29.1,20.8,20.7.

[0234] Example 25: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0235] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0236]

[0237] The specific synthesis steps are as follows:

[0238] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0239] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of o-bromobenzoyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0240] S3. After the reaction is completed, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 48) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 72%.

[0241] The specific NMR data are as follows:

[0242] 1 H NMR (600MHz, CDCl3) δ7.61 (dd, J=7.0, 2.4Hz, 1H), 7.34–7.26 (m, 5H), 7.25–7.21 (m, 1H), 7.18(dd,J=8.2,1.3Hz,2H),2.88(t,J=6.2Hz,2H),2.70–2.62(m,2H),2.29–2.19(m,2H).

[0243] 13 C NMR (150MHz, CDCl3) δ197.9,165.1,162.8,134.6,133.4,131.5,131.4,131.1,130.5,129.7,128.2,128.0,127.3,122.1,37.7,29.1,20.9.

[0244] Example 26: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0245] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0246]

[0247] The specific synthesis steps are as follows:

[0248] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0249] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of propionyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0250] S3. After the reaction is completed, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 49) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 80%.

[0251] The specific NMR data are as follows:

[0252] 1 H NMR(600MHz, CDCl3)δ7.33(t,J=7.5Hz,2H),7.28(dd,J=8.5,6.2Hz,1H),7.11–7.08(m, 2H),2.70(t,J=6.2Hz,2H),2.63–2.58(m,2H),2.24–2.12(m,4H),0.94(t,J=7.6Hz,3H).

[0253] 13 C NMR (150MHz, CDCl3) δ197.9,171.2,165.2,131.5,130.5,129.6,127.9,127.7,37.5,29.1,27.5,20.7,8.7.

[0254] Example 27: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0255] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0256]

[0257] The specific synthesis steps are as follows:

[0258] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0259] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2 mL × 3). After drying the organic phase, it is added to a round bottom flask with 2 mL of dichloromethane (DCM). 0.3 mmol of cyclopropionyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6 h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0260] S3. After the reaction is complete, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 50) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 59%.

[0261] The specific NMR data are as follows:

[0262] 1 H NMR(600MHz, CDCl3)δ7.34(t,J=7.4Hz,1H),7.31–7.27(m,1H),7.11–7.08(m,1H) ,2.70(t,J=6.2Hz,1H),2.61–2.57(m,1H),2.17–2.11(m,1H),0.82–0.78(m,2H).

[0263] 13 C NMR (150MHz, CDCl3) δ198.1,171.7,165.3,131.6,130.4,129.7,128.0,127.8,77.4,77.2,77.0,37.6,29.2,20.8,13.1,9.1.

[0264] Example 28: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0265] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0266]

[0267] The specific synthesis steps are as follows:

[0268] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0269] S2. After the reaction is completed, the reaction material A obtained in step S1 is extracted with ethyl acetate (2mL×3). After drying the organic phase, it is added to a round bottom flask with 2mL of dichloromethane (DCM). 0.3mmol of trifluoromethanesulfonyl chloride is added dropwise under ice bath. The reaction is stirred at room temperature for 6h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0270] S3. After the reaction is complete, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 51) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 44%.

[0271] The specific NMR data are as follows:

[0272] 1 H NMR(600MHz, CDCl3)δ9.06(d,J=8.3Hz,1H),8.29(d,J=7.9Hz,1H),7.82–7.76(m,1H) ,7.53(t,J=7.6Hz,1H),2.94(t,J=6.3Hz,2H),2.70–2.62(m,2H),2.22–2.13(m,2H).

[0273] 13 C NMR (150MHz, CDCl3) δ196.7, 162.1, 132.9, 130.1, 129.2, 128.9, 128.3, 118.1 (q, J = 320.3Hz), 37.3, 29.4, 20.6.

[0274] Example 29: A method for synthesizing a 2-aryl-2-cyclohexanedione enol ester compound

[0275] The synthetic route for the 2-aryl-2-cyclohexanedione enol ester compounds is as follows:

[0276]

[0277] The specific synthesis steps are as follows:

[0278] S1. Add 0.2 mmol of phenylboronic acid (compound 1), 0.2 mmol of iodine ylide compound (compound 2), and 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer to a pressure-resistant and sealed reaction tube. Add 1.0 mL of water (H2O) to the pressure-resistant and sealed reaction tube and stir the reaction at 50 °C for 30 min. During the reaction, the reaction time is monitored by TLC to obtain reactant A.

[0279] S2. After the reaction is complete, the reaction material A obtained in step S1 is extracted with ethyl acetate (2 mL × 3). After drying the organic phase, it is added to a round-bottom flask with 2 mL of dichloromethane (DCM). 0.3 mmol of 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl chloride is added dropwise under ice bath conditions. The mixture is stirred at room temperature for 6 h. The reaction time is monitored by TLC during the reaction to obtain reaction material B.

[0280] S3. After the reaction is completed, the reactant B obtained in step S2 is taken out from the pressure-resistant sealed reaction tube, the organic solvent is evaporated, and the product (compound 53) is obtained by silica gel purification and rinsing with eluent (petroleum ether: ethyl acetate = 3:1) with a yield of 85%.

[0281] The specific NMR data are as follows:

[0282] 1 H NMR (600MHz, CDCl3) δ7.31(td,J=8.3,5.9Hz,1H),7.20(d,J=8.2Hz,1H),7.17(dd,J=6.5,3.8Hz,3H),6.98(td,J=8.6,0.7Hz,1H),6.81–6.77(m,2H),2 .56(ddd,J=10.5,9.7,3.9Hz,2H),2.45(dd,J=18.1,10.1Hz,1H),2.41(s,3 H),2.37–2.29(m,1H),2.20(dd,J=16.2,12.1Hz,1H),1.05(d,J=6.5Hz,3H).

[0283] 13C NMR (150MHz, CDCl3) δ197.6,177.2,163.5,160.7(d,J=252.6Hz),157.8,155.4,135.1(d,J=3.7Hz),131.9(d,J=9.4Hz),131.0, 130.3,129.4,128.1,127.9,125.3(d,J=3.4Hz),116.8(d,J=18.7Hz),114.3(d,J=21.6Hz),108.6,45.8,36.9,28.3,20.9,13.3.

[0284] Example 30: A method for synthesizing a 2-phenyl-2-cyclohexanedione enol ester compound

[0285] The difference from Example 1 is that 1,4-dioxane is used to replace water (H2O) in this example, while the other parameters and operations are the same as in Example 1.

[0286] Compound 3 was prepared in 65% yield.

[0287] Example 31: A method for synthesizing a 2-phenyl-2-cyclohexanedione enol ester compound.

[0288] The difference from Example 1 is that the temperature of the stirring reaction in step S1 is set to room temperature in this example, while the other parameters and operations are the same as in Example 1.

[0289] Compound 3 was prepared in 51% yield.

[0290] Example 32: A method for synthesizing a 2-phenyl-2-cyclohexanedione enol ester compound

[0291] The difference from Example 1 is that in this example, palladium acetate Pd(OAc)2 (5 mol%) is used to replace the catalyst dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer [Cp*RhCl2]2, while the other parameters and operations are the same as in Example 1.

[0292] Compound 3 was prepared in 64% yield.

[0293] Example 33: A method for synthesizing a 2-phenyl-2-cyclohexanedione enol ester compound

[0294] The difference from Example 1 is that in this example, the catalyst dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer [Cp*RhCl2]2 is replaced with dichlorobis(4-methylisopropylphenyl)ruthenium(II)[RuCl2(p-cymene](2.5mol%). The other parameters and operations are the same as in Example 1.

[0295] Compound 3 was prepared in 29% yield.

[0296] Comparative Example 1

[0297] The difference from Example 1 is that [Cp*RhCl2]2 was replaced with dichloro(pentamethylcyclopentadienyl)iridium(III) dimer [Cp*IrCl2]2 (2.5 mol%) in this comparative example, while the other parameters and operations are the same as in Example 1.

[0298] Compound 3 could not be prepared.

[0299] Comparative Example 2

[0300] The difference from Example 1 is that this comparative example does not add the catalyst dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer [Cp*RhCl2]2, and the other parameters and operations are the same as in Example 1.

[0301] Compound 3 could not be prepared.

[0302] Experimental Example: Catalyst Cycling Experiment

[0303] The catalyst, dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer [Cp*RhCl2]2, from Example 1 was recovered and the reaction was repeated 5 times under the same conditions. The yield of intermediate compound III was calculated for each iteration. See the results below. Figure 3 As can be seen from the figure, the yield of the catalyst used in the synthesis method of this invention is still over 70% after five cycles of reaction.

[0304] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for synthesizing 2-aryl-2-cyclohexanedione enol esters, characterized in that, The synthesis route is as follows: Wherein, R1 is hydrogen, C 1~4 Alkyl or phenyl; R2 is an unsubstituted or substituted benzoyl group, C 1~4 Alkyl group, C 3~6 Cycloalkyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl; X represents unsubstituted or substituted phenyl or naphthyl groups; The substituted benzoyl group and substituted phenyl group are monosubstituted or polysubstituted, and the substituents are selected from halogen, phenyl, cyano, C 1~4 Alkoxy, C 1~4 Alkyl, C 1~4 Ester group, C 1~4 One or more of the alkyl or ketone groups; Specifically, the following steps are included: S1. Place the compound of formula I phenylboronic acid, the compound of formula II iodine ylide, and the transition metal complex catalyst in the reaction solvent, and react them completely at 30~80℃ under closed conditions. After post-treatment, the compound of formula III 3-hydroxy-2-aryl-2-cyclohexenone is obtained. S2. Place the compounds of formula III 3-hydroxy-2-aryl-2-cyclohexenone and the compounds of formula V acyl chloride obtained in step S1 in an organic solvent and react them completely at 0~50℃ under sealed conditions. After post-treatment, the compounds of formula IV 2-aryl-2-cyclohexanedione enol ester are obtained. In step S1, the transition metal complex catalyst is selected from dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer; The reaction solvent is selected from one or more of 1,4-dioxane, acetonitrile, and water; The amount of the transition metal complex catalyst added is 1 to 4% of the molar amount of the phenylboronic acid compound of formula I.

2. The synthesis method according to claim 1, characterized in that, R1 is hydrogen, C 1~4 Alkyl or phenyl; R2 is benzoyl, o-bromobenzoyl, acetyl, propionyl, cyclopropionyl, benzenesulfonyl, trifluoromethanesulfonyl, or 3-(2-chloro-6-fluorophenyl)-5-methylisozol-4-carboxyl; X represents unsubstituted or substituted phenyl or naphthyl groups; The substituted phenyl group may be monosubstituted or polysubstituted, and the substituent may be selected from halogen, phenyl, cyano, C 1~4 Alkoxy, C 1~4 Alkyl, C 1~4 Ester group, C 1~4 One or more of the alkyl ketone groups.

3. The synthesis method according to claim 1 or 2, characterized in that, In step S2, the organic solvent is selected from one or more of dichloromethane, dichloroethane, and tetrahydrofuran.

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