A synthesis method for preparing cinnamaldehyde derivative functional molecules by using a "one-pot two-step" strategy

Abstract

This invention discloses a synthetic method for preparing cinnamaldehyde derivative functional molecules using a "one-pot, two-step" strategy. The method includes: under inert gas protection, mixing a bromovinyl type compound and an acetal-acetic acid type compound in a molar ratio of 1:2, adding a photocatalyst, a cobalt catalyst, and a base, dissolving in a solvent, and reacting under blue light irradiation at room temperature for 24–72 hours; after the reaction is complete, acidification deprotection, ethyl acetate extraction, vacuum distillation, and column chromatography separation are performed to obtain the cinnamaldehyde derivative functional molecules. This invention is based on a visible-light-catalyzed free radical coupling reaction, achieving alkenylation and deprotection in a tandem under mild conditions. It has advantages such as simple operation, high atom economy, low cost, mild reaction conditions, no violent oxidation process, no introduction of toxic heavy metals or malodorous raw materials, and easy separation and purification of the product. This method has a wide range of applicable substrates and can rapidly construct a diverse library of cinnamaldehyde derivative molecules, providing raw material preparation solutions for fragrances, preservatives, and pharmaceuticals.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and functional molecule preparation technology, specifically relating to a synthetic method for preparing cinnamaldehyde derivative functional molecules using a "one-pot two-step" strategy. Background Technology

[0002] Cinnamaldehyde is a natural α,β-unsaturated aromatic aldehyde, primarily found in the essential oils of the bark of plants such as cinnamon and cassia. Since ancient times, cinnamon has been widely used in spices, food preservation, and traditional medicine. According to the *Compendium of Materia Medica*, cinnamon has effects such as "nourishing the spirit, improving complexion, promoting blood circulation, and warming the muscles and internal organs." Ancient Egyptians used cinnamon extracts to preserve mummies, representing an early, unintentional application of cinnamaldehyde's preservative properties. In the 19th century, French chemists first isolated cinnamaldehyde from cinnamon oil, and subsequently, Italian chemists achieved its artificial synthesis. Since the 20th century, scientific research has further confirmed that cinnamaldehyde and its derivatives possess broad-spectrum antibacterial, anti-inflammatory, antiviral, antioxidant, and antitumor biological activities.

[0003] Based on these characteristics, cinnamaldehyde and its derivatives have been widely used in multiple fields. In the food industry, cinnamaldehyde, due to its natural aroma and low toxicity, is recognized as a safe food additive by the US FDA and is commonly used in chewing gum, betel nuts, instant noodles, pastries, and other foods, enhancing aroma and providing antibacterial and preservative functions. In the daily chemical industry, cinnamaldehyde, due to its fragrance retention advantage, is often used as a flavoring additive in perfumes, soaps, detergents, and other products. In agriculture, cinnamaldehyde can be used as a green pesticide, mosquito repellent, and feed additive, not only attracting animals to eat but also preventing feed from becoming moldy for a long time without the need for additional preservatives. In the pharmaceutical field, modern medicine is actively exploring its enormous potential in anti-inflammatory, anti-diabetic, and anti-cancer applications. Furthermore, cinnamaldehyde derivatives are also used in everyday applications such as fruit and vegetable preservation, wood mold prevention, refrigerator deodorization, and insecticides.

[0004] Although cinnamaldehyde derivatives have broad application prospects, existing synthetic methods face many technical challenges that urgently need to be addressed. Currently reported synthetic routes mainly fall into the following categories:

[0005] (1) Classical aldol condensation route: Benzaldehyde and acetaldehyde are used as raw materials to undergo a condensation reaction under alkaline catalysis to generate cinnamaldehyde. This method is relatively common in industry, but the reaction conditions are relatively harsh, requiring the use of an excess of strong base, and the substrate applicability is narrow, making it difficult to introduce different substituents to construct a library of structurally diverse cinnamaldehyde derivatives.

[0006] (2) Wittig reaction route: α,β-unsaturated aldehyde structures are constructed by reacting phosphine ylides with aldehyde compounds. Although the product configuration is controllable, this method requires the use of equivalent organophosphine reagents, resulting in poor atom economy, generating a large amount of triphenylphosphine oxide byproducts, which are difficult to separate and purify, and are not conducive to large-scale production.

[0007] (3) Transition metal catalytic cross-coupling route: such as the Heck reaction and the Suzuki reaction, used to construct the cinnamaldehyde framework. This type of method usually requires high temperature, inert gas protection and expensive palladium catalysts, and some systems require the use of excess oxidant, so the reaction conditions are relatively harsh.

[0008] (4) Other methods: A few studies have reported methods using toxic heavy metal catalysts such as chromium, or introducing raw materials containing sulfur or other substances with destructive odors, which are not only unfriendly to the environment, but also have a negative impact on operators and product quality.

[0009] In summary, existing cinnamaldehyde derivative synthesis technologies suffer from the following drawbacks: ① Numerous reaction steps, cumbersome operation, and low overall yield; ② Narrow substrate applicability, making it difficult to rapidly prepare structurally diverse derivatives; ③ Harsh reaction conditions (high temperature, strong alkali, excess oxidant, etc.), resulting in high energy consumption; ④ Use of toxic heavy metal catalysts (such as chromium) or odorous raw materials (sulfur-containing compounds), which contradicts the principles of green chemistry; ⑤ Poor atom economy, numerous byproducts, and difficulties in product separation and purification. These problems severely restrict the in-depth development and large-scale application of cinnamaldehyde derivatives in fragrances, preservatives, and pharmaceuticals.

[0010] Therefore, developing a method for synthesizing cinnamaldehyde derivatives that is simple to operate, has mild reaction conditions, a wide range of applicable substrates, high atom economy, is environmentally friendly, and easy to separate and purify is of great significance for expanding its application in food additives, flavorings, pesticides, pharmaceuticals and other fields, and also provides a feasible technical solution for constructing a functional molecular library of cinnamaldehyde derivatives. Summary of the Invention

[0011] The purpose of this invention is to provide a synthetic method for preparing cinnamaldehyde derivative functional molecules using a "one-pot two-step" strategy, in order to overcome the shortcomings of existing technologies such as narrow substrate selection, long reaction time, low enantioselectivity, need for excessive oxidant, and introduction of toxic heavy metals or malodorous raw materials.

[0012] This invention is based on a visible-light-catalyzed radical coupling reaction mechanism. Under blue light irradiation, the photocatalyst is excited to an excited state and reacts with deprotonated acetal acetate ions via a single-electron transfer (SET) process, converting them into acetal radicals. Simultaneously, a bromovinyl compound, activated by a cobalt catalyst, undergoes a coupling reaction with the aforementioned acetal radical, achieving alkenylation. Notably, the addition of the cobalt catalyst significantly improves the feed conversion rate and product yield; without the cobalt catalyst, the reaction can proceed via another pathway, but the conversion rate and yield are lower. Subsequently, after acidification and deprotection, the acetal group is converted into an aldehyde group, ultimately yielding a cinnamaldehyde derivative functional molecule. This "one-pot, two-step" strategy tandemly performs the coupling reaction and deprotection step, eliminating the need for intermediate separation, simplifying the operation, and offering high atom economy.

[0013] The reaction process of this invention is as follows:

[0014]

[0015] To achieve the above objectives, the present invention adopts the following technical solution:

[0016] A synthetic method for preparing cinnamaldehyde derivative functional molecules using a "one-pot two-step" strategy includes the following steps:

[0017] (1) Under the protection of an inert gas, the bromovinyl type compound and the acetal acetic acid type compound were mixed in a molar ratio of 1:2, and a photocatalyst, a cobalt catalyst and a base were added. The mixture was dissolved in a solvent and irradiated with blue light at room temperature for 24 to 72 hours.

[0018] (2) After the reaction is completed, add 1-10 M hydrochloric acid aqueous solution for acidification and deprotection for 0.5-4 hours. Then extract with ethyl acetate, combine the organic phases, wash, dry, filter, concentrate under reduced pressure, and finally separate by column chromatography using petroleum ether-ethyl acetate mixed solvent as eluent to obtain cinnamaldehyde derivative functional molecules.

[0019] In the above synthetic method, the general chemical formula of the bromovinyl type compound is:

[0020]

[0021] R is selected from one or more of hydrogen, chlorine, phenyl, fluorine, methoxy, bromine, methyl, trifluoromethoxy, trifluoromethyl, acetoxy, dichlorodisubstituted, difluorodisubstituted, dimethoxydisubstituted, fluorobrominedisubstituted, trimethoxypolysubstituted, fluorochlorodisubstituted, trifluoropolysubstituted, piperidine, biphenyl, naphthalene, or thiophene.

[0022] In the above synthesis method, the general chemical formula of the acetal-acetic acid type compound is:

[0023]

[0024] R1 is either methyl or ethyl.

[0025] The photocatalyst is selected from [Ir(dF(CF3)ppy)2(5,5'-CF3)] 3- bby)]PF6, [Ir[dF(F)ppy]2(dCF3)]PF6, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, Ir(pt-Buppy)3, Mes-(10-Me)Acr + BF4 - , 4CzIPN, Mes-(10-Ph)Acr + BF4 - Mes-(t-Bu)Acr + BF4 - One or more of [Ir(dFFppy)2(dtbbpy)]PF6 and fac-Ir(ppy)3.

[0026] The cobalt catalyst is selected from one or more of Co(dmgH)2(DMPA)Cl, CoBr2, Co(II)Pc, Co(dmgH)2PyCl, Co(dmgH)2HCl2, Co(dmgH)(dmgH2)Cl2, Co(dmgH)2Py2PF6, and Co(II)TPP.

[0027] The alkali is selected from one or more of K2CO3, DMAP, Na2CO3, KOH, NaOH, Li2CO3, K4P2O7, K3PO4, DIPEA, Et3N, or DBU.

[0028] The solvent is selected from one or more of dimethyl sulfoxide, tetrahydrofuran, dimethylacetamide, acetonitrile, dichloromethane, trifluorotoluene, toluene, diethylene glycol dimethyl ether, N-methylpyrrolidone, or trichloromethane.

[0029] In this invention, some technical features can be further optimized:

[0030] Preferably, the molar ratio of the bromovinyl type compound to the acetal acetic acid type compound in step (1) is 1:2.

[0031] Preferably, the photocatalyst in step (1) is 4CzIPN.

[0032] Preferably, the cobalt catalyst in step (1) is Co(dmgH)2(DMPA)Cl.

[0033] Preferably, the alkali in step (1) is K3PO4.

[0034] Preferably, the solvent in step (1) is dimethyl sulfoxide.

[0035] Preferably, the reaction time in step (1) is based on the GC-MS detection results, and the reaction is terminated when the raw materials disappear or no longer decrease.

[0036] Preferably, the acidification and deprotection time in step (2) is determined based on the GC-MS detection results, and is based on the disappearance or no longer reduction of the raw material.

[0037] Preferably, the volume ratio of the petroleum ether-ethyl acetate mixed solvent in step (2) is 5:1 to 80:1.

[0038] Compared with the prior art, the synthesis method provided by the present invention has the following beneficial effects:

[0039] (1) Simple operation: The "one pot, two steps" strategy is adopted to carry out the coupling reaction and the deprotection step in series without intermediate separation, which simplifies the operation process.

[0040] (2) High atom economy: No excess oxidant is involved in the reaction process, there are few by-products, and the raw material utilization rate is high.

[0041] (3) Low cost: It uses visible light as energy, requires less photocatalyst and cobalt catalyst, and does not require expensive palladium metal or excessive strong base.

[0042] (4) Mild reaction conditions: The reaction is carried out at room temperature, normal pressure and blue light irradiation, avoiding high temperature, high pressure or strong oxidation conditions, with low energy consumption and good safety.

[0043] (5) Wide range of substrates: Bromovinyl compounds can be introduced with a variety of substituents (halogen, alkoxy, alkyl, trifluoromethyl, naphthalene ring, thiophene ring, etc.), which can quickly construct a functional molecular library of cinnamaldehyde derivatives with diverse structures.

[0044] (6) Green and environmentally friendly: It does not introduce toxic heavy metals such as chromium, and does not use raw materials containing sulfur or other harmful odors, which is in line with the concept of green chemistry.

[0045] (7) The product is easy to separate and purify: high-purity target products can be obtained by column chromatography, and the yield of some products can reach more than 85%.

[0046] The synthesis method provided by this invention offers a feasible technical solution for the wider application of cinnamaldehyde and its derivative functional molecules in the fields of fragrances, preservatives, and pharmaceuticals, and also provides a raw material preparation basis for the discovery and screening of novel functional molecules. Attached Figure Description

[0047] Figures 1 to 33 The proton nuclear magnetic resonance spectra of compounds C1 to C33 obtained in Examples 1 to 33 of this invention are respectively ( 1 (H NMR) image. Detailed Implementation

[0048] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to these embodiments. The raw materials and reagents used in the embodiments are all commercially available or prepared by known methods, and the photocatalysts, cobalt catalysts, etc., used can be obtained commercially or prepared according to literature methods. The structure of the product was confirmed by nuclear magnetic resonance (NMR) and mass spectrometry (MS).

[0049] Example 1

[0050] Cinnamaldehyde C1

[0051]

[0052] A magnetic flux, K3PO4 (53 mg, 0.25 mmol, 2.5 equiv), 4CzIPN (3 mg, 0.004 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (3 mg, 0.008 mmol, 8 mol%), and bromovinyl compound B1 (18 mg, 0.1 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (30 μL, 0.2 mmol, 2 equiv) and dimethyl sulfoxide (1 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.4 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 10 mL of H2O was added. The mixture was extracted with ethyl acetate (3 x 8 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.25, yielding the target product, a colorless oily liquid C1 (16 mg, 61% yield).

[0053] 1H NMR (400 MHz, Chloroform-d) δ 9.72 (d, J = 7.7 Hz, 1H), 7.59 –7.56 (m, 2H), 7.49 (d, J = 16.0 Hz, 1H), 7.44 (dd, J = 5.0, 1.9 Hz, 3H), 6.73(dd, J = 15.9, 7.7 Hz, 1H).

[0054] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.85, 152.92, 134.18, 131.43,129.28, 128.80, 128.65.

[0055] HRMS (ESI) m / z caled for C9H9O + [M+H] + : 133.0648; found: 133.0644.

[0056] Example 2

[0057] 4-Chlorocinnamaldehyde C2

[0058]

[0059] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B2 (44 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R.f =0.3, yielding the target product, pale yellow solid C2 (18.3 mg, 55% yield).

[0060] 1 H NMR (400 MHz, Chloroform-d) δ 9.70 (d, J = 7.6 Hz, 1H), 7.52 –7.48 (m, 2H), 7.46 – 7.41 (m, 2H), 7.40 (d, J = 4.1 Hz, 1H), 6.69 (dd, J =16.0, 7.6 Hz, 1H).

[0061] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.50, 151.17, 137.43, 132.64,129.75, 129.58, 129.11.

[0062] HRMS (ESI) m / z caled for C9H8ClO + [M+H] + : 167.0258; found: 167.0261.

[0063] Example 3

[0064] 4-Phenylacetaldehyde C3

[0065]

[0066] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B3 (52 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, and the target product, pale yellow solid powder C3 (7 mg, 17% yield), was obtained.

[0067] 1 H NMR (400 MHz, Chloroform-d) δ 9.73 (d, J = 7.7 Hz, 1H), 7.69 –7.61 (m, 6H), 7.52 (d, J = 16.0 Hz, 1H), 7.50 – 7.45 (m, 2H), 7.44 – 7.37 (m,1H), 6.77 (dd, J = 15.9, 7.7 Hz, 1H).

[0068] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.80, 152.42, 144.21, 140.03,133.09, 129.17, 129.12, 128.59, 128.25, 127.87, 127.22.

[0069] HRMS (ESI) m / z caled for C 15 H 13 O + [M+H] +: 209.0961; found: 209.0959.

[0070] Example 4

[0071] 3,4-Dichlorocinnamaldehyde C4

[0072]

[0073] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B4 (50 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetalacetic acid A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.25, yielding the target product, pale yellow solid C4 (27 mg, 68% yield).

[0074] 1 H NMR (400 MHz, Chloroform-d) δ 9.71 (d, J = 7.5 Hz, 1H), 7.64 (d, J= 2.0 Hz, 1H), 7.51 (d, J = 8.3 Hz, 1H), 7.42 – 7.34 (m, 2H), 6.68 (dd, J =16.0, 7.5 Hz, 1H).

[0075] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.10, 149.52, 135.39, 134.13,133.72, 131.28, 130.18, 130.03, 127.35.

[0076] HRMS (ESI) m / z caled for C9H7Cl2O + [M+H] + : 200.9869; found: 200.9872.

[0077] Example 5

[0078] 3,4-Dioxomethylenecinnamaldehyde C5

[0079]

[0080] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B5 (45 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, and the target product, a pale yellow oily liquid C5 (5 mg, 14% yield), was obtained.

[0081] 1H NMR (400 MHz, Chloroform-d) δ 9.65 (d, J = 7.7 Hz, 1H), 7.37 (d, J= 15.8 Hz, 1H), 7.08 – 7.05 (m, 2H), 6.89 – 6.83 (m, 1H), 6.56 (dd, J = 15.8,7.7 Hz, 1H), 6.04 (s, 2H).

[0082] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.68, 152.69, 150.65, 148.74,128.68, 127.03, 125.41, 108.90, 106.94, 101.96.

[0083] HRMS (ESI) m / z caled for C 10 H9O3 + [M+H] + : 177.0546; found: 177.0547.

[0084] Example 6

[0085] 2-Fluorocinaldehyde C6

[0086]

[0087] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B6 (40 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.3, yielding the target product, a pale yellow oily liquid C6 (14 mg, 45% yield).

[0088] 1 H NMR (400 MHz, Chloroform-d) δ 9.72 (d, J = 7.6 Hz, 1H), 7.66 (d, J= 16.2 Hz, 1H), 7.59 (td, J = 7.6, 1.7 Hz, 1H), 7.46 – 7.39 (m, 1H), 7.21(td, J = 7.6, 1.2 Hz, 1H), 7.14 (ddd, J = 10.6, 8.2, 1.2 Hz, 1H), 6.79 (dd, J= 16.1, 7.7 Hz, 1H).

[0089] 19 F NMR (376 MHz, Chloroform-d) δ -114.27 (s, 1F).

[0090] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.94, 161.36 (d, J = 254.9Hz), 144.90 (d, J = 3.6 Hz), 133.01 (d, J = 9.0 Hz), 130.69 (d, J = 5.4 Hz), 128.93 (d, J = 2.4 Hz), 124.83 (d, J = 3.7 Hz), 122.32 (d, J = 11.5 Hz), 116.50 (d, J = 21.8 Hz).

[0091] HRMS (ESI) m / z caled for C9H8FO + [M+H] + : 151.0554; found: 151.0556.

[0092] Example 7

[0093] 2-Methoxycinnamaldehyde C7

[0094]

[0095] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B7 (42 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetalacetic acid A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a flow of argon gas for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.25, yielding the target product, a pale yellow oily liquid C7 (4 mg, C7, 13% yield).

[0096] 1 H NMR (400 MHz, Chloroform-d) δ 9.69 (d, J = 7.8 Hz, 1H), 7.84 (d, J= 16.1 Hz, 1H), 7.55 (dd, J = 7.7, 1.7 Hz, 1H), 7.41 (ddd, J = 8.3, 7.3, 1.7Hz, 1H), 7.00 (td, J = 7.6, 1.1 Hz, 1H), 6.95 (dd, J = 8.4, 1.0 Hz, 1H), 6.80 (dd, J = 16.1, 7.9 Hz, 1H), 3.92 (s, 3H).

[0097] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 194.73, 158.45, 148.35, 132.82,129.27, 129.03, 123.14, 121.03, 111.43, 55.72.

[0098] HRMS (ESI) m / z caled for C 10 H 11 O2 + [M+H] + : 163.0754; found: 163.0750.

[0099] Example 8

[0100] 2-Bromocinnamaldehyde C8

[0101]

[0102] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B8 (52 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetalacetic acid A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, and the target product, white solid C8 (12 mg, 30% yield), was obtained.

[0103] 1 H NMR (400 MHz, Chloroform-d) δ 9.77 (d, J = 7.7 Hz, 1H), 7.90 (d, J= 15.9 Hz, 1H), 7.66 (dt, J = 7.8, 1.5 Hz, 2H), 7.40 – 7.35 (m, 1H), 7.29(td, J = 7.7, 1.7 Hz, 1H), 6.67 (dd, J = 15.9, 7.7 Hz, 1H).

[0104] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.62, 150.73, 133.99, 133.81,132.28, 130.89, 128.18, 128.10, 125.88.

[0105] HRMS (ESI) m / z caled for C9H8BrO + [M+H] +: 210.9753; found: 210.9756.

[0106] Example 9

[0107] 2-Chlorocinnamaldehyde C9

[0108]

[0109] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B9 (44 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetalacetic acid A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 25:1 as the eluent R. f =0.4, yielding the target product, white solid C9 (23 mg, 70% yield).

[0110] 1 H NMR (400 MHz, Chloroform-d) δ 9.77 (d, J = 7.7 Hz, 1H), 7.94 (d, J= 16.0 Hz, 1H), 7.67 (dd, J = 7.6, 1.9 Hz, 1H), 7.47 (dd, J = 7.9, 1.5 Hz, 1H), 7.35 (dtd, J = 17.7, 7.4, 1.7 Hz, 2H), 6.71 (dd, J = 16.0, 7.7 Hz, 1H).

[0111] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.71, 148.12, 135.37, 132.26,132.14, 130.71, 130.52, 128.01, 127.47.

[0112] HRMS (ESI) m / z caled for C9H8ClO + [M+H] + : 167.0258; found: 167.0256.

[0113] Example 10

[0114] 3-(naphthalen-1-yl)acrylaldehyde C10

[0115]

[0116] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B10 (46 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 35:1 as the eluent R. f =0.25, yielding the target product, a pale yellow oily liquid C10 (8.3 mg, 23% yield).

[0117] 1H NMR (400 MHz, Chloroform-d) δ 9.87 (d, J = 7.7 Hz, 1H), 8.34 (d, J= 15.7 Hz, 1H), 8.22 – 8.18 (m, 1H), 7.99 – 7.89 (m, 2H), 7.83 (dt, J = 7.3,0.9 Hz, 1H), 7.65 – 7.51 (m, 3H), 6.85 (dd, J = 15.8, 7.7 Hz, 1H).

[0118] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.79, 149.47, 133.92, 131.78,131.36, 131.13, 131.10, 129.15, 127.44, 126.58, 125.89, 125.65, 122.94.

[0119] HRMS (ESI) m / z caled for C 13 H 11 O + [M+H] + : 183.0805; found: 183.0806.

[0120] Example 11

[0121] 2,6-Difluorocinnamaldehyde C11

[0122]

[0123] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B11 (44 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 35:1 as the eluent R. f =0.5, yielding the target product, white solid C11 (16 mg, 48% yield).

[0124] 1 H NMR (400 MHz, Chloroform-d) δ 9.71 (dt, J = 7.7, 1.1 Hz, 1H), 7.58 (d, J = 16.4 Hz, 1H), 7.38 (tt, J = 8.4, 6.3 Hz, 1H), 6.99 (q, J = 8.0 Hz,3H).

[0125] 19 F NMR (376 MHz, Chloroform-d) δ -109.52 (s, 2F).

[0126] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 194.52, 161.67 (dd, J = 256.8,6.4 Hz), 138.59 (t, J = 2.3 Hz), 134.17 (t, J = 8.3 Hz), 132.50 (t, J = 11.1Hz), 113.84 – 113.17 (m), 112.51 – 111.86 (m).

[0127] HRMS (ESI) m / z caled for C9H7F2O + [M+H] + : 169.0460; found: 169.0457.

[0128] Example 12

[0129] 2,5-Dimethoxycinnamonaldehyde C12

[0130]

[0131] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B12 (48 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 35:1 as the eluent R. f =0.25, yielding the target product, a yellow oily liquid C12 (22 mg, 58% yield).

[0132] 1H NMR (400 MHz, Chloroform-d) δ 9.69 (d, J = 7.8 Hz, 1H), 7.83 (d, J= 16.1 Hz, 1H), 7.07 (d, J = 3.0 Hz, 1H), 6.98 (dd, J = 9.0, 3.1 Hz, 1H), 6.88 (d, J = 9.0 Hz, 1H), 6.75 (dd, J = 16.1, 7.8 Hz, 1H), 3.87 (s, 3H), 3.80(s, 3H).

[0133] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 194.56, 153.71, 152.94, 147.96,129.27, 123.59, 118.66, 113.07, 112.69, 56.24, 55.95.

[0134] HRMS (ESI) m / z caled for C 11 H 13 O3 + [M+H] + : 193.0859; found: 193.0857.

[0135] Example 13

[0136] 2-Methylcinnamaldehyde C13

[0137]

[0138] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B13 (39 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 35:1 as the eluent R. f =0.3, yielding the target product, a pale yellow oily liquid C13 (15 mg, 50% yield).

[0139] 1 H NMR (400 MHz, Chloroform-d) δ 9.73 (d, J = 7.7 Hz, 1H), 7.78 (d, J= 15.8 Hz, 1H), 7.61 – 7.57 (m, 1H), 7.33 (td, J = 7.1, 6.7, 1.4 Hz, 1H), 7.28 – 7.23 (m, 2H), 6.67 (dd, J = 15.8, 7.7 Hz, 1H), 2.48 (s, 3H).

[0140] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.98, 150.39, 138.07, 132.98,131.21, 131.17, 129.78, 126.99, 126.75, 19.89.

[0141] HRMS (ESI) m / z caled for C 10 H 11 O +[M+H] + : 147.0805; found: 147.0806.

[0142] Example 14

[0143] 3-Bromo-4-fluorocinnamaldehyde C14

[0144]

[0145] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B14 (56 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 35:1 as the eluent R. f =0.3, yielding the target product, a yellow oily liquid C14 (10 mg, 22% yield).

[0146] 1 H NMR (500 MHz, Chloroform-d) δ 9.69 (d, J = 7.5 Hz, 1H), 7.77 (dd,J = 6.5, 2.2 Hz, 1H), 7.50 (ddd, J = 8.5, 4.6, 2.2 Hz, 1H), 7.37 (d, J = 16.0Hz, 1H), 7.19 (t, J = 8.3 Hz, 1H), 6.64 (dd, J = 16.0, 7.5 Hz, 1H).

[0147] 19F NMR (471 MHz, Chloroform-d) δ -102.27 (s, 1F).

[0148] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.11, 160.73 (d, J = 253.8Hz), 149.61, 133.70, 131.91 (d, J = 4.1 Hz), 129.50 (d, J = 2.3 Hz), 129.19(d, J = 7.9 Hz), 117.40 (d, J = 23.0 Hz), 110.32 (d, J = 21.8 Hz).

[0149] HRMS (ESI) m / z caled for C9H7BrFO + [M+H] + : 228.9659; found: 228.9658.

[0150] Example 15

[0151] 4-Bromocinnamaldehyde C15

[0152]

[0153] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B15 (52 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, pale yellow solid C15 (31 mg, 74% yield).

[0154] 1 H NMR (400 MHz, Chloroform-d) δ 9.71 (d, J = 7.6 Hz, 1H), 7.60 –7.53 (m, 2H), 7.44 (d, J = 2.3 Hz, 2H), 7.41 (d, J = 10.0 Hz, 1H), 6.70 (dd,J = 16.0, 7.6 Hz, 1H).

[0155] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.49, 151.22, 133.06, 132.56,129.92, 129.19, 125.84.

[0156] HRMS (ESI) m / z caled for C9H8BrO + [M+H] + : 210.9753; found: 210.9752.

[0157] Example 16

[0158] 3-(thiophen-2-yl)acrylaldehyde C16

[0159]

[0160] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B16 (38 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.5, yielding the target product, a yellow oily liquid C16 (13.5 mg, 49% yield).

[0161] 1 H NMR (500 MHz, Chloroform-d) δ 9.63 (d, J = 7.7 Hz, 1H), 7.59 (d, J= 15.6 Hz, 1H), 7.51 (dt, J = 5.1, 1.0 Hz, 1H), 7.37 (d, J = 3.7 Hz, 1H), 7.12 (dd, J = 5.1, 3.7 Hz, 1H), 6.52 (dd, J = 15.6, 7.7 Hz, 1H).

[0162] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.02, 144.52, 139.45, 132.18,130.52, 128.67, 127.56.

[0163] HRMS (ESI) m / z caled for C7H7OS + [M+H] + : 139.0212; found: 139.0214.

[0164] Example 17

[0165] 3,4-Difluorocinnamaldehyde C17

[0166]

[0167] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B17 (44 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, pale yellow solid C17 (5 mg, 15% yield).

[0168] 1 H NMR (400 MHz, Chloroform-d) δ 9.70 (d, J = 7.5 Hz, 1H), 7.42 –7.36 (m, 2H), 7.34 – 7.30 (m, 1H), 7.23 (dt, J = 9.7, 8.1 Hz, 1H), 6.63 (dd,J = 16.1, 7.5 Hz, 1H).

[0169] 19F NMR (376 MHz, Chloroform-d) δ -132.29 (d, J = 20.6 Hz, 1F), -135.90 (d, J = 20.9 Hz, 1F).

[0170] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.14, 152.19 (dd, J = 255.5,12.9 Hz), 150.44 (dd, J = 256.54, 13.13 Hz), 149.99 (t, J = 2.2 Hz), 129.53(d, J = 2.4 Hz), 125.39 (dd, J = 6.7, 3.4 Hz), 118.29 (d, J = 17.8 Hz), 116.95 (d, J = 17.8 Hz).

[0171] HRMS (ESI) m / z caled for C9H7F2O + [M+H] + : 169.0460; found: 169.0457.

[0172] Example 18

[0173] 4-Trifluoromethoxycinnamaldehyde C18

[0174]

[0175] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B18 (53 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, a pale yellow oily liquid C18 (32 mg, 73% yield).

[0176] 1 H NMR (500 MHz, Chloroform-d) δ 9.72 (d, J = 7.6 Hz, 1H), 7.62 –7.59 (m, 2H), 7.46 (d, J = 15.9 Hz, 1H), 7.28 (d, J = 8.3 Hz, 2H), 6.69 (dd,J = 16.0, 7.6 Hz, 1H).

[0177] 19 F NMR (471 MHz, Chloroform-d) δ -57.72 (s, 3F).

[0178] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.42, 151.22 (q, J = 1.8 Hz), 150.75, 132.69, 130.12, 129.43, 121.47 – 121.31 (m), 120.25 (q, J = 127.7Hz).

[0179] HRMS (ESI) m / z caled for C 10 H8F3O2 + [M+H] + : 217.0471; found: 217.0470.

[0180] Example 19

[0181] 4-Bromo-2-fluorocinnamaldehyde C19

[0182]

[0183] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B19 (56 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.4, yielding the target product, white solid C19 (17 mg, 38% yield).

[0184] 1 H NMR (500 MHz, Chloroform-d) δ 9.76 (d, J = 7.6 Hz, 1H), 7.83 (d, J= 15.9 Hz, 1H), 7.66 (dd, J = 8.8, 5.8 Hz, 1H), 7.41 (dd, J = 8.1, 2.6 Hz, 1H), 7.11 (td, J = 8.5, 2.6 Hz, 1H), 6.62 (dd, J = 16.0, 7.6 Hz, 1H).

[0185] 19 F NMR (471 MHz, Chloroform-d) δ -106.50 (s, 1F).

[0186] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.36, 163.72 (d, J = 257.0Hz), 149.38, 130.66, 130.39 (d, J = 3.5 Hz), 129.47 (d, J = 9.0 Hz), 126.28(d, J = 9.8 Hz), 121.10 (d, J = 24.5 Hz), 115.79 (d, J = 21.8 Hz).

[0187] HRMS (ESI) m / z caled for C9H7BrFO + [M+H] + : 228.9659; found: 228.9660.

[0188] Example 20

[0189] 2,3,4-Trimethoxycinnamaldehyde C20

[0190]

[0191] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B20 (54 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 10:1 as the eluent R. f =0.2, yielding the target product, pale yellow solid C20 (7.4 mg, 17% yield).

[0192] 1 H NMR (400 MHz, Chloroform-d) δ 9.67 (d, J = 7.8 Hz, 1H), 7.72 (d, J= 16.0 Hz, 1H), 7.32 (d, J = 8.8 Hz, 1H), 6.74 – 6.71 (m, 1H), 6.72 – 6.66(m, 1H), 3.96 (s, 3H), 3.91 (s, 3H), 3.88 (s, 3H).

[0193] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 194.44, 156.62, 153.50, 147.99,142.46, 127.81, 123.57, 121.19, 107.87, 61.69, 61.06, 56.27.

[0194] HRMS (ESI) m / z caled for C 12 H 15 O4 +[M+H] + : 223.0965; found: 223.0968.

[0195] Example 21

[0196] 3-Fluorocinaldehyde C21

[0197]

[0198] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B21 (40 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a flow of argon for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.3, yielding the target product, a pale yellow oily liquid C21 (10 mg, 34% yield).

[0199] 1 H NMR (400 MHz, Chloroform-d) δ 9.72 (d, J = 7.6 Hz, 1H), 7.47 –7.40 (m, 2H), 7.35 (dt, J = 7.8, 1.3 Hz, 1H), 7.29 – 7.21 (m, 1H), 7.15 (tdd,J = 8.3, 2.6, 1.1 Hz, 1H), 6.70 (dd, J = 16.0, 7.6 Hz, 1H).

[0200] 19F NMR (376 MHz, Chloroform-d) δ -111.97 (s, 1F).

[0201] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.47, 163.20 (d, J = 247.3Hz), 151.12 (d, J = 2.8 Hz), 136.35 (d, J = 7.2 Hz), 130.86 (d, J = 8.2 Hz), 129.80, 124.54 (d, J = 3.1 Hz), 118.26 (d, J = 21.4 Hz), 114.88 (d, J = 21.9Hz).

[0202] HRMS (ESI) m / z caled for C9H8FO + [M+H] + : 151.0554; found: 151.0553.

[0203] Example 22

[0204] 2,5-Difluorocinnamaldehyde C22

[0205]

[0206] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B22 (44 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.45, yielding the target product, white solid C22 (4 mg, 12% yield).

[0207] 1 H NMR (400 MHz, Chloroform-d) δ 9.73 (d, J = 7.5 Hz, 1H), 7.60 (dd,J = 16.1, 1.2 Hz, 1H), 7.29 – 7.24 (m, 1H), 7.12 (td, J = 6.1, 1.7 Hz, 2H),6.74 (dd, J = 16.2, 7.6 Hz, 1H).

[0208] 19 F NMR (376 MHz, Chloroform-d) δ -117.55 (d, J = 18.2 Hz, 1F), -120.17 (d, J = 17.2 Hz, 1F).

[0209] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.31, 158.75 (dd, J = 244.1,2.7 Hz), 157.19 (dd, J = 251.0, 2.1 Hz), 143.18 (t, J = 2.8 Hz), 131.30 (d, J= 5.0 Hz), 123.34 (dd, J = 14.2, 7.8 Hz), 119.38 (dd, J = 24.5, 9.0 Hz), 117.61 (dd, J = 24.9, 8.5 Hz), 114.43 (dd, J = 24.7, 3.0 Hz).

[0210] HRMS (ESI) m / z caled for C9H7F2O + [M+H] + : 169.0460; found: 169.0457.

[0211] Example 23

[0212] 3-Bromocinnamaldehyde C23

[0213]

[0214] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B23 (52 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f=0.2, and the target product, yellow oily liquid C23 (19 mg, 45% yield), was obtained.

[0215] 1 H NMR (500 MHz, Chloroform-d) δ 9.71 (d, J = 7.5 Hz, 1H), 7.71 (t, J= 1.8 Hz, 1H), 7.57 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.49 (dt, J = 7.7, 1.3Hz, 1H), 7.40 (d, J = 15.9 Hz, 1H), 7.31 (t, J = 7.9 Hz, 1H), 6.70 (dd, J =16.0, 7.6 Hz, 1H).

[0216] 13 C{ 1 H} NMR (126 MHz, Chloroform-d) δ 193.37, 150.78, 136.19, 134.12,131.37, 130.74, 129.82, 127.05, 123.38.

[0217] HRMS (ESI) m / z caled for C9H8BrO + [M+H] + : 210.9753; found: 210.9750.

[0218] Example 24

[0219] 4-Fluorocinaldehyde C24

[0220]

[0221] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B24 (40 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 80:1 as the eluent R. f =0.2, and the target product, colorless oily liquid C24 (9 mg, 28% yield), was obtained.

[0222] 1 H NMR (400 MHz, Chloroform-d) δ 9.72 (d, J = 7.6 Hz, 1H), 7.46 –7.39 (m, 2H), 7.35 (d, J = 7.8 Hz, 1H), 7.28 – 7.23 (m, 1H), 7.19 – 7.10 (m,1H), 6.70 (dd, J = 16.0, 7.6 Hz, 1H).

[0223] 19 F NMR (471 MHz, Chloroform-d) δ -111.97 (s, 1F).

[0224] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.45, 163.20 (d, J = 247.7Hz), 151.10 (d, J = 2.7 Hz), 130.85 (d, J = 8.3 Hz), 129.80, 124.54 (d, J =2.8 Hz), 118.26 (d, J = 21.4 Hz).

[0225] HRMS (ESI) m / z caled for C9H8FO + [M+H] + : 151.0554; found: 151.0552.

[0226] Example 25

[0227] 2-Chloro-6-fluorocinnamaldehyde C25

[0228]

[0229] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B25 (47 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 80:1 as the eluent R. f =0.4, yielding the target product, white solid C25 (12 mg, 33% yield).

[0230] 1H NMR (400 MHz, Chloroform-d) δ 9.74 (dd, J = 7.7, 1.9 Hz, 1H), 7.71 (d, J = 16.4 Hz, 1H), 7.36 – 7.28 (m, 2H), 7.09 (ddd, J = 10.7, 7.5, 2.0 Hz,1H), 6.98 (ddd, J = 16.3, 7.6, 1.1 Hz, 1H).

[0231] 19 F NMR (376 MHz, Chloroform-d) δ -106.47 (s, 1F).

[0232] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 194.54, 162.13 (d, J = 258.3Hz), 142.53 (d, J = 1.9 Hz), 136.20 (d, J = 5.0 Hz), 135.00 (d, J = 14.0 Hz), 131.94 (d, J = 10.5 Hz), 126.31 (d, J = 3.5 Hz), 121.39 (d, J = 13.9 Hz), 115.29 (d, J = 23.1 Hz).

[0233] HRMS (ESI) m / z caled for C9H7ClFO + [M+H] + : 185.0164; found: 185.0161.

[0234] Example 26

[0235] 3,4,5-Trimethoxycinnamoaldehyde C26

[0236]

[0237] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B26 (54 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 10:1 as the eluent R. f =0.2, yielding the target product, a colorless oily liquid C26 (10.1 mg, 23% yield).

[0238] 1 H NMR (400 MHz, Chloroform-d) δ 9.68 (d, J = 7.7 Hz, 1H), 7.40 (d, J= 15.8 Hz, 1H), 6.79 (s, 2H), 6.64 (dd, J = 15.8, 7.7 Hz, 1H), 3.90 (s, 9H).

[0239] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.54, 153.70, 152.83, 141.12,129.59, 128.11, 105.86, 61.16, 56.36.

[0240] HRMS (ESI) m / z caled for C 12 H 15 O4 + [M+H] + : 223.0965; found: 223.0962.

[0241] Example 27

[0242] 3-(naphthalen-2-yl)acrylaldehyde C27

[0243]

[0244] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B27 (46 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by passing an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, pale yellow solid C27 (9.3 mg, 26% yield).

[0245] 1 H NMR (400 MHz, Chloroform-d) δ 9.77 (d, J = 7.7 Hz, 1H), 8.01 –7.99 (m, 1H), 7.91 – 7.85 (m, 3H), 7.69 (dd, J = 8.7, 1.8 Hz, 1H), 7.65 (d, J= 16.0 Hz, 1H), 7.59 – 7.52 (m, 2H), 6.84 (dd, J = 15.9, 7.7 Hz, 1H).

[0246] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.82, 152.92, 134.80, 133.36,131.72, 130.85, 129.15, 128.92, 128.90, 128.03, 127.98, 127.13, 123.69.

[0247] HRMS (ESI) m / z caled for C 13 H 11 O + [M+H] + : 183.0805; found: 183.0801.

[0248] Example 28

[0249] 4-Trifluoromethylcinnamaldehyde C28

[0250]

[0251] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B28 (50 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a flow of argon for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, a pale yellow oily liquid C28 (16 mg, 40% yield).

[0252] 1H NMR (400 MHz, Chloroform-d) δ 9.75 (d, J = 7.5 Hz, 1H), 7.69 (d, J = 1.9 Hz, 4H), 7.51 (d, J = 16.0 Hz, 1H), 6.78 (dd, J = 16.0, 7.5 Hz, 1H).

[0253] 19 F NMR (376 MHz, Chloroform-d) δ -63.01 (s, 3F).

[0254] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.29, 150.40, 137.46 (d, J =1.3 Hz), 132.75 (q, J = 32.5 Hz), 130.69, 128.72, 126.24 (q, J = 3.9 Hz),120.84 (q, J = 291.3 Hz).

[0255] HRMS (ESI) m / z caled for C 10 H8F3O + [M+H] + : 201.0522; found: 201.0520.

[0256] Example 29

[0257] 3-Trifluoromethylcinnamaldehyde C29

[0258]

[0259] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B29 (50 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, a pale yellow oily liquid C29 (19 mg, 48% yield).

[0260] 1 H NMR (400 MHz, Chloroform-d) δ 9.75 (d, J = 7.5 Hz, 1H), 7.81 –7.74 (m, 2H), 7.73 – 7.67 (m, 1H), 7.58 (t, J = 7.8 Hz, 1H), 7.51 (d, J =16.1 Hz, 1H), 6.77 (dd, J = 16.0, 7.5 Hz, 1H).

[0261] 19 F NMR (376 MHz, Chloroform-d) δ -62.98 (s, 3F).

[0262] 13 C{ 1H} NMR (101 MHz, Chloroform-d) δ 193.25, 150.49, 134.94, 131.90(q, J = 33.1 Hz), 131.34, 130.19, 129.86, 127.71 (q, J = 3.7 Hz), 125.31 (q,J = 3.6 Hz), 125.20 – 119.27 (m).

[0263] HRMS (ESI) m / z caled for C 10 H8F3O + [M+H] + : 201.0522; found: 201.0525.

[0264] Example 30

[0265] 4-Acetoxycinnamaldehyde C30

[0266]

[0267] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B30 (48 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.3, yielding the target product, a pale yellow oily liquid C30 (5 mg, 12% yield).

[0268] 1H NMR (400 MHz, Chloroform-d) δ 9.70 (d, J = 7.7 Hz, 1H), 7.61 –7.57 (m, 2H), 7.46 (d, J = 15.9 Hz, 1H), 7.21 – 7.15 (m, 2H), 6.68 (dd, J =15.9, 7.6 Hz, 1H), 2.33 (s, 3H).

[0269] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.66, 169.16, 152.98, 151.64,131.86, 129.84, 128.85, 122.56, 21.29.

[0270] Example 31

[0271] 3,4,5-Trifluorocinnamaldehyde C31

[0272]

[0273] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B31 (47 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by purging with an argon gas stream for 5 minutes and then sealed. The mixture was irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, and the target product, colorless oily liquid C31 (5 mg, 13% yield), was obtained.

[0274] 1H NMR (400 MHz, Chloroform-d) δ 9.71 (d, J = 7.4 Hz, 1H), 7.32 (d, J= 15.9 Hz, 1H), 7.20 (dd, J = 8.0, 6.5 Hz, 2H), 6.62 (dd, J = 15.9, 7.4 Hz,1H).

[0275] 19 F NMR (376 MHz, Chloroform-d) δ -132.42, -132.48, -154.86 (d, J =20.1 Hz).

[0276] HRMS (ESI) m / z caled for C9H6F3O + [M+H] + : 187.0365; found: 187.0368.

[0277] Example 32

[0278] 3,4-Dimethoxycinnamonaldehyde C32

[0279]

[0280] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B32 (48 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 × 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 10:1 as the eluent R. f=0.2, yielding the target product, a yellow oily liquid C32 (11 mg, 29% yield).

[0281] 1 H NMR (400 MHz, Chloroform-d) δ 9.66 (d, J = 7.7 Hz, 1H), 7.41 (d, J= 15.8 Hz, 1H), 7.16 (dd, J = 8.3, 2.0 Hz, 1H), 7.08 (d, J = 2.0 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 6.61 (dd, J = 15.8, 7.7 Hz, 1H), 3.93 (s, 3H), 3.93(s, 3H).

[0282] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.74, 153.01, 152.14, 149.53,127.19, 126.85, 123.59, 111.27, 110.01, 56.18, 56.08.

[0283] Example 33

[0284] 3-Chlorocinnamaldehyde C33

[0285]

[0286] A magnetic flux, K3PO4 (106 mg, 0.5 mmol, 2.5 equiv), 4CzIPN (6 mg, 0.008 mmol, 4 mol%), Co(dmgH)2(DMPA)Cl (7 mg, 0.016 mmol, 8 mol%), and bromovinyl compound B33 (43 mg, 0.2 mmol, 1.0 equiv) were added to a dry 10 mL reaction tube. Then, 2,2-diethoxyacetal acetate A (60 μL, 0.4 mmol, 2 equiv) and dimethyl sulfoxide (2 mL) were added under an argon atmosphere. The mixture was degassed by a 5-minute argon gas flow and sealed. The mixture was then irradiated with a blue LED lamp and stirred at room temperature for 24–72 h; the specific reaction time was determined based on GC-MS and TLC results. After the reaction was complete, 0.8 mL of 3.0 M HCl was added to quench the reaction, and the mixture was stirred for 1–5 h. Then, 20 mL of H2O was added. The mixture was extracted with ethyl acetate (3 x 15 mL), the organic phases were combined, washed with water and saturated NaCl aqueous solution, dried over anhydrous Na2SO4, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography using PE:EA = 40:1 as the eluent R. f =0.2, yielding the target product, a yellow oily liquid C33 (28 mg, 85% yield).

[0287] 1 H NMR (400 MHz, Chloroform-d) δ 9.72 (d, J = 7.6 Hz, 1H), 7.55 (t, J= 1.9 Hz, 1H), 7.47 – 7.42 (m, 2H), 7.41 – 7.35 (m, 2H), 6.71 (dd, J = 16.0,7.6 Hz, 1H).

[0288] 13 C{ 1 H} NMR (101 MHz, Chloroform-d) δ 193.42, 150.90, 135.94, 135.35, 131.22, 130.50, 129.83, 128.41, 126.64.

Claims

1. A synthetic method for preparing cinnamaldehyde derivative functional molecules using a "one-pot two-step" strategy, characterized in that, Includes the following steps: (1) Under the protection of an inert gas, the bromovinyl type compound and the acetal acetic acid type compound are mixed in a molar ratio of 1:1 to 1:3, and a photocatalyst, a cobalt catalyst and a base are added. The mixture is dissolved in a solvent and irradiated with blue light at room temperature for 24 to 72 hours. (2) After the reaction is complete, add 1-10 M hydrochloric acid aqueous solution for acidification and deprotection for 0.5-4 hours. Then extract with ethyl acetate, combine the organic phases, wash, dry, filter, concentrate under reduced pressure, and finally separate by column chromatography using petroleum ether-ethyl acetate mixed solvent as eluent to obtain cinnamaldehyde derivative functional molecules.

2. The synthesis method according to claim 1, characterized in that, The photocatalyst mentioned in step (1) is 4CzIPN, or selected from [Ir(dF(CF3)ppy)2(5,5'-CF 3- bby)]PF6, [Ir[dF(F)ppy]2(dCF3)]PF6, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6, Ir(pt-Buppy)3, Mes-(10-Me)Acr + BF4 - Mes-(10-Ph)Acr + BF4 - Mes-(t-Bu)Acr + BF4 - One or more of [Ir(dFFppy)2(dtbbpy)]PF6 and fac-Ir(ppy)3.

3. The synthesis method according to claim 1, characterized in that, The cobalt catalyst mentioned in step (1) is Co(dmgH)2(DMPA)Cl, or one or more selected from CoBr2, Co(II)Pc, Co(dmgH)2PyCl, Co(dmgH)2HCl2, Co(dmgH)(dmgH2)Cl2, Co(dmgH)2Py2PF6, and Co(II)TPP.

4. The synthesis method according to claim 1, characterized in that, The base mentioned in step (1) is K3PO4, or selected from one or more of K2CO3, DMAP, Na2CO3, KOH, NaOH, Li2CO3, K4P2O7, DIPEA, Et3N, and DBU; the solvent is dimethyl sulfoxide, or selected from one or more of tetrahydrofuran, dimethylacetamide, acetonitrile, dichloromethane, trifluorotoluene, toluene, diethylene glycol dimethyl ether, N-methylpyrrolidone, and chloroform.

5. The synthesis method according to claim 1, characterized in that, The general chemical formula of the bromovinyl type compound mentioned in step (1) is: R is selected from one or more of hydrogen, chlorine, phenyl, fluorine, methoxy, bromine, methyl, trifluoromethoxy, trifluoromethyl, acetoxy, dichlorodisubstituted, difluorodisubstituted, dimethoxydisubstituted, fluorobrominedisubstituted, trimethoxypolysubstituted, fluorochlorodisubstituted, trifluoropolysubstituted, piperidine, biphenyl, naphthalene, or thiophene.

6. The synthesis method according to claim 1, characterized in that, The general chemical formula of the acetal-acetic acid type compound mentioned in step (1) is: R1 is either methyl or ethyl.

7. The synthesis method according to claim 1, characterized in that, The volume ratio of the petroleum ether-ethyl acetate mixed solvent in step (2) is 5:1 to 80:

1.

8. The cinnamaldehyde derivative functional molecule prepared by the synthetic method according to any one of claims 1-7, having the general chemical formula: R is selected from one or more of hydrogen, chlorine, phenyl, fluorine, methoxy, bromine, methyl, trifluoromethoxy, trifluoromethyl, acetoxy, dichlorodisubstituted, difluorodisubstituted, dimethoxydisubstituted, fluorobrominedisubstituted, trimethoxypolysubstituted, fluorochlorodisubstituted, trifluoropolysubstituted, piperidine, biphenyl, naphthalene, or thiophene.

9. The use of the cinnamaldehyde derivative functional molecule according to claim 8 in the preparation of fragrances, preservatives, food additives, pesticides or pharmaceuticals.

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