Method for breaking and forming tetravalent uranium photocatalytic carbon-carbon bond

Abstract

The divisional application provides a method for breaking and forming a tetravalent uranium photocatalytic carbon-carbon bond, which comprises the following steps: dissolving a tetravalent uranium catalyst with a molecular formula of L-U (NO3) 3 (OMe) in an organic solvent in an environment of-40 DEG C to 80 DEG C under the conditions of inert gas and blue light with a light source of 440-450 nm; and then adding olefin with a chemical structural formula shown in the specification and cyclic alcohol with a chemical structural formula shown in the specification for reaction to obtain a product. According to the forming method, tetravalent uranium serves as a photocatalyst, olefin which is almost not reacted originally reacts with cyclic alcohol with ring tension, the conversion rate of the reaction is increased, the conversion rate can reach 99% at most, and the excellent yield and the high atom economy are achieved.

Description

[0001] This invention is a divisional application. The original application number is 202311550884.3, the application date is November 20, 2023, and the invention title is "A method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium". Technical Field

[0002] This invention belongs to the fields of organic formation chemistry and organometallic chemistry, specifically to a method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium. Background Technology

[0003] The formation of carbon-carbon bonds is a crucial issue in modern formation chemistry. While transition metal-catalyzed CH functionalization has proven to be a powerful transformation strategy, C(sp...) 3 )-C(sp 3 The construction of chemical bonds remains a significant challenge. In recent decades, photoinduction has become an important tool in formation chemistry, characterized by high atom economy, good functional group compatibility, and high efficiency in chemical bond construction. Currently, most uranium catalysts in the literature are hexavalent uranium photocatalysts. Common hexavalent uranium photocatalysts are mainly used in biodegradation and environmental applications; there are no previously reported cases of tetravalent uranium acting as a photocatalyst for organic synthesis reactions. In existing technologies, alkenes and ring-strained cyclic alcohols hardly react under conventional reaction conditions. Therefore, to efficiently obtain the products of the reaction between alkenes and ring-strained cyclic alcohols, it is necessary to find a catalyst that can efficiently catalyze this reaction and control suitable reaction conditions.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The primary objective of this invention is to provide a method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium. This method enables alkenes that would otherwise hardly react to react with cyclic alcohols with ring strain, and improves the conversion rate of the reaction, which can reach up to 99%, while also exhibiting excellent yield and high atom economy.

[0006] To achieve the above-mentioned objectives of this invention, the following technical solution is adopted: A method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium, characterized by comprising the following steps: Under inert gas and ultraviolet-visible light of 300nm-760nm, a tetravalent uranium catalyst with the molecular formula LU(NO3)3(OMe) was dissolved in an organic solvent at an temperature of -40℃ to 80℃. Subsequently, an olefin and a ring-strained cyclic alcohol were added to react and give the product.

[0007] Preferably, as a further specific embodiment, the chemical structural formula of the olefin is as follows: or ; R 1 It is a terminal substituent of an olefin, and is any one of hydrogen atom, alkyl, aryl, heteroaryl, Ar, alkyl bromide, ester group, silyl ether or alkoxy group; R 2 It is a terminal substituent of an olefin, and can be any one of alkyl, aryl, or alkoxy. R 4 It is a substituent for olefins, and is any one of hydrogen atom, alkyl, aryl, alkoxy or ester group; R 5 It is a substituent for olefins, and is any one of hydrogen atom, alkyl, aryl, alkoxy or ester group; R 6 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; R 7 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; The chemical structural formula of the ring-strained cyclic alcohol is as follows: or ; R 3 The substituent on the cyclic alcohol can be either aryl or alkyl. X is a heteroatom on the cyclic alcohol, which can be any one of oxygen, nitrogen, sulfur or CH2. n' is the number of carbon atoms in the cyclic alcohol, which can be either zero or one; n is the number of carbon atoms in the cyclic alcohol, which can be any one of zero, one, two, three, four, five, six, nine, or twelve.

[0008] Preferably, as a further specific embodiment, the substituent on the aryl group in Ar is any one of hydrogen atom, fluorine atom, chlorine atom, bromine atom, alkoxy, cyano, nitro, or phenyl; Preferably, as a further specific embodiment, the heteroaryl group is any one of furan and thiophene; Preferably, as a further specific embodiment, the organic solvent is one or more selected from tetrahydrofuran, toluene, 1,2-dichloroethane, chloroform, acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylpropenylurea, N-methylpyrrolidone, trifluorotoluene, methanol, ethanol, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dimethyl sulfoxide.

[0009] Preferably, as a further specific embodiment, the light source is ultraviolet-visible light of 300nm-760nm, and more preferably, the light source is blue light of 440nm-450nm.

[0010] Preferably, as a further specific embodiment, the reaction temperature is -40℃ to 80℃, and more preferably, the reaction temperature is 18℃ to 35℃.

[0011] Preferably, as a further specific embodiment, the reaction under the light source irradiation lasts for 1 hour to 72 hours, and more preferably, the reaction time is 12 hours to 24 hours.

[0012] Preferably, as a further specific embodiment, the molar ratio of the tetravalent uranium catalyst to the reactants is greater than or equal to 1 mol%, and preferably, the molar ratio of the tetravalent uranium catalyst to the reactants is 5 mol%. Preferably, as a further specific embodiment, the molar ratio of tetravalent uranium catalyst: alcohol compound: olefin is (0.01-0.02):(0.2-0.3):(0.2-0.3).

[0013] Preferably, as a further specific embodiment, the tetravalent uranium catalyst has the molecular formula LU(NO3)3(OMe), wherein the L ligand is a pyridine ligand with coordination of... Any one of them.

[0014] The literature commonly uses hexavalent uranium to catalyze reactions, primarily for biodegradation and environmental applications. Previous reports lacked examples of tetravalent uranium as a photocatalyst for organic synthesis. Compared to conventional hexavalent uranium catalysts, the tetravalent uranium catalyst used in this invention generates a tetravalent cyclic alcohol intermediate during its formation. This intermediate confirms that the catalytic cycle of tetravalent uranium begins with the breaking of the hydroxyl bond, unlike the carbon-hydrogen bond breaking in hexavalent uranium catalysts. Essentially, this invention involves a charge transfer process on a metal-metal LMCT ligand, distinct from the hydrogen atom transfer process in hexavalent uranium catalysis. Therefore, the tetravalent uranium catalyst is compatible with the reactions of olefins and alcohols described in this invention. Under conventional reaction conditions, the reaction efficiency of the selected alcohols and olefins is extremely low, with almost no reaction occurring. This invention, through careful selection of reaction conditions and catalysts, ultimately enables the selected olefins and alcohols to react.

[0015] The preparation method used in this invention requires the reaction to be carried out in an inert gas environment. Since the olefins and alcohols used in the reaction are unstable in a non-inert gas environment, the olefins are prone to oxidation or addition reactions and deterioration, ultimately preventing the reaction from occurring. The reaction process requires ultraviolet-visible light in the 300nm-760nm range. Under irradiation with this light, the tetravalent uranium catalyst can be activated. The tetravalent uranium catalyst can convert the absorbed photon energy into chemical energy, ultimately breaking the chemical bonds and initiating the reaction. The selection of a pyridine ligand for the tetravalent uranium catalyst is crucial. Without a pyridine ligand, the tetravalent uranium catalyst lacks catalytic activity and the reaction cannot occur. Furthermore, terpyridine ligands can stabilize the tetravalent uranium catalyst, enabling it to catalyze the reaction stably. The alcohol selected in this invention is a ring-strained alcohol. Due to the ring strain, this alcohol is more prone to bond breaking and chemical reaction compared to other alcohols without ring strain. The reaction efficiency is highest when the molar ratio of the tetravalent uranium catalyst selected in this invention is greater than or equal to 1 mol% and the molar ratio of the tetravalent uranium catalyst to alcohols to olefins is (0.01-0.02):(0.2-0.3):(0.2-0.3).

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) This invention uses a tetravalent uranium catalyst. The ligand used can coordinate with metallic uranium and change the properties of uranium during the reaction, so that uranium reacts with alcohols. Under the condition of no other additives, it can enable cycloaddition reactions of cyclopropanol, cyclobutanol and other cycloalcohols with alkenes to produce cycloalcohol products with excellent yield and high atom economy. It has good tolerance to functional groups.

[0017]

[0018] Further research into the application of the substrates can lead to the formation of bridged epoxide imine compounds. .

[0019]

[0020] (2) The reaction method used in this invention, when the alcohol is a tertiary alcohol, the carbon-carbon bond is broken and then added to the acceptor to generate a chain ketone compound. The reaction conditions are mild, the yield is high, it is compatible with different types of substituents and functional groups, and it can participate in the reaction well for cyclic alcohols of different sizes. (3) The cyclic alcohols and chain ketones formed in this invention can achieve functional group transformation. At the same time, the obtained cyclic alcohols and chain ketones can be modified again to generate products with medicinal value, which are potential drug active molecules. Attached Figure Description

[0021] Figure 1 The H-spectrum formed in Examples 1-4; Figure 2 C-spectrums formed in Examples 1-4; Figure 3 H-spectrum of isomers formed in Examples 1-4; Figure 4 C-spectrum of the isomers formed in Examples 1-4; Figure 5 The H spectrum formed in Example 5; Figure 6 The C spectrum formed in Example 5; Figure 7 The H spectrum formed in Example 6; Figure 8 The C spectrum formed in Example 6; Figure 9 The H spectrum formed in Example 7; Figure 10 The C spectrum formed in Example 7; Figure 11 The H spectrum formed in Example 8; Figure 12 The C spectrum formed in Example 8; Figure 13 The H spectrum formed in Example 9; Figure 14 The C spectrum formed in Example 9; Figure 15 The H spectrum formed in Example 10; Figure 16 The C spectrum formed in Example 10; Figure 17 The H spectrum formed in Example 11; Figure 18 The C spectrum formed in Example 11; Figure 19 The H spectrum formed in Example 12; Figure 20 The C spectrum formed in Example 12; Figure 21 The H spectrum formed in Example 13; Figure 22 C spectrum formed in Example 13: Figure 23 The H spectrum formed in Example 14; Figure 24 C spectrum formed in Example 14: Figure 25 The H spectrum formed in Example 15; Figure 26 C spectrum formed in Example 15: Figure 27 The H spectrum formed in Example 16; Figure 28 The C spectrum formed in Example 16; Figure 29 The H spectrum formed in Example 17; Figure 30 The C spectrum formed in Example 17; Figure 31 : The structural model; Figure 32 : The H spectrum. Detailed Implementation

[0022] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0023] In the following embodiments, L refers to , LU(NO3)3(OMe) refers to MeCN refers to acetonitrile, and blue LEDs refers to blue LEDs.

[0024] Example 1 Case 1

[0025] In a nitrogen-filled glove box, cyclobutanol (0.4 mmol, 28.8 mg) and electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 96%). The NMR spectrum of the product is shown below. Figure 1-4 As shown.

[0026] Example 1 Case 2 Under unchanged experimental conditions, the reaction was placed under a purple LED lamp (wavelength 300nm-435nm) and irradiated at 25℃ for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product (colorless oil, yield 96%) was obtained by column chromatography purification. The nuclear magnetic resonance spectrum of the product is shown below. Figure 1-4 As shown.

[0027] Experimental Example 1, Case 3 With all other experimental conditions unchanged, the reaction was placed under a red LED lamp (wavelength 610nm-700nm) at 25℃ for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product (colorless oil, 95% yield) was obtained by column chromatography purification. The nuclear magnetic resonance spectrum of the product is shown below. Figure 1-4 As shown.

[0028] Example 2

[0029] In a nitrogen-filled glove box, cyclobutanol (0.4 mmol, 28.8 mg) and electron-deficient olefin (0.4 mmol, 68.9 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp at 25 °C for 12–24 hours. The reaction solvent was removed by vacuum concentration, and the target product (colorless oil, 95% yield) was purified by column chromatography. The NMR spectrum of the product is shown below. Figure 1-4 As shown.

[0030] Example 3 In a nitrogen-filled glove box, cyclobutanol (0.4 mmol, 28.8 mg) and electron-deficient olefin (0.4 mmol, 75.4 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 98%). The NMR spectrum of the product is shown below. Figure 1-4 As shown.

[0031] Example 4

[0032] In a nitrogen-filled glove box, cyclobutanol (0.4 mmol, 28.8 mg) and electron-deficient olefin (0.4 mmol, 79.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 91%). The NMR spectrum of the product is shown below. Figure 1-4 As shown.

[0033] Example 5

[0034] In a nitrogen-filled glove box, oxadiazon-3-ol (0.4 mmol, 29.6 mg) and electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 83%). The NMR spectrum of the product is shown below. Figure 5-6 As shown.

[0035] Example 6

[0036] In a nitrogen-filled glove box, 3-thiabutyronol (0.4 mmol, 36.0 mg) and electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 91%). The NMR spectrum of the product is shown below. Figure 7-8 As shown.

[0037] Example 7

[0038] In a nitrogen-filled glove box, N-Boc-3-hydroxyazacyclobutane (0.4 mmol, 69.3 mg) and electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 91%). The NMR spectrum of the product is shown below. Figure 9-10 As shown.

[0039] Example 8

[0040] In a nitrogen-filled glove box, cyclopropanol (0.4 mmol, 23.2 mg) and electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 99%). The NMR spectrum of the product is shown below. Figure 11-12 As shown.

[0041] Example 9

[0042] In a nitrogen-filled glove box, ethyl 1-hydroxycyclopropanecarboxylate (0.4 mmol, 52.0 mg) and an electron-deficient olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 89%). The NMR spectrum of the product is shown below. Figure 13-14 As shown.

[0043] Example 10

[0044] In a nitrogen-filled glove box, ethyl 1-hydroxycyclopropanecarboxylate (0.4 mmol, 85.3 mg) and an electron-deficient olefin (0.4 mmol, 92.1 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 55%). The NMR spectrum of the product is shown below. Figure 15-16 As shown.

[0045] Example 11

[0046] In a nitrogen-filled glove box, 1-phenylcyclobutanol (0.4 mmol, 59.3 mg) and an olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 88%). The NMR spectrum of the product is shown below. Figure 17-18 As shown.

[0047] Example 12

[0048] In a nitrogen-filled glove box, 1-phenylcyclobutanol (0.4 mmol, 59.3 mg) and an olefin (0.4 mmol, 67.3 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 81%). The NMR spectrum of the product is shown below. Figures 19-20 As shown.

[0049] Example 13

[0050] In a nitrogen-filled glove box, 1-phenylcyclobutanol (0.4 mmol, 59.3 mg) and an olefin (0.4 mmol, 57.6 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 85%). The NMR spectrum of the product is shown below. Figure 21-22 As shown.

[0051] Example 14

[0052] In a nitrogen-filled glove box, 1-phenylcyclopropanol (0.4 mmol, 53.7 mg) and an olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 95%). The NMR spectrum of the product is shown below. Figure 23-24 As shown.

[0053] Example 15

[0054] In a nitrogen-filled glove box, 3-phenylthion-3-ol (0.4 mmol, 66.5 mg) and an olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 88%). The NMR spectrum of the product is shown below. Figure 25-26 As shown.

[0055] Example 16

[0056] In a nitrogen-filled glove box, 1-phenylcyclododecyl alcohol (0.4 mmol, 104.1 mg) and an olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, yield 88%). The NMR spectrum of the product is shown below. Figure 21-28 As shown.

[0057] Example 17

[0058] In a nitrogen-filled glove box, 1-phenylcyclopentadecanol (0.4 mmol, 120.8 mg) and an olefin (0.4 mmol, 61.7 mg) were dissolved in dry acetonitrile (2 mL, 0.20 M). Then, the photocatalyst 4'-phenyl-2,2':6',2''-terpyridine-U(NO3)3(OMe) (15.3 mg, 5 mol%) was added. The resulting mixture was sealed with a screw cap and removed from the glove box. The reaction was then irradiated under a blue LED lamp (wavelength 440 nm-450 nm) at 25 °C for 12-24 hours. The reaction solvent was removed by vacuum concentration, and the product was purified by column chromatography to obtain the target product (colorless oil, 90% yield). The NMR spectrum of the product is shown below. Figures 29-30 As shown.

[0059] Comparative Example 1 Case 1: The reaction conditions and reactants are the same as in Example 1, except that the catalyst is replaced with a hexavalent uranium photocatalyst.

[0060] Case 2: The reaction conditions and reactants are the same as in Example 1 and Case 1, except that the catalyst is replaced with BiVO4 photocatalyst.

[0061] Case 3: The reaction conditions and raw materials are the same as in Example 1 and Case 1, except that the catalyst is replaced with g-C3N4 photocatalyst.

[0062] Case 4: The reaction conditions and raw materials are the same as in Example 1 and Case 1, except that the catalyst is replaced with TiO2 photocatalyst.

[0063] Case 5: The reaction conditions and reactants are the same as in Example 1 and Case 1, using the same tetravalent uranium catalyst, except that no ligands are used.

[0064] Table 1: Catalytic effects of different catalysts

[0065] Comparative Example 2 Case 1: The reaction materials are the same as those in Example 1, except that the reaction system is placed in the air for the reaction, and the other reaction conditions are not changed.

[0066] Case 2: The reaction materials are the same as in Example 1. In Example 1, the reaction was carried out only under dark conditions without light, and the other reaction conditions remained unchanged.

[0067] Case 3: The reaction raw materials are the same as those in Example 1, except that the reaction time is changed to 80 hours, and the other reaction conditions remain unchanged.

[0068] Case 4: The reaction raw materials are the same as those in Example 1, except that the catalyst content is changed to 0.5 mol%, and the other reaction conditions remain unchanged.

[0069] Case 5: The reaction raw materials are the same as those in Example 1, except that the molar amount of alcohol is in excess, and the other reaction conditions remain unchanged.

[0070] Case 6: The reaction raw materials are the same as in Example 1. In Example 1, only the organic solvent is not used in the reaction system, and the other reaction conditions are unchanged.

[0071] Table 2: Yields under different reaction conditions

[0072] As can be seen from Example 1, Case 1, and Comparative Examples 1-4 of Example 1, the catalyst used in this invention cannot be replaced; other photocatalysts cannot induce the reaction. The tetravalent uranium catalyst used in this invention can break the hydrogen-oxygen bonds in the reactants, thereby enabling the formation of alcohols and alkenes that cannot react under other conditions, while simultaneously increasing the reaction rate. As can be seen from Comparative Example 1 and Comparative Example 5, the tetravalent uranium catalyst needs to be used in conjunction with ligands. The tetravalent uranium catalyst used in this invention contains nitrogen coordination sites, and the coordination of terpyridine ligands with tetravalent uranium stabilizes the tetravalent uranium. When these coordination sites are removed, the tetravalent uranium catalyst loses its catalytic activity.

[0073] As can be seen from Examples 1-6 of Example 1 and Comparative Examples 2, since the present invention uses a photocatalyst, without light energy to activate the catalyst during the reaction, the catalyst is inactive and cannot catalyze the reaction. Too short a reaction time prevents the reaction from proceeding fully, resulting in a low yield. Since organic reactions involve multiple reactions occurring simultaneously, too long a reaction time leads to the complete occurrence of side reactions, producing excessive non-target products and reducing the reaction yield. If no organic solvent is added to the reaction system, consisting only of alcohols and alkenes, the reaction cannot proceed. Therefore, a certain amount of organic solvent needs to be added during the reaction. The alcohol needs to be in slight excess; adding too much alcohol will destroy the catalytic activity of tetravalent uranium, preventing the reaction from occurring.

[0074] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for photocatalytic breaking and formation of carbon-carbon bonds using tetravalent uranium, characterized in that, Includes the following steps: Under inert gas and blue light conditions of 440nm-450nm, a tetravalent uranium catalyst with the molecular formula LU(NO3)3(OMe) was dissolved in an organic solvent at -40℃ to 80℃; then, a catalyst with the chemical structural formula […]. The olefin and its chemical structural formula are The cyclic alcohol reacts to form the product; Among them, R 3 It is a substituent on a cyclic alcohol, and is an aryl group; R 4 It is a substituent for olefins, and is any one of hydrogen atom, alkyl, aryl, alkoxy or ester group; R 5 It is a substituent for olefins, and is any one of hydrogen atom, alkyl, aryl, alkoxy or ester group; R 6 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; R 7 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; X is a heteroatom on the cyclic alcohol, which can be any one of oxygen, nitrogen, sulfur or CH2. n is the number of carbon atoms in the cyclic alcohol, which can be any one of zero, one, two, three, four, five, six, nine, or twelve.

2. The method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium according to claim 1, characterized in that, The organic solvent mentioned therein is one or more of tetrahydrofuran, toluene, 1,2-dichloroethane, chloroform, acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylpropenylurea, N-methylpyrrolidone, trifluorotoluene, methanol, ethanol, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dimethyl sulfoxide.

3. The method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium according to claim 1, characterized in that, The reaction temperature is -40℃ to 80℃; Preferably, the reaction temperature is 18℃-35℃.

4. The method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium according to claim 1, characterized in that, The reaction is carried out for 1-72 hours under the irradiation of the light source. Preferably, the reaction time is 12h-24h.

5. The method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium according to claim 1, characterized in that, The molar ratio of the tetravalent uranium catalyst to the reactants is greater than or equal to 1 mol% (in molar terms). Preferably, the molar ratio of tetravalent uranium catalyst to reactants is 5 mol%; Preferably, the molar ratio of tetravalent uranium catalyst: alcohol compound: olefin is (0.01-0.02):(0.2-0.3):(0.2-0.3).

6. The method for photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium according to claim 1, characterized in that, The tetravalent uranium catalyst has the molecular formula LU(NO3)3(OMe), where the L ligand is a pyridine ligand with coordination of... Any one of them.

7. A product formed by the method of photocatalytic breaking and formation of carbon-carbon bonds by tetravalent uranium as described in any one of claims 1-6, characterized in that, Chemical formula is ; Among them, R 3 It is a substituent on a cyclic alcohol, and is an aryl group; R 4 It is a substituent for olefins, and can be any one of hydrogen atom, alkyl, aryl or ester group; R 5 It is a substituent for olefins, and is any one of hydrogen atom, alkyl, aryl, alkoxy or ester group; R 6 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; R 7 It is a substituent for olefins, and can be any one of ester, cyano, or sulfonyl groups; X is a heteroatom on the cyclic alcohol, which can be any one of oxygen, nitrogen, sulfur or CH2. n is the number of carbon atoms in the cyclic alcohol, which can be any one of zero, one, two, three, four, five, six, nine, or twelve.

8. The product prepared by the method according to any one of claims 1-6 and the use of the product according to claim 7 as a pharmaceutical intermediate.

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