A palladium catalyzed synthetic method for carbon-carbon bond formation

Abstract

The application relates to the technical field of organic synthesis, in particular to a synthesis method for forming carbon-carbon bonds under palladium catalysis, which comprises the following steps: mixing an olefin derivative and an iodine-substituted aromatic compound to form a mixed reaction system, and reacting under the catalysis of a palladium catalyst and ultrasonic conditions to obtain an aromatic hydrocarbon compound. The synthesis method effectively avoids the use of a solvent, and has the advantages of mild reaction conditions, low reaction temperature and simple post-treatment process.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for synthesizing carbon-carbon bonds using palladium catalysis. Background Technology

[0002] Carbon-carbon bond formation is one of the most widely studied organic synthesis reactions, with broad applications in industries such as agricultural chemistry and pharmaceuticals. However, developing a reaction scheme for aryl carbon-carbon coupling that can be performed at room temperature, over a wide substrate range, and under solvent-free conditions remains a challenge. The Heck coupling reaction is one of the classic and effective methods for forming carbon-carbon bonds in modern organic compounds. Traditional Heck coupling reactions generally refer to the coupling reaction of unsaturated haloalkanes (or trifluoromethanesulfonates) with alkenes under strong base and palladium catalysis to form substituted alkenes; the reaction conditions are not mild. Chinese invention patent CN102010279A discloses a method for preparing aryl ethylene derivatives. Using PEG-400 as a solvent and palladium chloride as a catalyst, iodoaryl hydrocarbons and olefin compounds react in an alkaline environment at a molar ratio of 1:1 to 1:3 for 10 to 15 minutes under focused microwave irradiation. This reaction is simpler and faster than the traditional Heck coupling reaction, but its reaction conditions still have shortcomings. For example, it requires the use of PEG-400 as a solvent and the reaction temperature needs to be controlled above 100°C. Therefore, to address the deficiencies of the existing technology, it is still necessary to develop a carbon-carbon coupling method that conforms to the principles of green chemistry, is easy to operate, and has good substrate applicability. Summary of the Invention

[0003] To address the aforementioned technical problems, the present invention aims to provide a palladium-catalyzed method for synthesizing carbon-carbon bonds, which effectively reduces the use of organic solvents while improving reaction efficiency and safety.

[0004] To achieve the above-mentioned technical effects, the present invention adopts the following technical solution:

[0005] A method for synthesizing carbon-carbon bonds using palladium catalysis involves reacting a mixed reaction system of an olefin derivative and an iodinated aromatic compound under palladium catalysis and ultrasonic conditions to obtain aromatic hydrocarbon compounds.

[0006] Furthermore, the general reaction formula for the above-mentioned palladium-catalyzed carbon-carbon bond formation synthesis method is shown in Formula I or Formula II:

[0007]

[0008] Preferably, in Formula I, R1 is any one or more of carbonyl, ester, aldehyde, or carboxyl groups; more preferably, it is any one or more of carbonyl, ester, aldehyde, or carboxyl groups from C1 to C5; most preferably, it is any one or more of -COCH3, -COOMe, -COOH, and -CHO.

[0009] Preferably, in Formula I, the iodinated aromatic compound Iodinated aromatic compounds of alkyl, alkoxy, hydroxy, phenyl, aldehyde, ester, chlorine, or bromine groups that are unsubstituted or ortho-substituted, meta-substituted, or para-substituted; more preferably, ortho-, meta-, or para-substituted iodobenzoates; most preferably, para-substituted iodobenzoates.

[0010]

[0011] Preferably, in Formula II, R2 is any one or more of hydrogen, alkyl, carbonyl, ester, aldehyde or carboxyl, more preferably R2 is any one of hydrogen, alkyl or aldehyde; most preferably hydrogen or a C1 to C4 aldehyde.

[0012] Preferably, in Formula II, R3 is any one or more of alkyl, alkoxy, ester, aryl, and benzenesulfonyl groups; more preferably, it is any one of -CH2OBn, -COOMe, -Ph, and benzenesulfonyl groups.

[0013] Preferably, in Formula I, the iodinated aromatic compound It is any one or more of the following iodoaromatic compounds: unsubstituted or ortho-, meta-, or para-substituted alkyl, alkoxy, hydroxy, phenyl, aldehyde, ester, chlorine, or bromine.

[0014] Preferably, the mixed reaction system does not include a solvent, and the molar ratio of the olefin derivative to the iodinated aromatic compound is 1:2 to 5.

[0015] Preferably, the mixed reaction system further includes silver trifluoroacetate, and preferably, the molar ratio of silver trifluoroacetate to olefin derivative is 1:2 to 3.

[0016] Preferably, the palladium catalyst is selected from any one or more of PdCl2, Pd(dba)2, Pd2(dba)3, Pd(OAc)2, Pd(TFA)2, PdCl2(dppf), PdCl2(PPh3)2 or Pd(PPh3)4; preferably, the amount of palladium catalyst added is 0.001 to 0.3 equivalents.

[0017] Preferably, the reaction time under ultrasonic conditions is 10 to 30 hours.

[0018] Furthermore, after the reaction under ultrasonic conditions, the process also includes extraction and purification steps.

[0019] More preferably, the extraction step is as follows: extraction is performed using a mixture of organic solvent and water, followed by phase separation to obtain an organic phase and an aqueous phase, and the organic phase is dried and concentrated to obtain a crude product; the purification step is as follows: the crude product obtained after extraction is purified by silica gel column chromatography, and the fraction containing the target product is concentrated to obtain the target product.

[0020] Preferably, the reaction temperature under ultrasonic conditions is 0–40°C, and more preferably, the reaction temperature is 15–25°C.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] This invention provides a palladium-catalyzed method for the formation of carbon-carbon bonds. This method employs an ultrasound-assisted reaction, replacing traditional heating methods. Ultrasonic treatment also increases the reaction rate, avoids high-temperature reactions, and reduces the use of organic solvents, thus improving efficiency, safety, and environmental impact. It is a green, inexpensive, efficient, and mild synthetic method. Furthermore, this palladium-catalyzed carbon-carbon bond formation method is solvent-free. Solvent-free synthesis, as a developing direction in organic synthesis, offers advantages such as reduced environmental pollution, simplified processes and treatments, and atom economy, aligning with the development concept of green chemistry. In addition, the synthesis process is carried out at room temperature, which is a relatively mild reaction condition, and the method is compatible with various functional groups, resulting in high reaction yields.

[0023] In summary, there are many reports on the Heck coupling reaction of haloaromatics with unsaturated alkenes, but the reaction conditions are not ideal. Compared with existing synthetic methods, this method has the advantages of novel synthesis, simple conditions, ease of operation, atom economy and environmental friendliness. Attached Figure Description

[0024] Figure 1 The proton nuclear magnetic resonance spectrum of compound 1a synthesized in Example 1 of this invention ( 1 H NMR spectrum;

[0025] Figure 2 The proton nuclear magnetic resonance spectrum of compound 1b synthesized in Example 1 of this invention ( 1 H NMR spectrum;

[0026] Figure 3 The proton nuclear magnetic resonance spectrum of compound 1c synthesized in Example 1 of this invention (… 1 H NMR spectrum;

[0027] Figure 4The proton nuclear magnetic resonance spectrum of compound 1d synthesized in Example 1 of this invention (… 1 H NMR spectrum;

[0028] Figure 5 The proton nuclear magnetic resonance spectrum of compound 2e synthesized in Example 1 of this invention ( 1 H NMR spectrum;

[0029] Figure 6 The proton nuclear magnetic resonance spectrum of compound 2f synthesized in Example 1 of this invention ( 1 H NMR spectrum;

[0030] Figure 7 The proton nuclear magnetic resonance spectrum of 2g of the compound synthesized in Example 1 of this invention (… 1 H NMR spectrum;

[0031] Figure 8 The proton nuclear magnetic resonance spectrum of the compound synthesized in Example 1 of this invention (2h) 1 H NMR spectrum;

[0032] Figure 9 The proton nuclear magnetic resonance spectrum of compound 3i synthesized in Example 2 of this invention ( 1 H NMR spectrum;

[0033] Figure 10 The proton nuclear magnetic resonance spectrum of compound 3j synthesized in Example 2 of this invention (… 1 H NMR spectrum;

[0034] Figure 11 The proton nuclear magnetic resonance spectrum of compound 3k synthesized in Example 2 of this invention (… 1 H NMR spectrum;

[0035] Figure 12 The proton nuclear magnetic resonance spectrum of compound 3l synthesized in Example 2 of this invention ( 1 H NMR spectrum;

[0036] Figure 13 The proton nuclear magnetic resonance spectrum of compound 3m synthesized in Example 2 of this invention ( ) 1 H NMR spectrum;

[0037] Figure 14 The proton nuclear magnetic resonance spectrum of compound 3n synthesized in Example 2 of this invention (NMR spectrum). 1 H NMR spectrum;

[0038] Figure 15 The proton nuclear magnetic resonance spectrum of compound 3o synthesized in Example 2 of this invention (NMR spectrum). 1 H NMR spectrum;

[0039] Figure 16 The proton nuclear magnetic resonance spectrum of compound 3p synthesized in Example 2 of this invention (NMR spectrum). 1 H NMR spectrum. Detailed Implementation

[0040] The embodiments of the technical solution of the present invention will now be described in detail with reference to the accompanying drawings. These embodiments are merely illustrative of the technical solution of the present invention and are therefore intended to limit the scope of protection of the present invention.

[0041] The specific embodiments listed in this invention are merely examples, and the invention is not limited to the specific embodiments described below. For those skilled in the art, any equivalent modifications and substitutions to the embodiments described below are also within the scope of this invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of this invention should be covered within its scope. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer should be followed. All reagents or instruments without specified manufacturers are commercially available conventional products.

[0042] To better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art will understand that the present invention can be practiced without certain specific details. In other embodiments, methods, means, apparatus, and steps well known to those skilled in the art are not described in detail in order to highlight the spirit of the invention.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Unless otherwise specified, all units used in this specification are International Standard Units (SI), and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors unavoidable in industrial production.

[0044] Example 1

[0045] This embodiment provides a method for synthesizing carbon-carbon bonds catalyzed by palladium, the specific steps of which are as follows:

[0046] First, palladium chloride (10 mmol%) and silver trifluoroacetate (1.5 equivalents, 0.3 mmol) were added to a 5 ml centrifuge tube, followed by the addition of an iodoaromatic compound (1 equivalent, 0.2 mmol) and an olefin derivative (3 equivalents). After adding the raw materials, the mixture was stirred and then sonicated at room temperature.

[0047] After the reaction was complete, the mixture of dichloromethane and water was used for extraction. The organic and aqueous phases were then separated. The organic phase was dried over anhydrous magnesium sulfate, and the filtrate was concentrated under vacuum to obtain crude product 1. Product 1 (1a-1d) was purified by silica gel column chromatography. The separation yield was calculated, and the structure was identified using NMR. The synthetic route is shown in Equation I:

[0048]

[0049] The following are several specific examples of synthesis based on Equation I above, including:

[0050] 1.1 Synthesis of Compound 1a

[0051] The structural formula of compound 1a is as follows:

[0052]

[0053] The synthesis route is shown in Equation 1A:

[0054]

[0055] Formula 1a: Methyl 6'-acetyl-2',3',4',5'-tetrahydro-[1,1'-biphenyl]-4-carboxylic acid: white solid (yield 85%); R f (Petroleum ether:ethyl acetate = 10:1): 0.5.

[0056] 1 1H NMR (400MHz, CDCl3) δ 7.92 (d, J = 9.36Hz, 2H), 7.19 (d, J = 8.00Hz, 1H), 7.17 (d, J = 8.22Hz, 2H), 4.05 (s, 1H), 3.88 (s, 3H), 2.45–2.39 (m, 1H), 2.34–2.3 (m, 1H), 2.25 (s, 3H), 1.95–1.85 (m, 1H), 1.79–1.75 (m, 1H), 1.55–1.45 (m, 2H); 1H NMR spectrum ( 1 (H NMR) see Figure 1 .

[0057] 13 C NMR (400MHz, CDCl3) δ198.16,167.07,150.70,142.57,140.65,129.58,127.71,51.89,38.60,31.01,26.10,25.67,16.95.

[0058] 1.2 Synthesis of Compound 1b

[0059] The structural formula of compound 1b is as follows:

[0060]

[0061] The synthesis route is shown in Equation 1B:

[0062]

[0063] Formula 1b: 4'-(methoxycarbonyl)-1,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylic acid: white solid (75% yield), R f (Petroleum ether:ethyl acetate = 10:1): 0.5.

[0064] 1 1H NMR (400MHz, CDCl3) δ 7.93 (d, J = 8.31Hz, 2H), 7.39 (t, J = 3.77Hz, 1H), 7.18 (d, J = 8.26Hz, 2H), 3.91 (s, 1H), 3.88 (s, 3H), 2.40–2.52 (m, 2H), 1.95–1.89 (m, 1H), 1.78–1.72 (m, 1H), 1.56–1.50 (m, 1H), 1.47–1.41 (m, 1H); 1H NMR spectrum ( 1 (H NMR) see Figure 2 .

[0065] 13 C NMR (400MHz, CDCl3) δ171.82,167.13,150.30,144.89,130.66,129.60,128.05,127.73,51.95,39.22,31.03,26.03,16.64.

[0066] 1.3 Synthesis of Compound 1c

[0067] The structural formula of compound 1c is as follows:

[0068]

[0069] The synthesis route is shown in Equation 1C:

[0070]

[0071] Formula 1c: Dimethyl 1,4,5,6-tetrahydro-[1,1'-biphenyl]-2,4'-dicarboxylic acid: white solid (70% yield), R f (Petroleum ether:ethyl acetate = 10:1): 0.5.

[0072] 11H NMR (400MHz, CDCl3) δ 7.87 (d, J = 8.24Hz, 2H), 7.21 (t, J = 3.85Hz, 1H), 7.14 (d, J = 8.25Hz, 2H), 3.81 (s, 3H), 3.50 (s, 3H), 2.30–2.20 (m, 2H), 1.85–1.65 (m, 3H), 1.47–1.40 (m, 2H); 1H NMR spectrum ( 1 (H NMR) see Figure 3 .

[0073] 13 C NMR (400MHz, CDCl3) δ167.27,167.11,150.66,142.22,131.32,129.59,128.01,127.71,51.94,51.53,39.75,31.21,25.83,17.03.

[0074] 1.4 Synthesis of Compound 1d

[0075] The structural formula of compound 1d is as follows:

[0076]

[0077] The synthesis route is shown in Equation 1D:

[0078]

[0079] Formula 1d: Methyl 6'-formyl-1',2',3',4'-tetrahydro-[1,1'-biphenyl]-4-carboxylic acid: white solid (65% yield). f (Petroleum ether:ethyl acetate = 10:1): 0.5.

[0080] 1 ¹H NMR (400MHz, CDCl₃) δ 9.37 (s, 1H), 7.86 (d, J = 8.50Hz, 2H), 7.09 (d, J = 8.26Hz, 2H), 7.06 (d, J = 3.80Hz, 1H), 3.86 (s, 1H), 3.81 (s, 3H), 2.40–2.52 (m, 2H), 1.87–1.75 (m, 1H), 1.73–1.68 (m, 1H), 1.54–1.48 (m, 2H); ... 1 (H NMR) see Figure 4 .

[0081] 13C NMR (400MHz, CDCl3) δ193.25,167.09,153.46,149.45,142.71,129.63,128.10,127.78,37.45,26.57,17.57.

[0082] Example 2

[0083] This embodiment provides a method for synthesizing carbon-carbon bonds catalyzed by palladium, the specific steps of which are as follows:

[0084] First, palladium chloride (10 mmol%) and silver trifluoroacetate (1.5 equivalents, 0.3 mmol) were added to a 5 ml centrifuge tube, followed by the addition of an iodoaromatic compound (1 equivalent, 0.2 mmol) and an olefin derivative (3 equivalents). After adding the raw materials, the mixture was stirred and then sonicated at room temperature.

[0085] After the reaction was completed, the mixture of dichloromethane and water was used for extraction. The organic phase and aqueous phase were separated after extraction. The organic phase was then dried with anhydrous magnesium sulfate. After filtering to remove the anhydrous magnesium sulfate, the filtrate was concentrated under vacuum to obtain crude product 2. The crude product was purified by silica gel column chromatography (2e-2h). The separation yield was calculated, and the structure was identified by NMR. The synthetic route is shown in Formula II.

[0086]

[0087] The following are several specific examples of synthesis based on Equation II above, including:

[0088] 2.1 Synthesis of compound 2e

[0089] The structural formula of compound 2e is as follows:

[0090]

[0091]

[0092] The synthesis route is shown in Equation 2E:

[0093]

[0094] Formula 2e: (Z)-4-(2-formyl-3-phenylallyl)methyl benzoate; white solid (75% yield). f (Petroleum ether:ethyl acetate = 10:1): 0.4.

[0095] 11H NMR (400MHz, CDCl3) δ 9.73 (s, 1H), 7.96 (d, J = 8.05Hz, 2H), 7.57 (s, 1H), 7.46 (d, J = 7.00Hz, 2H), 7.42–7.40 (m, 3H), 7.24 (d, J = 8.50Hz, 2H), 4.01 (s, 2H), 3.91 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 5 .

[0096] 13 C NMR (400MHz, CDCl3) δ194.92,194.78,166.99,152.04,143.91,139.73,134.28,130.17,129.97,129.69,128.93,128.30,128.01,52.02,30.56.

[0097] 2.2 Synthesis of compound 2f

[0098] The structural formula of compound 2f is as follows:

[0099]

[0100] The synthesis route is shown in Equation 2F:

[0101]

[0102] Formula 2f: (E)-4-(3-(benzyloxy)-1-en-1-yl)benzoate: colorless oil (yield 75%). f (Petroleum ether:ethyl acetate = 10:1): 0.3.

[0103] 1 ¹H NMR (400MHz, CDCl₃) δ 8.01 (d, J = 8.90Hz, 2H), 7.46 (d, J = 7.37Hz, 2H), 7.41–7.30 (m, 5H), 6.70 (d, J = 16.00Hz, 1H), 6.50–6.43 (m, 1H), 4.61 (d, J = 6.99Hz, 2H), 4.25 (dd, J = 6.00Hz, 2H), 3.93 (d, J = 2.66Hz, 3H); ... 1 (H NMR) see Figure 6 .

[0104] 13C NMR (400MHz, CDCl3) δ166.89,141.26,131.12,129.94,129.10,128.98,128.48,127.81,127.76,126.35,72.49,40.46,52.08.

[0105] 2.3 Synthesis of Compound 2g

[0106] The structural formula of compound 2g is as follows:

[0107]

[0108] The synthesis route is shown in Equation 2G:

[0109]

[0110] Formula 2g: (E)-4-(2-(phenylsulfonyl)vinyl)benzoate: white solid (yield 75%). f (Petroleum ether:ethyl acetate = 3:1): 0.4.

[0111] 1 ¹H NMR (500MHz, CDCl₃) δ 7.98–7.85 (m, 4H), 7.65–7.56 (m, 2H), 7.50–7.45 (m, 4H), 6.88 (dd, J = 16.00 Hz, 1H), 3.83 (d, J = 4.89 Hz, 3H); ... 1 (H NMR) see Figure 7 .

[0112] 13 C NMR (500MHz, CDCl3) δ166.14,140.89,136.51,133.64,132.23,130.22,129.79,129.44,128.44,127.80,52.37.

[0113] 1.4 Synthesis of compound 2h

[0114] The structural formula of compound 2h is as follows:

[0115]

[0116] The synthetic route is shown in Equation 2H:

[0117]

[0118] Formula 2h: (E)-4-(3-methoxy-3-oxopropyl-1-en-1-yl)benzoate: white solid (95% yield).f (Petroleum ether:ethyl acetate = 10:1): 0.3.

[0119] 1 1H NMR (400MHz, CDCl3) δ 7.97 (d, J = 7.86Hz, 2H), 7.62 (d, J = 16.05Hz, 1H), 7.50 (d, J = 8.06Hz, 2H), 6.44 (d, J = 16.05Hz, 1H), 3.85 (d, J = 0.86Hz, 3H), 3.74 (d, J = 0.82Hz, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 8 .

[0120] 13 C NMR (400MHz, CDCl3) δ166.96,166.42,143.44,138.57,131.39,130.10,127.91,120.17,52.29,51.89.

[0121] Example 3

[0122] This embodiment provides a method for synthesizing carbon-carbon bonds catalyzed by palladium, specifically including:

[0123] First, palladium chloride (10 mmol%) and silver trifluoroacetate (1.5 equivalents, 0.3 mmol) were added to a 5 ml centrifuge tube, followed by the addition of iodoaromatic compound (1 equivalent, 0.2 mmol) and methyl acrylate (3 equivalents). After adding the raw materials, the mixture was stirred well and then sonicated at room temperature for 24 hours.

[0124] After the reaction was complete, the product was extracted with a mixture of dichloromethane and water. The organic phase was dried over anhydrous magnesium sulfate, filtered to remove the precipitate, and concentrated under vacuum to obtain crude product 3. The product (3i-3p) was purified by silica gel column chromatography, the separation yield was calculated, and the structure was identified by NMR. The synthetic route is shown in Formula III:

[0125]

[0126] The following are several specific examples of synthesis based on Equation III above, including:

[0127] 3.1 Synthesis of Compound 3i

[0128] The structural formula of compound 3i is as follows:

[0129]

[0130] The synthesis route is shown in Equation 3I:

[0131]

[0132] Formula 3i: (E)-3-(o-tolyl)methyl acrylate: colorless oil (yield 94%). R f (Petroleum ether:ethyl acetate = 10:1): 0.3.

[0133] 1 1H NMR (400MHz, CDCl3) δ 7.9 (d, J = 15.91Hz, 1H), 7.48–7.43 (m, 1H), 7.15–7.20 (m, 1H), 7.12 (t, J = 6.99Hz, 2H), 6.28 (d, J = 15.90Hz, 1H), 3.73 (s, 3H), 2.35 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 9 .

[0134] 13 C NMR (400MHz, CDCl3) δ167.48,142.56,137.67,133.39,130.80,130.04,126.42,126.35,118.88,51.68,19.79.

[0135] 3.2 Synthesis of Compound 3j

[0136] The structural formula of compound 3j is as follows:

[0137]

[0138] The synthesis route is shown in Equation 3J:

[0139]

[0140] Formula 3j: (E)-3-(3-methoxy-3-oxopropyl-1-en-1-yl)benzoate: white solid (95% yield). f (Petroleum ether:ethyl acetate = 10:1): 0.3.

[0141] 1 1H NMR (400MHz, CDCl3) δ 8.21 (d, J = 16.01Hz, 1H), 8.06 (d, J = 14.00Hz, 1H), 7.75–7.68 (m, 2H), 7.46 (dd, J = 15.00Hz, 1H), 6.57–6.48 (m, 1H), 4.45–4.48 (m, 2H), 3.85–3.80 (m, 3H), 1.45–1.38 (m, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 10 .

[0142] 13 C NMR (400MHz, CDCl3) δ167.08,165.95,143.69,134.67,132.07,131.29,131.07,128.96,119.07,61.25,51.77,14.30.

[0143] 3.3 The structural formula of compound 3k is as follows:

[0144]

[0145] The synthesis route is shown in equation 3k:

[0146]

[0147] Formula 3k: (E)-3-(4-chlorophenyl)acrylate methyl acrylate: white solid (yield 93%). f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0148] 1 1H NMR (400MHz, CDCl3) δ 7.55 (d, J = 16.03Hz, 1H), 7.36 (d, J = 6.50Hz, 2H), 7.27 (d, J = 6.50Hz, 2H), 6.32 (d, J = 16.02Hz, 1H), 3.72 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 11 .

[0149] 13 C NMR (400MHz, CDCl3) δ167.15,143.39,136.21,132.88,129.22,129.17,118.40,51.77.

[0150] 3.4 The structure of the product is shown in Formula 3l:

[0151]

[0152] The synthesis route is shown in Equation 3L:

[0153]

[0154] Formula 3l: (E)-3-(3,4-dimethoxyphenyl)methyl acrylate (3l): colorless oil (yield 90%). R f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0155] 11H NMR (400MHz, CDCl3) δ 7.64 (d, J = 15.94Hz, 1H), 7.12–7.05 (m, 2H), 6.85 (d, J = 2.00Hz, 1H), 6.31 (d, J = 15.93Hz, 1H), 3.91 (s, 6H), 3.80 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 12 .

[0156] 13 C NMR (400MHz, CDCl3) δ167.64,151.14,149.21,144.77,127.36,122.58,115.48,111.05,109.66,55.95,55.87,51.59.

[0157] 3.5 The product structure is shown in Equation 3m:

[0158]

[0159] The synthesis route is shown in Equation 3M:

[0160]

[0161] Formula 3m: (E)-3-(4-chloro-2-hydroxyphenyl)methyl acrylate: white solid (yield 80%). f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0162] 1 ¹H NMR (400MHz, CDCl₃) δ 7.87 (d, J = 16.18 Hz, 1H), 7.48 (d, J = 2.57 Hz, 1H), 7.18 (dd, J = 8.20 Hz, 1H), 6.82 (d, J = 8.73 Hz, 1H), 6.59 (d, J = 16.17 Hz, 1H), 4.89 (s, 1H), 3.77 (s, 3H); ... 1 (HNMR) see Figure 13 .

[0163] 13 C NMR (400MHz, CDCl3) δ169.13,155.55,139.34,130.68,127.80,124.07,122.72,118.02,117.02,50.75.

[0164] 3.6 The product structure is shown in Equation 3n:

[0165]

[0166] The synthesis route is shown in Equation 3N:

[0167]

[0168] Formula 3n: (E)-3-(thiophen-3-yl)methyl acrylate: white solid (yield 85%). f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0169] 1 1H NMR (400MHz, CDCl3) δ 7.60 (d, J = 15.92Hz, 1H), 7.41 (d, J = 2.24Hz, 1H), 7.26–7.18 (m, 2H), 6.18 (d, J = 15.91Hz, 1H), 3.71 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 14 .

[0170] 13 C NMR (400MHz, CDCl3) δ167.64,138.31,137.55,128.07,126.96,125.17,117.49,51.62.

[0171] 3.7 The structure of the product is shown in Formula 3o:

[0172]

[0173] The synthetic route is shown in Equation 30:

[0174]

[0175] Formula 3o: (E)-3-(benzo[d][1,3]dioxo-5-yl)methyl acrylate: white solid (yield 85%). f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0176] 1 1H NMR (400MHz, CDCl3) δ 7.51 (d, J = 15.92Hz, 1H), 6.95–6.91 (m, 2H), 6.73 (d, J = 8.00Hz, 1H), 6.18 (d, J = 15.91Hz, 1H), 5.92 (s, 2H), 3.71 (s, 3H); 1H NMR spectrum ( 1 (H NMR) see Figure 15 .

[0177] 13C NMR (400MHz, CDCl3) δ167.60,149.02,148.35,144.56,128.81,124.44,115.72,108.54,106.48,101.57,51.62.

[0178] 3.8 The product structure is shown in Equation 3p:

[0179]

[0180] The synthesis route is shown in equation 3P:

[0181]

[0182] Formula 3p: (E)-3-(9-phenyl-9H-carbazole-3-yl)methyl acrylate: colorless oil (yield 85%). R f (Petroleum ether:ethyl acetate = 3:1):0.5.

[0183] 1 ¹H NMR (400MHz, CDCl₃) δ 8.20 (s, 1H), 8.05 (d, J = 7.66Hz, 1H), 7.82 (d, J = 15.89Hz, 1H), 7.51 (d, J = 12.00Hz, 3H), 7.42 (d, J = 12.85Hz, 3H), 7.33–7.24 (m, 4H), 6.4 (d, J = 15.91Hz, 1H), 3.73 (s, 3H); ... 1 (H NMR) see Figure 16 .

[0184] 13 C NMR (400MHz, CDCl3) δ167.98,130.03,127.92,127.08,126.59,125.95,120.65,120.48,114.96,110.23,110.17,51.61.

[0185] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications and substitutions should be covered within the scope of the claims of the present invention. Technical aspects, shapes, and structures not described in detail in this invention are all well-known technologies.

Claims

1. A synthetic method for palladium catalyzed formation of carbon-carbon bonds characterized by: The olefin derivative, the iodine derivative aromatic compound, the silver trifluoroacetate and the palladium catalyst are mixed to form a solvent-free reaction system, and the reaction is carried out under ultrasonic condition to obtain the aromatic hydrocarbon compound, and the reaction general formula is shown in formula I or formula II. Formula I Formula II In formula I, R1 is a carbonyl group; an iodoaromatic compound an iodoaromatic compound which is unsubstituted or ortho-, meta- or para-substituted by alkyl, alkoxy, hydroxy, phenyl, aldehyde, ester, chlorine, bromine In formula II, R2 is any one of hydrogen, alkyl and carbonyl; and R3 is any one of alkyl, alkoxy, ester group, aryl and phenylsulfonyl.

2. A palladium catalyzed synthesis method for forming carbon-carbon bonds according to claim 1, wherein, In formula I, the iodoaromatic compound is an ortho, meta or para substituted iodo benzoate; In formula II, R2 is any one of hydrogen, alkyl and aldehyde group; and R3 is any one of -CH2OBn, -COOMe, -Ph and phenylsulfonyl.

3. A palladium catalyzed synthesis method for forming carbon-carbon bonds as claimed in claim 1, wherein, In formula I, R1 is any one of -COCH3, -COOMe, -COOH, -CHO; an iodinated aromatic compound is a para-substituted iodinated benzoate; In formula II, R2 is hydrogen or C1-C4 aldehyde group.

4. A palladium catalyzed synthesis method for forming carbon-carbon bonds according to claim 1, wherein: The palladium catalyst is any one of PdCl2, Pd(dba)2, Pd2(dba)3, Pd(OAc)2, Pd(TFA)2, PdCl2(dppf), PdCl2(PPh3)2 or Pd(PPh3)4.

5. A palladium catalyzed synthesis method for forming carbon-carbon bonds according to claim 4, wherein, The palladium catalyst is added in an amount of 0.001-0.3 equivalent.

6. The method for synthesizing carbon-carbon bonds catalyzed by palladium as described in claim 1, characterized in that: The reaction under ultrasonic condition lasts for 10-30 hours.

7. The method for synthesizing carbon-carbon bonds catalyzed by palladium as described in claim 1, characterized in that: After the reaction under ultrasonic condition, the method further comprises an extraction step and a purification step.

8. A palladium catalyzed synthesis method for forming carbon-carbon bonds according to claim 7, wherein, The extraction step is that the organic solvent and water are mixed for extraction, then the phases are separated to obtain an organic phase and an aqueous phase, and the organic phase is dried and concentrated to obtain a crude product.

9. A palladium catalyzed synthesis method for forming carbon-carbon bonds according to claim 7, wherein, The purification step is that the crude product obtained after extraction is purified by silica gel column chromatography, and the fraction containing the target product is concentrated to obtain the target product. ​ 10. The palladium catalyzed synthesis method for forming carbon-carbon bonds as claimed in claim 1, wherein: The reaction under ultrasonic condition is carried out at a temperature of 0-40℃.

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