Preparation method of organic and light concerted catalysis germanium-containing ketone compound

Abstract

The invention provides a preparation method of an organic and light synergistic catalysis germanium-containing ketone compound, and relates to the technical field of synthesis of organic ketone compounds. The germanium-containing organic ketonide is generated through a bifunctionalization reaction of germanium hydride and acyl azonium on olefin. Alkyl germanium free radicals and acyl nitrogen onium salt anion free radicals are obtained through a hydrogen transfer process and a photooxidation reduction process of two times of single electron transfer, the alkyl germanium free radicals and olefin are subjected to addition to obtain alkyl free radicals, then the alkyl free radicals are coupled with the acyl nitrogen onium salt anion free radicals, and finally carbene and trifluoromethanesulfonic acid acyl anions are separated, so that the compound is obtained. The germanium-containing ketonide is obtained. According to the invention, the raw materials which are easy to obtain are used for preparing germanium-containing ketone compounds with potential biological activity under the concerted catalysis of organic and photooxidation reduction, and the germanium-containing ketone compounds have the value of developing the germanium alkyl ketones which can be used in industry and can be used as functional germanium alkyl ketones.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic ketone compound synthesis, in particular to a preparation method of organic and light synergistically catalyzed germanium-containing ketone compound. BACKGROUND

[0002] As a kind of core functional organic molecules, organic ketone compounds are widely present in natural products, drug molecules and functional material systems. Among them, germanium-based units have important value in the fields of bioactive compounds and innovative drug research and development due to their unique chemical properties; and the rich chemical transformation characteristics of carbonyl groups provide multiple possibilities for the functional modification of molecules. Therefore, efficient construction of highly functionalized ketone skeletons has always been one of the core research directions in the field of organic chemical synthesis.

[0003] The traditional method for synthesizing germanium-containing ketone compounds mainly relies on nucleophilic carbonyl addition and Friedel-Crafts acylation reaction. However, although these methods can achieve the synthesis of organic ketone compounds, they require sensitive metal reagents or strong acidic conditions, resulting in harsh reaction conditions and poor functional group tolerance, which greatly limits the scope of applicable substrates. In recent years, visible light-mediated olefin acyl functionalization strategy has become a research hotspot due to its advantages in building complex molecular structures and step economy. This strategy combines photo-oxidation-reduction catalysis and hydrogen atom transfer (HAT) mechanism to convert free radical precursors into active species, which then couple with olefins to generate acylated products. Although photo-catalyzed radical reactions have the characteristics of mild conditions and good functional group compatibility, there are still significant bottlenecks in the synthesis of germanium-containing ketone compounds: existing photo-catalyzed germanium hydrogenation reactions only achieve single functionalization (such as germanium hydride of olefins), and cannot simultaneously introduce carbonyl groups and other key functional groups; the high activity of acyl radicals and the difficulty in controlling selectivity, especially in the coupling process with alkyl germanium radicals, which is prone to side reactions; lack of suitable carbonyl radical precursors, traditional acyl sources (such as aldehydes and anhydrides) have low efficiency in photo-catalytic systems.

[0004] As a kind of cheap and easy-to-obtain acyl radical precursor, acyl nitrogen ylide has been applied in some photo-catalyzed reactions, but its reaction with germanium hydride in a synergistic catalytic system has not been broken through. The existing synthesis path driven by high temperature or strong oxidizing agent not only has high energy consumption and strict equipment requirements, but also contradicts the concept of green chemistry, and is difficult to meet the needs of industrial production. Therefore, developing a new method for efficient synergy between germanium hydride and acyl nitrogen ylide under mild conditions is a key breakthrough to solve the problem of synthesis of germanium-containing ketone compounds. SUMMARY

[0005] In view of this, the present application provides a preparation method of organic and light synergistically catalyzed germanium-containing ketone compound to solve the above problems existing in the prior art.

[0006] To achieve the above object, the present invention proposes a method for preparing a germanium-containing ketone compound by organic and photocatalytic synergism, comprising the following steps: Add olefin, acyl nitrogen salt, alkyl germanium hydride, photocatalyst, hydrogen transfer reagent and base to an organic solvent and react under light conditions. The reaction formula is as follows:

[0007] In the formula, R1 is selected from aryl or substituted aryl, and the substituent of the substituted aryl is one of halogen, trimethylsilyl, trifluoromethyl, acetyl or -CO2Me; R2 is selected from one of hydrogen or methyl; R3 is selected from hydrogen; R4 is selected from one of methoxy, n-butyl or fluorine; R5 is selected from one of ethyl, n-butyl or phenyl; R6 is selected from one of ethyl, butyl or phenyl; R7 is selected from one of ethyl, n-butyl or phenyl.

[0008] Furthermore, R1 is selected from aryl or substituted aryl, and the substituent of the substituted aryl is one of fluorine, chlorine, trimethylsilyl, trifluoromethyl or -CO2Me; R2 is selected from hydrogen or methyl.

[0009] In the above technical solution, a hydrogen transfer reagent is used to oxidize the photocatalyst to generate a thiol radical and a reduced photocatalyst. The generated reduced photocatalyst simultaneously reduces the acyl nitrogen onium salt to generate a carbon radical. The thiol radical transfers the hydrogen proton of the alkyl germanium hydride to obtain an alkyl germanium radical. The generated acyl nitrogen onium salt anion radical and alkyl germanium radical are sequentially coupled with olefins, and then leave through carbene and trifluoromethanesulfonic acid acyl anion to generate a product containing a germanium ketone compound. At the same time, organic hydrogen transfer and photoredox catalysis realize regeneration cycle.

[0010] Further, the photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile or (4,4'-di-tert-butyl-2,2'-bipyridyl)bis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl]phenyl]iridium(III) hexafluorophosphate; The hydrogen transfer reagent is triisopropylsilanethiol or ethyl mercaptoacetate.

[0011] Furthermore, the alkylgermanium hydride is selected from one of tri-n-butylgermanium hydride, dimethylphenylgermanium hydride, triphenylgermanium hydride, diphenylgermanium hydride, triethylgermanium hydride and diphenylmethylgermanium hydride.

[0012] Further, the acyl azinium salt is selected from one of 2-(4-methoxybenzoyl)-1,3-dimethylimidazol-3-ium triflate, 2-(4-methylbenzoyl)-1,3-dimethylimidazol-3-ium triflate, 2-(4-tert-butylbenzoyl)-1,3-dimethylimidazol-3-ium triflate, 2-(4-fluorobenzoyl)-1,3-dimethylimidazol-3-ium triflate or 2-(4-trifluoromethoxybenzoyl)-1,3-dimethylimidazol-3-ium triflate.

[0013] Further, the base is selected from one of sodium acetate, potassium carbonate, cesium carbonate, sodium carbonate, 4-dimethylaminopyridine or potassium phosphate.

[0014] Further, the organic solvent is selected from at least one of acetonitrile, tetrahydrofuran, ethyl acetate, dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide.

[0015] Further, the molar ratio of the acyl azinium salt, the olefin, the germane hydride, the photocatalyst, the hydrogen transfer reagent and the base is 1-2:1:1-2:0.02-0.1:0.1-0.4:1-2.

[0016] Further, the light source in the reaction is a blue light source of 450-455 nm, and the light source power is 8-40 watts.

[0017] Further, the temperature of the reaction is 20-30℃, the time is 20-48 hours, and the reaction is carried out under inert gas protection.

[0018] The application also provides a germanium-containing ketone compound prepared by the above preparation method, which has any one of the following structures: .

[0019] In the above technical solution, the olefin, the acyl azinium salt, the alkyl germane hydride, the photocatalyst, the hydrogen transfer reagent and the base are used as starting materials to synthesize the germanium-containing ketone compound, and the method is further used for the post-modification of functional organic ketone compound molecules having nitrogen-containing, halogen-containing and other bioactive groups.

[0020] The present application takes olefin, acyl azoniun salt, alkyl germanium hydride, photocatalyst, hydrogen transfer reagent and base as starting materials, and the product of organic ketone compound is obtained by reaction. The preparation method uses hydrogen transfer reagent to oxidize photocatalyst to generate mercaptan radical and reduced photocatalyst, the generated reduced photocatalyst synchronously reduces acyl azoniun salt to generate carbon radical, the mercaptan radical transfers hydrogen proton of alkyl germanium hydride to obtain alkyl germanium radical, the generated acyl azoniun salt negative ion radical and alkyl germanium radical are coupled with olefin in turn, and then the carbene and trifluoromethanesulfonic acid acyl negative ion are removed to generate the product of germanium-containing ketone compound. Meanwhile, organic hydrogen transfer and photo-redox catalysis realize regeneration cycle. The germanium-containing ketone compound with potential biological activity is synthesized, the reaction is compatible with drug active groups such as hydroxyl groups, can be used for post-modification conversion of functional organic molecules, and has the value of developing a new method for industrial synthesis of organic ketone functional molecules.

[0021] Compared with the prior art, the present application has the advantages that: The present application solves the problem that the traditional synthesis route depends on high reaction temperature and use of high-energy light source, avoids harsh reaction conditions and environmental unfriendliness caused by use of high temperature and high-energy light source, and has mild reaction conditions and facilitates industrial scale production. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The reaction mechanism route map of the germanium-containing ketone compound of the present application is shown in the figure. DETAILED DESCRIPTION

[0023] The present application will be described in detail below with reference to a plurality of exemplary embodiments. The detailed description should not be considered as limiting the present application, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present application.

[0024] All raw materials of the present application are not particularly limited in source, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0025] All raw materials of the present application are not particularly limited in purity, and the present application preferably uses analytically pure raw materials or raw material purity commonly used in the field of chemical synthesis. All reactions are carried out under the protection of inert gas (nitrogen), using 450-455 nm blue LED light source (power 8-40 W) for irradiation, and the reaction container is a sealed light-resistant glass reaction tube.

[0026] As Figure 1As shown, the present invention provides a method for preparing a germanium-containing ketone compound by organic and photoredox synergistic catalysis. The method utilizes a hydrogen transfer reagent to oxidize a photocatalyst to generate a thiol radical and a reduced photocatalyst. The generated reduced photocatalyst simultaneously reduces an acyl nitrogen onium salt to generate a carbon radical. The thiol radical transfers the hydrogen proton of an alkyl germanium hydride to obtain an alkyl germanium radical. The generated acyl nitrogen onium salt anion radical and alkyl germanium radical are sequentially coupled with an olefin, and then leave through a carbene and a trifluoromethanesulfonic acid acyl anion to generate a product containing the germanium ketone compound.

[0027]

[0028] In the formula, R1 is selected from aryl or substituted aryl, and the substituent of the substituted aryl is one of halogen, trimethylsilyl, trifluoromethyl, acetyl or -CO2Me; R2 is selected from one of hydrogen or methyl; R3 is selected from hydrogen; R4 is selected from one of methoxy, n-butyl or fluorine; R5 is selected from one of ethyl, n-butyl or phenyl; R6 is selected from one of ethyl, butyl or phenyl; R7 is selected from one of ethyl, n-butyl or phenyl.

[0029] In an organic solvent, olefins, acyl nitrogen salts, alkyl germanium hydrogens, photocatalysts, hydrogen transfer reagents and bases are used as starting materials, and a germanium ketone compound is prepared by reaction under the synergistic action of organic and photoredox.

[0030] The present invention relates to the synthesis of the following known compounds:

[0031] Example 1 4'-methoxy-2-(2-chlorophenyl)-3-(tri-n-butylgermanyl)propiophenone, the structural formula is:

[0032] Its synthesis method is: To o-chlorostyrene (0.2 mmol, 27.7 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3- dimethylimidazolium-3-ium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium-3-ium triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL) were added under nitrogen protection, sealed, irradiated with blue light (wavelength 455 nm) at room temperature for 24 h, cooled, extracted, and the solvent was recovered under reduced pressure. The product was separated by preparative thin layer chromatography to obtain 76.6 mg of the compound of Example 1, with a yield of 74%.

[0033] The structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 8.7 Hz, 2H), 7.46 (d, J = 7.4Hz, 1H), 7.39 (d, J = 7.4 Hz, 1H), 7.26 – 7.18 (m, 2H), 6.98 (d, J = 8.7 Hz,2H), 5.32 – 5.25 (m, 1H), 3.91 (s, 3H), 1.79 – 1.69 (m, 1H), 1.40 – 1.25 (m,13H), 0.94 (t, J = 6.7 Hz, 9H), 0.81 – 0.69 (m, 6H). 13 C{ 1 H} NMR (100 MHz, CDCl3): δ198.7, 163.4, 140.4, 132.6, 130.9,129.8, 129.5, 129.0, 128.0, 127.4, 113.8, 55.5, 45.4, 27.4, 26.7, 17.9, 13.8,13.0 ppm. Example 2 4'-Methoxy-2-(2-fluorophenyl)-3-(tri-n-butylgermyl)propiophenone, with the structural formula:

[0034] The synthesis method is as follows: To o-fluorostyrene (0.2 mmol, 24.4 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3- dimethylimidazolium-3-yl trifluoromethanesulfonate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium-3-yl trifluoromethanesulfonate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, sealed, blue light irradiation (wavelength 455 nm) at room temperature for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 67.3 mg of the compound of example 2, yield 67%.

[0035] Its structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.99 (d, J = 8.9 Hz, 2H), 7.39 – 7.35 (m,1H), 7.18 – 7.12 (m, 1H), 7.06 – 6.97 (m, 2H), 6.89 (d, J = 8.9 Hz, 2H), 5.07(t, J = 7.5 Hz, 1H), 3.82 (s, 3H), 1.65 – 1.56 (m, 1H), 1.32 – 1.14 (m, 13H),0.84 (t, J = 7.0 Hz, 9H), 0.67 – 0.54 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 198.7, 163.5, 160.7, 158.3, 130.8,129.3, 129.2 (d, J = 15.1 Hz), 128.4 (d, J = 8.3 Hz), 124.7 (d, J = 3.1 Hz),115.5 (d, J = 23.0 Hz), 113.8, 55.5, 40.3, 27.4, 26.7, 17.4, 13.8, 12.8 ppm. 19 F NMR (376 MHz, CDCl3) δ -118.6 ppm. Example 3 4'-Methoxy-3-(triethylgermyl)-2-[4-(trimethylsilyl)phenyl]propiophenone, having the structure:

[0036] The synthesis method is as follows: Take 4-trimethylsilylphenylstyrene (0.2 mmol, 35.2 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), triethylgermane (0.4 mmol, 64.3 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) at room temperature for 24 h, cool, extract, recover the solvent under reduced pressure, and separate by thin layer chromatography to obtain 56.5 mg of the compound of Example 3, with a yield of 60%.

[0037] The structure is confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.9 Hz, 2H), 7.42 (d, J = 7.9Hz, 2H), 7.32 (d, J = 7.9 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.66 (dd, J =8.6, 6.6 Hz, 1H), 3.81 (s, 3H), 1.76 – 1.68 (d, J = 7.9 Hz, 1H), 1.31 – 1.25(m, 1H), 0.96 (t, J = 7.9 Hz, 9H), 0.68 – 0.54 (m, 6H), 0.22 (s, 9H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 198.8, 163.2, 143.1, 138.7, 133.9,131.0, 129.7, 127.3, 113.8, 55.4, 49.7, 17.6, 9.0, 4.4, -1.0 ppm. Example 4 4-(4-methoxybenzoyl)-3-(tri-n-butylgermyl)benzyl acetate, having the structure:

[0038] The synthesis method is as follows: Take 4-vinylbenzyl acetate (0.2 mmol, 35.2 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium-3- triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3- benzenedicarbonitrile (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) room temperature reaction for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 67.7 mg of the compound of Example 4, yield 61%.

[0039] The structure is confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 8.7 Hz, 2H), 7.29 (d, J = 8.0Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 4.98 (s, 2H),4.63 (t, J = 7.5 Hz, 1H), 3.78 (s, 3H), 2.02 (s, 3H), 1.64 – 1.54 (m, 1H),1.27 – 1.10 (m, 13H), 0.79 (t, J = 6.6 Hz, 9H), 0.61 – 0.45 (m, 6H) ppm. 13 C{ 1H} NMR (100 MHz, CDCl3): δ 198.8, 170.9, 163.3, 142.5, 134.4,130.9, 129.5, 128.9, 128.3, 113.8, 66.1, 55.5, 49.4, 27.4, 26.7, 21.0, 18.5,13.8, 12.9 ppm. Example 5 4'-Methoxy-3-(tributylgermanyl)-2-[3-(trifluoromethyl)phenyl]propanal, having the structure:

[0040] The synthesis method is as follows: Take 3-trifluoromethylstyrene (0.2 mmol, 34.4 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) room temperature reaction for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 67.0 mg of example 5 compound, yield 61%.

[0041] The structure is confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 8.7 Hz, 2H), 7.61 (s, 1H),7.55 (d, J = 7.5 Hz, 1H), 7.47 – 7.37 (m, 2H), 6.91 (d, J = 8.7 Hz, 2H), 4.73(t, J = 7.6 Hz, 1H), 3.84 (s, 3H), 1.68 – 1.56 (m, 1H), 1.23 (s, 13H), 0.84(t, J = 6.4 Hz, 9H), 0.64 – 0.51 (m, 6H) ppm. 13 C{ 1H} NMR (100 MHz, CDCl3): δ 198.5, 163.6, 143.1, 131.6, 131.1,131.0, 129.2, 125.5, 125.0, 124.1 (q, J = 272.5 Hz), 123.8, 122.8, 113.9,55.5, 49.2, 27.4, 26.7, 18.8, 13.8, 12.9 ppm. 19 F NMR (376 MHz, Chloroform-d)δ -62.4 ppm. Example 6 3-[(Methoxybenzoyl-tributylgermanylpropyl)]benzoic acid methyl ester, with the structure:

[0042] The synthesis method is as follows: Take 3-vinylbenzoic acid methyl ester (0.2 mmol, 32.4 mg, 1.0 equiv.), 2-(4- methoxybenzoyl)-1,3-dimethylimidazolium-3-yl triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3- benzenedicarbonitrile (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) at room temperature for 24 h, cool, extract, recover the solvent under reduced pressure, and separate by preparative thin layer chromatography to obtain 76.8 mg of Example 6 compound, with a yield of 71%.

[0043] The structure is confirmed by NMR detection: 1H NMR (400 MHz, CDC13): δ 8.02 (s, 1H), 7.96 (d, J = 8.8 Hz, 2H), 7.87 (d, J = 7.7 Hz, 1H), 7.54 (d, J = 7.7 Hz, 1H), 7.34 (t, J = 7.7 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 4.72 (t, J = 7.6 Hz, 1H), 3.90 (s, 3H), 3.82 (s, 3H), 1.68 - 1.60 (m, 1H), 1.32 - 1.17 (m, 13H), 0.83 (t, J = 6.8 Hz, 9H), 0.64 - 0.50 (m, 6H). 13 C{ 1 H} NMR (100 MHz, CDC13): δ 198.7, 167.0, 163.4, 142.7, 132.6, 131.0, 130.6, 129.4, 129.3, 128.9, 128.2, 113.9, 55.5, 52.2, 49.4, 27.4, 26.7, 18.6, 13.8, 12.9 ppm. Example 7 4'-Methoxy-2-(perfluorophenyl)-3-(tributylgermanyl)propiophenone, having the structure:

[0044] The synthesis method is as follows: Take 2,3,4,5,6-pentafluorostyrene (0.2 mmol, 38.8 mg, 1.0 equiv.), 2-(4- methoxybenzoyl)-1,3-dimethylimidazolium trifluoromethanesulfonate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3- benzenedicarbonitrile (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) room temperature reaction for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 65.3 mg of Example 7 compound, yield 57%.

[0045] The structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.9 Hz, 2H), 6.91 (d, J = 8.9Hz, 2H), 4.89 – 4.83 (m, 1H), 3.85 (s, 3H), 1.71 – 1.64 (m, 1H), 1.37 – 1.18(m, 13H), 0.93 – 0.78 (m, 9H), 0.70 – 0.56 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 195.3, 163.6, 146.2, 143.8, 139.0,130.6, 128.4, 115.9, 114.1, 55.6, 39.9, 27.3, 26.7, 14.4, 13.8, 12.7 ppm. 19 FNMR (376 MHz, CDCl3): -137.2 – 143.7 (m, 2F), -154.6 – -156.8 (m, 1F), -160.2– -164.2 (m, 2F) ppm. Example 8 4'-Methoxy-3-(tributylgermanyl)-2-(3-pyridinyl)propiophenone, having the structure:

[0046] The synthesis method is: To 3-vinylpyridine (0.2 mmol, 21.0 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-l,3-dimethylimidazolium-3-yl triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-l,3-dimethylimidazolium-3-yl triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL) were added under nitrogen protection, sealed, irradiated with blue light (wavelength 455 nm) at room temperature for 24 h, cooled, extracted, and the solvent was recovered under reduced pressure. The compound 58 of Example 8 was obtained by preparative thin layer chromatography, 58.1 mg, yield 60%.

[0047] The structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 8.59 (d, J = 1.8 Hz, 1H), 8.43 (d, J = 4.6Hz, 1H), 7.94 (d, J = 8.8 Hz, 2H), 7.68 (d, J = 7.9 Hz, 1H), 7.19 (dd, J =7.5, 5.1 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 4.68 (t, J = 7.6 Hz, 1H), 3.82(s, 3H), 1.66 – 1.59 (m, 1H), 1.29 – 1.16 (m, 13H), 0.82 (t, J = 6.8 Hz, 9H),0.64 – 0.50 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 198.4, 163.6, 149.7, 148.3, 137.8,135.4, 130.9, 129.0, 123.7, 113.9, 55.5, 46.6, 27.3, 26.6, 18.5, 13.8, 12.8ppm. Example 9 4'-Methoxy-3-(tributylgermyl)-2-(4-pyridyl)propiophenone, with the structure:

[0048] The synthesis method is as follows: Take 4-vinylpyridine (0.2 mmol, 21.0 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) room temperature reaction for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 66.8 mg of the compound of Example 9, the yield is 69%.

[0049] The structure is confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 8.48 (d, J = 5.3 Hz, 2H), 7.92 (d, J = 8.8Hz, 2H), 7.25 (d, J = 5.4 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 4.62 (t, J = 7.5Hz, 1H), 3.83 (s, 3H), 1.70 – 1.63 (m, 1H), 1.29 – 1.19 (m, 13H), 0.83 (t, J= 6.8 Hz, 9H), 0.67 – 0.51 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 197.7, 163.7, 151.2, 150.2, 130.9,129.1, 123.3, 114.0, 55.5, 49.0, 27.3, 26.6, 18.3, 13.8, 12.9 ppm. Example 10 4'-Methoxy-3-(tributylgermanyl)-2-(4-thienyl)propiophenone, the structural formula is:

[0050] The synthesis method is as follows: 2-Vinylthiophene (0.2 mmol, 22.0 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (3.2 mg, 2 mol%), triisopropylsilanethiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL) were taken and sealed under nitrogen protection and irradiated with blue light (wavelength 455 nm) at room temperature for 24 h. h, cooled, extracted, and the solvent was recovered under reduced pressure. 42.1 mg of Example 10 compound was obtained by preparative thin-layer chromatography (yield: 43%).

[0051] Its structure was confirmed by NMR analysis: 1 H NMR (400 MHz, CDCl3): δ 8.00 (d, J = 8.9 Hz, 2H), 7.14 (dd, J =5.0, 1.0 Hz, 1H), 6.95 – 6.87 (m, 4H), 4.97 (t, J = 7.6 Hz, 1H), 3.85 (s,3H), 1.65 – 1.59 (m, 1H), 1.41 (dd, J = 13.7, 8.1 Hz, 1H), 1.31 – 1.17 (m,12H), 0.85 (t, J = 6.9 Hz, 9H), 0.67 – 0.54 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 198.0, 163.5, 145.0, 131.1, 129.0,126.7, 125.0, 124.5, 113.9, 55.5, 44.2, 27.4, 26.7, 19.6, 13.8, 12.8ppm. Example 11 4'-methoxy-2-(2-chlorophenyl)-3-(dimethylphenylgermanyl)propiophenone, the structural formula is:

[0052] Its synthesis method is: To 2-chlorostyrene (0.2 mmol, 27.6 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), dimethylphenylgermane (0.4 mmol, 72.3 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dimethylimidazolium triflate (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL) were added under nitrogen protection, sealed, irradiated with blue light (wavelength 455 nm) at room temperature for 24 h, cooled, extracted, and the solvent was recovered under reduced pressure. The compound 53.5 mg of Example 11 was obtained by preparative thin layer chromatography, with a yield of 59%.

[0053] Its structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.89 – 7.81 (m, 2H), 7.48 – 7.41 (m, 2H),7.35 – 7.27 (m, 4H), 7.23 (dd, J = 7.2, 2.3 Hz, 1H), 7.17 – 7.08 (m, 2H),6.87 – 6.82 (m, 2H), 5.17 – 5.12 (m, 1H), 3.83 (s, 3H), 1.91 – 1.84 (m, 1H),1.43 – 1.37 (m, 1H), 0.38 – 0.33 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 198.5, 163.4, 141.1, 140.0, 133.4,132.7, 130.9, 129.8, 129.3, 128.9, 128.4, 128.1, 128.0, 127.5, 113.8, 55.5,45.7, 21.0, -2.6, -3.1 ppm. Example 12 4'-Methoxy-2-(2-chlorophenyl)-3-(triphenylgermyl)propiophenone, with the structural formula:

[0054] The synthesis method is: To 2-chlorostyrene (0.2 mmol, 27.6 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3- dimethylimidazolium-3-ium triflate (0.4 mmol, 151.7 mg, 2.0 equiv.), triphenylgermane (0.4 mmol, 135 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dicyanobenzene (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL) were added under nitrogen protection, sealed, irradiated with blue light (wavelength 455 nm) at room temperature for 24 h, cooled, extracted, and the solvent was recovered under reduced pressure. The compound 101 of Example 12 was obtained by preparative thin layer chromatography, 101.6 mg, yield 88%.

[0055] Its structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.54 – 7.48 (m, 8H), 7.31 – 7.23 (m, 10H),7.20 – 7.16 (m, 1H), 7.05 (dd, J = 6.3, 2.8 Hz, 2H), 6.67 – 6.62 (m, 2H),5.24 – 5.17 (m, 1H), 3.72 (s, 3H), 2.61 – 2.51 (m, 1H), 1.90 – 1.82 (m, 1H)ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 197.8, 163.1, 140.1, 136.8, 135.2,132.6, 130.6, 129.9, 129.3, 128.9, 128.7, 128.2, 128.1, 127.5, 113.3, 55.4,45.9, 18.5 ppm. Example 13 2-phenyl-3-(tributylgermanyl)-4'-tert-butylpropiophenone, the structural formula is:

[0056] The synthesis method is: To styrene (0.2 mmol, 20.8 mg, 1.0 equiv.), 2-(4-tert-butylbenzoyl)-1,3- dimethylimidazolium-3-ium trifluoromethanesulfonate (0.4 mmol, 162.6 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3- benzenedicarbonitrile (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, sealed, blue light irradiation (wavelength 455 nm) at room temperature for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 44.8 mg of the compound of Example 13, with a yield of 44%.

[0057] Its structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 7.3 Hz, 2H), 7.27 (s, 2H), 7.18 (t, J = 7.3 Hz, 1H), 4.69 (t, J = 7.6 Hz, 1H), 1.63 (dd, J = 13.8, 7.6 Hz, 1H), 1.30 (s, 9H), 1.27– 1.16 (m, 13H), 0.83 (t, J = 6.9 Hz, 9H), 0.67 – 0.51 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 200.2, 156.4, 142.1, 134.1, 128.9, 128.7, 128.2, 126.9, 125.6, 50.0, 35.1, 31.1, 27.4, 26.7, 18.5, 13.8, 12.9 ppm. Example 14 2-phenyl-3-(tributylgermanyl)-4'-fluorophenylpropio- none, with the structural formula:

[0058] The synthesis method is: To styrene (0.2 mmol, 20.8mg, 1.0 equiv.), 2-(4-fluorobenzoyl)-l,3-dimethylimidazol-3-ium triflate (0.4 mmol, 147 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-l,3-dicyano-benzene (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, sealed, blue light irradiation (wavelength 455 nm) at room temperature for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 39.5 mg of compound 14 of example 14, yield 42%.

[0059] Its structure was confirmed by NMR detection: 1 H NMR (400 MHz, CDCl3): δ 8.00 - 7.88 (m, 2H), 7.27 - 7.20 (m, 4H), 7.16 - 7.10 (m, 1H), 7.00 (t, J = 8.6 Hz, 2H), 4.58 (t, J = 7.6 Hz, 1H), 1.61 - 1.52 (m, 1H), 1.25 - 1.12 (m, 13H), 0.78 (t, J = 7.0 Hz, 9H), 0.60 - 0.46 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ 199.0, 165.5 (d, J = 254.5 Hz), 141.8, 133.1, 131.35 (d, J = 9.2 Hz), 129.0, 128.1, 127.1, 115.72 (d, J = 21.8 Hz), 50.3, 27.4, 26.7, 18.4, 13.8, 12.9 ppm. 19 F NMR (376 MHz, Chloroform-d) δ -105.6 ppm. Example 15 Tetramethyldioxanyl methyl-4-[(S)-methoxybenzoyl-tributylgermylpropyl]benzoate, of formula:

[0060] The synthesis method is: Take (2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxol)[4,5-b:4',5'-d]pyran-3a-yl) methyl 4-vinylbenzoate (0.2 mmol, 78.0 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-1,3-dimethylimidazolium trifluoromethanesulfonate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-1,3-dicyanobenzene (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, seal, blue light (wavelength 455 nm) room temperature reaction for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain the compound of example 15 120.0 mg, yield 78%.

[0061] The structure is confirmed by NMR detection: 1H NMR (400 MHz, CDC13): δ 7.97 (d, J = 7.9 Hz, 2H), 7.92 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 7.9 Hz, 2H), 6.87 (d, J = 8.4 Hz, 2H), 4.70 (t, J = 7.6 Hz, 1H), 4.64 - 4.56 (m, 2H), 4.41 (s, 1H), 4.30 (dd, J = 12.0, 3.7 Hz, 1H), 4.24 (d, J = 8.0 Hz, 1H), 3.93 (d, J = 13.0 Hz, 1H), 3.80 (d, J = 9.4 Hz, 4H), 1.66 (dd, J = 13.8, 7.9 Hz, 1H), 1.52 (s, 3H), 1.42 (s, 3H), 1.33 (d, J = 13.7 Hz, 6H), 1.28 (d, J = 6.9 Hz, 1H), 1.23 (d, J = 7.1 Hz, 12H), 0.87 - 0.78 (m, 9H), 0.66 - 0.51 (m, 6H) ppm. 13 C{ 1 H} NMR (100 MHz, CDC13): δ 198.4, 165.8, 163.5, 147.9, 130.9, 130.3, 129.3, 128.4, 128.2, 113.8, 109.2, 108.9, 101.7, 70.8, 70.5, 70.1, 65.3, 61.4, 55.5, 49.7, 27.4, 26.6, 26.6, 25.9, 25.6, 24.0, 18.4, 13.8, 12.9 ppm. Example 16 4-[3-tri-n-butylgermanium-1-(4-methoxyphenyl)propylidene]benzyl-2-[1-(4- chlorobenzoyl)-5-methoxy-2-methylindolyl]acetate, having the structure:

[0062] which was synthesized by the method: To 4-vinylbenzyl 2-(l-(4-methoxybenzoyl)-2-methyl-lH-indol-3-yl)acetate (0.2 mmol, 91.1 mg, 1.0 equiv.), 2-(4-methoxybenzoyl)-l,3-dimethylimidazol-3-ium trifluoromethanesulfonate (0.4 mmol, 151.7 mg, 2.0 equiv.), tributylgermane (0.4 mmol, 97.9 mg, 2.0 equiv.), potassium carbonate (0.4 mmol, 55.2 mg, 2.0 equiv.), 2,4,5,6-tetrakis(9-carbazolyl)-l,3-dicyano-benzene (3.2 mg, 2 mol%), triisopropylsilane thiol (7.6 mg, 20 mol%) and ethyl acetate (1.0 mL), under nitrogen protection, sealed, blue light irradiation (wavelength 455 nm) at room temperature for 24 h, cooling, extraction, recovery of solvent under reduced pressure, separation by preparative thin layer chromatography to obtain 70.4 mg of the compound of example 16, with a yield of 43%.

[0063] Its structure was confirmed by NMR: 1 H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 8.6 Hz, 2H), 7.64 (d, J = 8.3Hz, 2H), 7.46 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 7.9 Hz, 2H), 7.22 (d, J = 7.9Hz, 2H), 6.94 – 6.85 (m, 4H), 6.68 – 6.63 (m, 1H), 5.07 (s, 2H), 4.66 (t, J =7.5 Hz, 1H), 3.83 (s, 3H), 3.73 (s, 3H), 3.68 (s, 2H), 2.36 (s, 3H), 1.69 –1.60 (m, 1H), 1.28 – 1.19 (m, 13H), 0.84 (t, J = 6.6 Hz, 9H), 0.66 – 0.50 (m,6H) ppm. 13 C{ 1H} NMR (100 MHz, CDCl3): δ 198.8, 170.7, 168.4, 163.3, 156.1, 142.7, 139.3, 136.0, 134.3, 133.9, 131.3, 131.0, 130.8, 130.6, 129.5, 129.2, 128.7, 128.3, 115.0, 113.8, 112.5, 111.9, 101.2, 66.5, 55.7, 55.5, 49.3, 30.4, 27.4, 26.7, 18.6, 13.8, 13.5, 12.9 ppm. The above described embodiments are only to illustrate the preferred modes of the present application, and are not intended to limit the scope of the present application. Any modification and improvement made by those skilled in the art to the technical solutions of the present application without departing from the design spirit of the present application shall fall within the protection scope defined by the claims of the present application.

Claims

1. A method for preparing a germanium-containing ketone compound by organic and photocatalytic synergy, characterized in that: The following steps are involved: Add olefin, acyl nitrogen salt, alkyl germanium hydride, photocatalyst, hydrogen transfer reagent and base to an organic solvent and react under light conditions. The reaction formula is as follows: ， In the formula, R1 is selected from aryl or substituted aryl, and the substituent of the substituted aryl is one of halogen, trimethylsilyl, trifluoromethyl, acetyl or -CO2Me; R2 is selected from one of hydrogen or methyl; R3 is selected from hydrogen; R4 is selected from one of methoxy, n-butyl or fluorine; R5 is selected from one of ethyl, n-butyl or phenyl; R6 is selected from one of ethyl, butyl or phenyl; R7 is selected from one of ethyl, n-butyl or phenyl.

2. The preparation method according to claim 1, characterized in that The photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile or (4,4'-di-tert-butyl-2,2'-bipyridyl)bis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl]phenyl]iridium(III) hexafluorophosphate; The hydrogen transfer reagent is triisopropylsilanethiol or ethyl mercaptoacetate.

3. The preparation method according to claim 1, characterized in that The alkylgermanium hydride is selected from one of tri-n-butylgermanium hydride, dimethylphenylgermanium hydride, triphenylgermanium hydride, diphenylgermanium hydride, triethylgermanium hydride and diphenylmethylgermanium hydride.

4. The preparation method according to claim 1, characterized in that The acyl nitrogen salt is selected from one of 2-(4-methoxybenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate, 2-(4-methylbenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate, 2-(4-tert-butylbenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate, 2-(4-fluorobenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate or 2-(4-trifluoromethoxybenzoyl)-1,3-dimethylimidazol-3-ium trifluoromethanesulfonate.

5. The preparation method according to claim 1, characterized in that The base is selected from one of sodium acetate, potassium carbonate, cesium carbonate, sodium carbonate, 4-dimethylaminopyridine or potassium phosphate.

6. The preparation method according to claim 1, characterized in that The organic solvent is selected from at least one of acetonitrile, tetrahydrofuran, ethyl acetate, dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide.

7. The preparation method according to claim 1, characterized in that The molar ratio of the acyl nitrogen onium salt, olefin, germanium hydrogen compound, photocatalyst, hydrogen transfer reagent and base is 1-2:1:1-2:0.02-0.1:0.1-0.4:1-2.

8. The preparation method according to claim 1, characterized in that The light source in the reaction is a blue light source of 450-455 nm, and the light source power is 8-40 watts.

9. The preparation method according to claim 1, characterized in that The reaction temperature is 20-30° C., the reaction time is 20-48 hours, and the reaction is carried out under the protection of an inert gas.

10. A germanium-containing ketone compound prepared by the preparation method according to any one of claims 1 to 9, characterized in that: Has any of the following structures: 。

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