Synthesis method of allyl ester compound

Abstract

The invention discloses a synthesis method of an allyl ester compound, and belongs to the technical field of organic synthesis. According to the synthesis method disclosed by the invention, a reaction equation is # imgabs0 #, and direct coupling of fatty aldehyde and olefin is realized by utilizing a cobalt oxime catalyst and a halogen atom transfer (XAT) mechanism, so that the allyl ester compound is synthesized. The adopted raw materials are cheap and easy to obtain, the operation is simple, the reaction conditions are mild, and high temperature or high pressure is not needed; the low-toxicity solvent (acetonitrile) and the blue light LED are used for irradiation, so that the energy consumption is low, the synthesis cost is effectively reduced, and industrial production is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing an allyl ester compound. Background Art

[0002] Allyl alcohols are important organic synthesis intermediates, widely used in the synthesis of pharmaceuticals, natural products, and functional materials. Traditional synthetic methods often rely on the coupling reaction of preformed alkenyl metal reagents (such as Grignard reagents) with carbonyl compounds. However, such methods require the use of stoichiometric metal reducing agents, harsh reaction conditions, and limited functional group compatibility. Although transition metal-catalyzed reductive coupling strategies have developed in recent years, they still face the following challenges: low coupling efficiency of aliphatic aldehydes, requiring strong reducing agents (such as SmI2 or sodium metal); the reaction requires additional photosensitizers or activators, resulting in poor atom economy; and the limited applicability of existing methods to complex molecules (such as drug derivatives).

[0003] Therefore, it is of great significance to develop a mild, efficient and pre-functionalization-free carbonyl enylation method. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a method for synthesizing an allyl ester compound. The raw materials used in the present invention are cheap and easily available, the operation is simple, and the reaction conditions are mild, without the need for high temperature or high pressure; low-toxic solvents and blue light LED irradiation are used, energy consumption is low, and it is conducive to industrial production.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a method for synthesizing an allyl ester compound, and the reaction equation is:

[0007]

[0008] By adopting the above technical solution and utilizing cobaloxime catalyst and halogen atom transfer (XAT) mechanism, direct coupling of aliphatic aldehydes and olefins is achieved to synthesize allyl ester compounds.

[0009] Preferably, in the compound (1), R1 is tert-butyl, cyano, methoxy, estrone or menthyl ester; and Ar is a benzene ring or pyrimidine.

[0010] Preferably, in the compound (2), R2 is n-butyl, 3-methylbutanal, 2-methylpropanal, 2,2-dimethylpropanal or cyclopentanal.

[0011] As a preference, the specific steps are:

[0012] Compound (1), compound (2), a catalyst, a base, and a reducing agent are mixed in a solvent under a nitrogen atmosphere and then reacted under light to obtain compound (3).

[0013] Preferably, the molar ratio of the compound (1), compound (2), catalyst, base and reducing agent is 1:2:0.02:2:1.5.

[0014] Preferably, the catalyst is a cobalt oxime complex, and the cobalt oxime complex includes Co(dmgH)(dmgH2)Cl2.

[0015] Preferably, the base is (NH4)2CO3.

[0016] Preferably, the reducing agent is indium powder.

[0017] Preferably, the solvent is acetonitrile.

[0018] Preferably, the illumination is a blue light LED with a power of 12W; and the reaction time is 12h.

[0019] Contains at least the following beneficial technical effects:

[0020] (1) The present invention directly utilizes cheap and readily available fatty aldehydes (such as valeraldehyde) and acetyl iodide (AcI) to in situ generate α-acetoxy iodide, which is then coupled with olefins, avoiding the pre-functionalization step and significantly improving atom economy.

[0021] (2) The raw materials used in the present invention are cheap and readily available, the operation is simple, and the reaction conditions are mild, without the need for high temperature or high pressure. Low-toxicity solvents and blue LED irradiation are used, resulting in low energy consumption. This effectively reduces synthesis costs and facilitates industrial production.

[0022] (3) The cobaloxime catalyst (such as Co(dmgH)(dmgH2)Cl2) used in the present invention is used in a low amount (2 mol%), and cobalt is an abundant metal on earth, which is low in cost and environmentally friendly.

[0023] (4) The present invention uses indium powder (In) as a reducing agent, avoiding the use of strong reducing agents such as SmI2 and metallic sodium in traditional methods, thereby reducing side reactions and waste generation. DETAILED DESCRIPTION

[0024] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0025] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0026] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0027] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the present invention. The present description and examples are intended to be illustrative only.

[0028] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0029] Unless otherwise specified, the "room temperature" and "normal temperature" mentioned in the present invention are all calculated as 25±2°C.

[0030] Unless otherwise specified, all raw materials and instruments used in the following examples of the present invention are commercially available.

[0031] Example 1

[0032] In this example, (E)-1-[4-(tert-butyl)phenyl]hept-1-en-3-yl acetate compound (3a) was synthesized by reacting 1-(tert-butyl)-4-vinylbenzene (1a) containing electron donors among aromatic olefins with 1-iodopentyl acetate (2a):

[0033] The reaction equation is:

[0034]

[0035] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1a (16.0 mg, 0.10 mmol, 1.0 equiv), 2a (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (3a) in a yield of 78%.

[0036] The characterization data of compound (3a) are:

[0037] Colorless oily liquid: 1 H NMR (400MHz, CDCl3) δ7.38-7.30 (m, 4H), 6.58 (d, J=15.9Hz, 1H), 6.08 (dd, J=15.9, 7.5Hz, 1H), 5.38 (dd, J =14.0, 6.9Hz, 1H), 2.07(s, 3H), 1.81-1.64(m, 2H), 1.35-1.32(m, 4H), 1.31(s, 9H), 0.90(t, J=6.4Hz, 3H).

[0038] 13 C NMR (151MHz, CDCl3) δ170.4, 151.1, 133.6, 132.3, 127.1, 126.3, 125.5, 75.0, 34.6, 34.3, 31.3, 27.4, 22.5, 21.4, 14.0.

[0039] HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 28 O2Na 311.1982; found311.1982.

[0040] Example 2

[0041] In this example, (E)-1-(4-cyanophenyl)hept-1-en-3-yl acetate (3b) was synthesized by reacting electron-withdrawing 4-vinylbenzonitrile (1b) with 1-iodopentyl acetate (2a) in an aromatic olefin. The reaction equation is:

[0042]

[0043] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1b (12.9 mg, 0.10 mmol, 1.0 equiv), 2a (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (3b) in a yield of 67%.

[0044] The characterization data of compound (3b) are:

[0045] Colorless oily liquid: 1 H NMR (400MHz, CDCl3) δ7.60 (d, J=8.3Hz, 2H), 7.45 (d, J=8.4Hz, 2H), 6.59 (d, J=16.0Hz, 1H), 6.25 (dd, J=16.0, 7.0 Hz, 1H), 5.40 (dd, J=13.5, 6.8Hz, 1H), 2.09 (s, 3H), 1.73-1.67 (m, 2H), 1.37-1.32 (m, 4H), 0.91 (t, J=6.7Hz, 3H).

[0046] 13 C NMR (151MHz, CDCl3) δ170.4, 140.9, 132.4, 132.0, 130.4, 127.1, 118.9, 111.1, 74.2, 34.1, 27.3, 22.5, 21.3, 14.0.

[0047] HRMS(ESI)m / z:[M+Na] + Calcd for C 16 H 19 O2NNa 280.1308; found280.1308.

[0048] Example 3

[0049] In this example, the (E)-1-(2-methoxypyrimidin-5-yl)hept-1-en-3-yl acetate compound (3c) was synthesized by reacting the heterocyclic olefin 2-methoxy-5-vinylpyrimidine (1c) with 1-iodopentyl acetate (2a):

[0050] The reaction equation is:

[0051]

[0052] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1c (13.6 mg, 0.10 mmol, 1.0 equiv), 2a (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (3c) in a yield of 53%.

[0053] The characterization data of compound (3c) are:

[0054] Colorless oily liquid: 1 H NMR (400MHz, CDCl3) δ8.51 (s, 2H), 6.47 (d, J=16.1Hz, 1H), 6.11 (dd, J=16.1, 7.1Hz, 1H), 5.37 (dd, J=13 .7, 6.8Hz, 1H), 4.01 (s, 3H), 2.09 (s, 3H), 1.80-1.62 (m, 2H), 1.39-1.27 (m, 4H), 0.90 (t, J=6.7Hz, 3H).

[0055] 13 C NMR (151MHz, CDCl3) δ169.4, 164.1, 156.0, 128.4, 124.0, 123.0, 73.4, 54.0, 33.1, 26.3, 21.4, 20.3, 12.9.

[0056] HRMS(ESI)m / z:[M+Na] + Calcd for C 14 H 20 O3N2Na 287.1366; found287.1363.

[0057] Example 4

[0058] In this example, a complex molecule such as (8S,9S,13S,14S)-9,13-dimethyl-3-vinyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthrene-17-one (1d) was reacted with 1-iodopentyl acetate (2a) to synthesize (E)-1-(9,13-dimethyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthrene-3-yl)hept-1-en-3-yl acetate compound (3d):

[0059] The reaction equation is:

[0060]

[0061] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1d (28.0 mg, 0.10 mmol, 1.0 equiv), 2a (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (3d) in a yield of 69%.

[0062] The characterization data of compound (3d) are:

[0063] Colorless oily liquid: 1 H NMR (400MHz, CDCl3) δ7.24 (d, J=8.3Hz, 1H), 7.18 (d, J=8.1Hz, 1H), 7.12 (s, 1H), 6. 54 (d, J=15.9Hz, 1H), 6.07 (dd, J=15.9, 7.4Hz, 1H), 5.37 (dd, J=13.8, 6.9Hz, 1H), 2. 90 (dd, J=8.8, 4.0Hz, 2H), 2.53-2.43 (m, 2H), 2.30 (dd, J=15.0, 5.5Hz, 1H), 2.19-2 .12(m, 2H), 2.07(s, 3H), 2.03-1.89(m, 3H), 1.69-1.40(m, 10H), 0.96-0.85(m, 6H).

[0064] 13 C NMR (151MHz, CDCl3) δ170.4, 139.7, 136.7, 134.0, 132.2, 127.25, 127.24, 127.18, 125.6, 124.00, 123.9 4, 75.0, 50.5, 48.0, 44.5, 38.2, 35.9, 34.3, 31.6, 29.4, 27.4, 26.5, 25.7, 22.5, 21.6, 21.4, 14.0, 13.9.

[0065] HRMS(ESI)m / z:[M+Na] + Calcd for C 29 H 31 O2Na 431.2557; found431.2557.

[0066] Example 5

[0067] In this example, a complex molecule such as 5-isopropyl-2-methylcyclohexyl 4-vinyl benzoate (1e) is reacted with 1-iodopentyl acetate (2a) to synthesize 5-isopropyl-2-methylcyclohexyl 4-[(E)-3-acetoxyhept-1-en-1-yl]benzoate compound (3e):

[0068] The reaction equation is:

[0069]

[0070] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1e (28.6 mg, 0.10 mmol, 1.0 equiv), 2a (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (3e) in a yield of 72%.

[0071] The characterization data of compound (3e) are:

[0072] Colorless oily liquid: 1 H NMR (600MHz, CDCl3) δ7.98 (d, J=8.3Hz, 2H), 7.42 (d, J=8.3Hz, 2H), 6.62 (d, J=15.9Hz, 1H) , 6.23 (dd, J=16.0, 7.1Hz, 1H), 5.41 (q, J=6.6Hz, 1H), 4.92 (td, J=10.9, 4.4Hz, 1H), 2.16-2 .11 (m, 1H), 2.09 (s, 3H), 1.94 (dtd, J=14.0, 7.0, 2.8Hz, 1H), 1.77-1.66 (m, 4H), 1.59-1.5 1 (m, 2H), 1.34-1.29 (m, 2H), 1.13-1.07 (m, 2H), 0.93-0.89 (m, 12H), 0.79 (d, J=6.9Hz, 3H).

[0073] 13 C NMR (151MHz, CDCl3) δ170.4, 165.8, 140.7, 131.27, 131.26, 130.0, 129.9, 126.4, 74.9, 7 4.5, 47.3, 41.0, 34.3, 34.2, 31.5, 27.3, 26.6, 23.7, 22.5, 22.1, 21.3, 20.8, 16.6, 14.0.

[0074] HRMS(ESI)m / z:[M+Na] + Calcd for C 26 H 38 O4Na 437.2662; found 437.2663.

[0075] Example 6

[0076] In this example, a fatty aldehyde derivative, such as 1-iodo-3-methylbutyl acetate (2b) having a secondary α-carbon, is reacted with 1-(tert-butyl)-4-vinylbenzene (1a) to synthesize (E)-1-(4-(tert-butyl)phenyl)-5-methylhex-1-en-3-yl acetate compound (4a):

[0077] The reaction equation is:

[0078]

[0079] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1a (16.0 mg, 0.10 mmol, 1.0 equiv), 2b (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (4a) in a yield of 77%.

[0080] The characterization data of compound (4a) are:

[0081] Colorless oily liquid: 1H NMR (600MHz, CDCl3) δ7.36-7.31 (m, 4H), 6.60 (d, J=15.9Hz, 1H), 6.07 (dd, J=15.9, 7.6Hz, 1H), 5.48 (q, J= 6.7Hz, 1H), 2.06 (s, 3H), 1.70-1.61 (m, 2H), 1.52-1.43 (m, 1H), 1.31 (s, 9H), 0.94 (dd, J=6.3, 5.1Hz, 6H).

[0082] 13 C NMR (151MHz, CDCl3) δ170.4, 151.1, 133.6, 132.3, 127.2, 126.3, 125.5, 73.5, 43.6, 31.3, 24.6, 22.7, 22.6, 21.4.

[0083] HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 28 O2Na 311.1982; found311.1981.

[0084] Example 7

[0085] In this example, a fatty aldehyde derivative, such as 1-iodo-2-methylpropyl acetate (2c) having a tertiary α-carbon, is reacted with 1-(tert-butyl)-4-vinylbenzene (1a) to synthesize (E)-1-(4-(tert-butyl)phenyl)-4-methylpent-1-en-3-yl acetate (4b):

[0086] The reaction equation is:

[0087]

[0088] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1a (16.0 mg, 0.10 mmol, 1.0 equiv), 2c (48.4 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (4b) in a yield of 67%.

[0089] The characterization data of compound (4b) are:

[0090] Colorless oily liquid: 1 H NMR (600MHz, CDCl3) δ7.36-7.31 (m, 4H), 6.57 (d, J=15.9Hz, 1H), 6.08 (dd, J=15.9, 7.7Hz, 1H), 5.21-5.18 (m, 1H), 2.08 (s, 3H), 1.31 (s, 9H), 1.28-1.27 (m, 1H), 0.95 (dd, J=10.4, 6.8Hz, 6H).

[0091] 13 C NMR (151MHz, CDCl3) δ170.4, 151.0, 133.7, 133.2, 126.3, 125.5, 125.3, 79.6, 34.6, 32.3, 31.3, 21.3, 18.3, 18.2.

[0092] HRMS(ESI)m / z:[M+Na] + Calcd for C 18 H 26 O2Na 297.1825; found297.1825.

[0093] Example 8

[0094] In this example, a fatty aldehyde derivative, such as 1-iodo-2,2-dimethylpropyl acetate (2d) with a quaternary carbon as the α-carbon, is reacted with 1-(tert-butyl)-4-vinylbenzene (1a) to synthesize (E)-1-(4-(tert-butyl)phenyl)-4,4-dimethylpent-1-en-3-yl acetate (4c):

[0095] The reaction equation is:

[0096]

[0097] The synthesis steps and process were as follows: To an 8 mL reaction vial equipped with a stirrer were added: 1a (16.0 mg, 0.10 mmol, 1.0 equiv), 2d (51.2 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv). The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum cap and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (4c) in a yield of 56%.

[0098] The characterization data of compound (4c) are:

[0099] Colorless oily liquid: 1 H NMR (600MHz, CDCl3) δ7.36-7.32 (m, 4H), 6.57 (d, J=15.9Hz, 1H), 6.12 (dd, J=15.9 , 7.9Hz, 1H), 5.16 (dd, J=7.9, 0.9Hz, 1H), 2.08 (s, 3H), 1.31 (s, 9H), 0.96 (s, 9H).

[0100] 13 C NMR (151MHz, CDCl3) δ169.4, 150.0, 132.7, 132.6, 125.3, 124.5, 123.2, 80.8, 33.7, 33.6, 30.2, 24.9, 20.2.

[0101] HRMS(ESI)m / z:[M+Na]+ Calcd for C 19 H 28 O2Na 311.1982; found311.1982.

[0102] Example 9

[0103] In this example, a fatty aldehyde derivative such as the cyclic aldehyde cyclopentyl iodomethyl acetate (2e) is reacted with 1-(tert-butyl)-4-vinylbenzene (1a) to synthesize (E)-3-[4-(tert-butyl)phenyl]-1-cyclopentylallyl acetate compound (4d):

[0104] The reaction equation is:

[0105]

[0106] The synthesis steps and process were as follows: 1a (16.0 mg, 0.10 mmol, 1.0 equiv), 2e (53.6 mg, 0.20 mmol, 2.0 equiv), Co(dmgH)(dmgH2)Cl2 (0.7 mg, 2 mol%), (NH4)2CO3 (19.2 mg, 0.20 mmol, 2.0 equiv), and indium powder (17.2 mg, 0.15 mmol, 1.5 equiv) were added sequentially to an 8 mL reaction vial equipped with a stirrer. The reaction vial was sealed with a polytetrafluoroethylene (TFE)-lined silicone septum and a nitrogen atmosphere was established by three evacuation and nitrogen replacement cycles. Under nitrogen protection, acetonitrile (1.0 mL, 0.1 M) was added to the mixture via syringe. The reaction mixture was stirred at room temperature and reacted under blue LED illumination for 12 hours. After completion, the reaction was quenched with saturated brine (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was separated and purified by column chromatography (n-hexane:ethyl acetate=30:1) to obtain the target product (4d) in a yield of 67%.

[0107] The characterization data of compound (4d) are:

[0108] Colorless oily liquid: 1 H NMR (600MHz, CDCl3) δ7.36-7.30 (m, 4H), 6.58 (d, J=15.9Hz, 1H), 6.08 (dd, J=15.9, 7.7Hz, 1H), 5.27 ( t, J=7.7Hz, 1H), 2.25-2.16 (m, 1H), 2.06 (s, 3H), 1.79-1.61 (m, 4H), 1.31 (s, 9H), 1.29-1.23 (m, 4H).

[0109] 13 C NMR (151MHz, CDCl3) δ170.5, 151.0, 133.7, 132.7, 126.4, 126.3, 125.5, 78.6, 43.9, 34.6, 31.3, 29.0, 28.7, 25.6, 25.4, 21.4.

[0110] HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 28 O2Na 323.1982;found323.1982

[0111] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for synthesizing an allyl ester compound, characterized in that: The reaction equation is:

2. The synthesis method according to claim 1, characterized in that In the compound (1), R 1 is tert-butyl, cyano, methoxy, estrone or menthyl ester; Ar is a benzene ring or pyrimidine.

3. The synthesis method according to claim 1, wherein In the compound (2), R 2 It is n-butyl, 3-methylbutanal, 2-methylpropanal, 2,2-dimethylpropanal or cyclopentanal.

4. The synthesis method according to claim 1, characterized in that The specific steps are: Compound (1), compound (2), a catalyst, a base, and a reducing agent are mixed in a solvent under a nitrogen atmosphere and then reacted under light to obtain compound (3).

5. The synthesis method according to claim 4, characterized in that The molar ratio of the compound (1), the compound (2), the catalyst, the base and the reducing agent is 1:2:0.02:2:1.

5.

6. The synthesis method according to claim 4, characterized in that The catalyst is a cobalt oxime complex, and the cobalt oxime complex includes Co(dmgH)(dmgH2)Cl2.

7. The synthesis method according to claim 4, characterized in that The base is (NH4)2CO3.

8. The synthesis method according to claim 4, characterized in that The reducing agent is indium powder.

9. The synthesis method according to claim 4, characterized in that The solvent is acetonitrile.

10. The synthesis method according to claim 4, characterized in that The light is a blue light LED with a power of 12 to 20W; and the reaction time is 12 to 15 hours.

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