Dihydrotriazole aromatization precursors and their use in deacylative arylation of ketones

Abstract

The application discloses a kind of dihydrotriazole aromatization precursor, preparation method and the dihydrotriazole aromatization precursor in the deacyl arylation of ketone, and the application includes: (1) ketone and 2-pyridyl hydrazine amide are dissolved in solvent, then active additive is added, and heating activation reaction is carried out under inert gas atmosphere, to obtain dihydrotriazole aromatization precursor;(2) the product of step (1) is mixed with aryl halide after or without purification, and is carried out under the conditions of photocatalyst, nickel catalyst, base, solvent and light irradiation photocatalytic reaction, to obtain the deacyl arylation product of ketone.The deacyl arylation reaction method of ketone of the application has the advantages that raw material is simple and easy to obtain, reaction condition is mild, substrate applicability is wide, etc., meets the requirements of developing green environment-friendly chemistry.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and in particular to a dihydrotriazole aromatization precursor and its application in the deacylation reaction of ketones. Background Technology

[0002] Carbon-carbon bonds are widely present in organic compounds; however, due to their large steric hindrance and high bond energy, research on their activation reactions has been lagging and stagnant. Ketones, as one of the most common organic compounds, are widely found in natural products and drug molecules. Furthermore, ketones are among the most frequently used functional groups in organic synthesis; they can be readily converted from other functional groups and undergo various derivatization reactions at the α and β positions. Therefore, achieving efficient carbon-carbon bond activation (deacylation) and conversion of ketones is of great significance.

[0003] In recent years, the carbon-carbon bond activation of ketones catalyzed by transition metals has developed rapidly. However, research on the generation of carbon radicals through carbon-carbon bond activation of ketones has lagged behind, mainly due to the weak driving force of the reaction and the scarcity and instability of radical precursors.

[0004] Aromalation plays an important role as a thermodynamic driving factor in enzyme-catalyzed biotransformation and organic synthesis. In organic chemistry, free radicals appear as key intermediates in many valuable synthetic transformations. With the deepening research on free radical precursors, strategies for aromalation-driven free radical generation have begun to attract attention.

[0005] Professor Guangbin Dong's research group at the University of Chicago has long been engaged in the field of C-C bond activation. In 2019, the group achieved the deacetylation transformation of ketones through aromatization-driven C-C bond activation (Nature, 2019, 567, 373). This process involves a pre-aromatic intermediate formed from the ketone substrate and two activators (hydrazine and 1,3-diene). The pre-aromatic intermediate undergoes Ir(III)-mediated C-C bond cleavage to generate an aromatic heterocyclic pyrazole and a highly reactive alkyl radical-metal complex, which is then eliminated via CH bond reduction to yield the deacylated product. However, this transformation requires a high temperature of 160 °C, which limits the substrate range and synthetic applications of this reaction.

[0006] In recent years, some progress has been made in using aromatization as a driving force to achieve the deacylation transformation of ketones, but there are also some shortcomings, mainly including: 1) the means of generating carbon radicals are relatively limited, often requiring high temperature or equivalent oxidants; 2) the reaction types are relatively limited, and it is extremely challenging whether this strategy has universality and can be applied to a wider range of reaction types or substrate types.

[0007] Therefore, it is of great significance to develop an efficient and mild method to achieve the deacylation conversion of ketones. Summary of the Invention

[0008] This invention provides a dihydrotriazole aromatization precursor and its application in the deacylation reaction of ketones, achieving efficient and mild deacylation conversion of ketones.

[0009] The technical solution of the present invention is as follows:

[0010] A dihydrotriazole aromatized precursor, the structural formula of which is shown in formula (I) or formula (II):

[0011]

[0012] In formula (I), R1 and R2 are independently selected from: any substituted alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl, alkoxy, and alkyl ester groups;

[0013] In formula (II), Cy is an arbitrarily substituted 5- to 7-membered cycloalkyl group, or Cy is an arbitrarily substituted heterocyclic group containing one or more nitrogen or oxygen atoms as ring members.

[0014] Preferably, in formula (I), R1 and R2 are independently selected from:

[0015] Any substituted C1-C6 alkyl, any substituted C3-C6 cycloalkyl, any substituted C1-C6 alkoxy,

[0016]

[0017] In formula (II), Cy is selected from:

[0018]

[0019] In Cy, * refers to the position where it is attached to the parent nucleus.

[0020] The present invention also provides a method for preparing a dihydrotriazole aromatized precursor, comprising: dissolving a ketone and a 2-pyridylhydrazone in a solvent, adding an activating additive, and heating to 50-100°C under an inert gas atmosphere to carry out an activation reaction to obtain the precursor.

[0021] This invention also discloses a method for deacylation of ketones driven by visible light-induced aromatization, comprising:

[0022] (1) Dissolve the ketone and 2-pyridylhydrazone in a solvent, add an activating additive, and heat under an inert gas atmosphere to activate the reaction to obtain the dihydrotriazole aromatization precursor;

[0023] (2) The product of step (1) is mixed with an aryl halide, with or without purification, and subjected to photocatalytic reaction under the conditions of photocatalyst, nickel catalyst, base, solvent and light, to obtain the deacylated aryl product of the ketone.

[0024] The reaction route is as follows:

[0025]

[0026] or:

[0027]

[0028] In formula (I), R1 and R2 are independently selected from: alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl, and alkoxy groups with arbitrary substitution;

[0029] In formula (II), Cy is an arbitrarily substituted 5- or 6-membered cycloalkyl group, or Cy is an arbitrarily substituted heterocyclic group containing one or more nitrogen or oxygen atoms as ring members.

[0030] R3 is a substituent formed by the ring opening of Cy.

[0031] The activating additive is at least one of camphor sulfonic acid, p-toluene sulfonic acid, and acidic alumina.

[0032] In step (1), the solvent is at least one of acetonitrile, 1,4-dioxane, ethyl acetate, tetrahydrofuran, dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), methyl tert-butyl ether (MTBE), hexafluoroisopropanol (HFIP), dichloromethane (DCM), 1,2-dichloroethane (DCE), and N-methylpyrrolidone (NMP).

[0033] The ketones mentioned are 2-acetylindane (S1), acetylcyclohexane (S2), cyclopentyl ethyl ketone (S3), cyclobutylmethyl ketone (S4), 1-BOC-3-acetyl acridine (S5), 1-N-BOC-4-acetylpiperidine (S6), phenoxyethyl ketone (S7), 4-(3,4-dimethoxyphenyl)butane-2-one (S8), 4-(benzyloxy)butane-2-one (S9), 6-methyl-2-heptanone (S10), methyl 4-acetylbutyrate (S11), ethyl levulinate (S12), 4-acetylbutyl ethyl ester (S13), n-propyl levulinate (S14), methyl 5-acetylvalerate (S15), and 4-(4-methoxyphenyl)-2-... 1-Butanone (S16), 6-Methyl-5-hepten-2-one (S17), Cyclohexylacetone (S18), Naphthylbutyrenone (S19), BETA-dihydroionone (S20), 1-(tetrahydro-2H-pyran-4-yl)acetone (S21), 3,7-dimethyl-1-(5-oxohexyl)-3,7-dihydro-1H-purine-2,6-dione (S22), 8R,9S,13S,14S)-13-methyl-3-(5-oxohexyl)oxy)-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopentanphenanthroline-17-one (S23), 5-nonanone (S24), Cyclohexanone (S25) Tetrahydropyranone (S26), 4-propylcyclohexane-1-one (S27), 4-phenylcyclohexane-1-one (S28), 2-(4-oxocyclohexyl)isoindoline-1,3-dione (S29), N-tert-butoxycarbonyl-4-piperidinone (S30), 4-(4'-benzonitrile)cyclohexanone (S31), 1,4-cyclohexanedione monoethylene glycol ketal (S32), ethyl p-cyclohexanone formate (S33), 1-tert-butoxycarbonyl-2-methyl-piperidinone (S34), N-BOC-3-methyl-4-piperidinone (S35), 4-N-benzyloxycarbonylaminocyclohexanone (S36), N-tert-butoxycarbonyl-nortropinone (S37), cis-5-oxo At least one of the following: hexahydrocyclopentadieno[C]pyrrole-2(1H)-carboxylic acid tert-butyl ester (S38), 2-((4-oxocyclohexyl)carbamoyl)pyrrolidin-1-carboxylic acid tert-butyl ester (S39), (S)-2-(6-methoxynaphthyl-2-yl)-N-(4-oxocyclohexyl)propionamide (S40), 5-(2,5-dimethylphenoxy)-2,2-dimethyl-N-(4-oxocyclohexyl)pentanamide (S41), 2-(3-benzoylphenyl)-N-(4-oxocyclohexyl)propionamide (S42), and 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-N-(4-oxocyclohexyl)thiazole-5-carboxamide (S43).

[0034]

[0035] The aryl halide is selected from at least one of the following groups of compounds:

[0036]

[0037] The photocatalyst is 2,4,5,6-tetra(diphenylamino)isophthalonitrile (4DPAIPN);

[0038] [2,2'-Bi(4-tert-butylpyridine)]bis[2-(4-fluorophenyl)pyridine]iridium(III)hexafluorophosphate (Ir[(Fppy)2dtbbpy]PF6; [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridyl-KN,KN]bis[5-fluoro-2-(5-methyl-2-pyridyl-KN)phenylKC]iridiumhexafluorophosphate (Ir[(FMeCF3ppy)2dtbbpy]PF6); 4,4'-bis(trifluoromethyl)-2,2'-bipyridinebis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl)phenyl]iridium(III)hexafluorophosphate (Ir[(dFdCF3ppy)2dtbbpy]PF6); fac-tri( At least one of the following: (2-phenylpyridine)iridium (fac-Ir(ppy)3); (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridyl)phenyl]iridium(III)hexafluorophosphate (Ir(ppy)2(dtbbpy)PF6); bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridiumhexafluorophosphate (Ir[dF(CF3)ppy]2(dtbbpy)PF6); 3,6-di-tert-butyl-9-mesethyl-10-phenylacridin-10-onium tetrafluoroborate ((Mes-Acr-Ph)BF4); 2,4,5,6-tetracarbazolyl-1,3-dicyanophenyl (4CzIPN).

[0039] The nickel catalyst is at least one of the following: nickel(II) bromide diethylene glycol dimethyl ether complex (Ni(DME)Br2), (1,1'-bis(diphenylphosphine)ferrocene) nickel dichloride (Ni(dppf)Cl2), dibromobis(tributylphosphine) nickel(II) (Ni(PBu3)2Br2), dibromobis(triphenylphosphine) nickel (Ni(PPh3)2Br2), [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridine] nickel dichloride (Ni(dtbbpy)Br2), 1,10-o-phenanthroline nickel dibromide (Ni(Phenanthroline)Br2), dichloride bis(tricyclohexylphosphine) nickel(II) (Ni(PCy3)2Br2), nickel acetylacetonate (Ni(acac)2), and 1,3-bis(diphenylphosphine propane) nickel dichloride (Ni(dppp)Cl2).

[0040] The solvent in step (2) is at least one of acetonitrile (MeCN), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), 1,4-dioxane (Dioxane), acetonitrile (CH3CN), acetone (Acetone), ethanol (EtOH), dichloromethane (DCM), 1,2-dichloroethane (DCE), chloroform (CHCl3), ethyl acetate (EA), and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP).

[0041] The base is at least one of cesium carbonate (Cs₂CO₃), hydrated cesium hydroxide (CsOH·H₂O), potassium tert-butoxide (t-BuOK), sodium methoxide (MeONa), lithium hydroxide (KOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium phosphate (K₃PO₄), dipotassium hydrogen phosphate (K₂HPO₄), potassium dihydrogen phosphate (KH₂PO₄), tetramethylguanidine (TMG), sodium carbonate (Na₂CO₃), sodium bicarbonate (NaHCO₃), and potassium carbonate (K₂CO₃).

[0042] Preferably, in step (1), the molar amount of ketone is 100-120% of the molar amount of 2-pyridylhydrazone; the molar amount of activating additive is 2-10% of the molar amount of 2-pyridylhydrazone.

[0043] Preferably, in step (2), the molar amount of photocatalyst is 1-2% of the molar amount of 2-pyridylhydrazone; the molar amount of nickel catalyst is 10-20% of the molar amount of 2-pyridylhydrazone; and the molar amount of base is 300-400% of the molar amount of 2-pyridylhydrazone.

[0044] Preferably, in step (1), the temperature of the ketone activation reaction is 78-95°C and the reaction time is 12-24h; in step (2), the temperature of the photocatalytic reaction is room temperature to 80°C and the reaction time is 24-48h.

[0045] Preferably, the wavelength of the illumination is 370-467nm. The wavelength can be selected from 370, 390, 427, 440, 356, 467nm, etc.

[0046] In the visible light-induced aromatization-driven deacylation reaction method of ketones disclosed in this invention, under the conditions of photocatalyst, organic solvent, nickel catalyst, base and light irradiation, the dihydrotriazole aromatization precursor activated by the visible light-induced aromatization-driven ketone can efficiently generate alkyl radicals, which are then coupled with aryl halides under the action of nickel catalyst, thereby obtaining a series of arylated coupling products.

[0047] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0048] (1) The dihydrotriazole aromatization precursor provided by this invention can generate highly active alkyl radicals through a single-electron transfer process with an excited-state photocatalyst. This dihydrotriazole aromatization precursor is simple to synthesize, convenient to store, and can even be used directly for subsequent reactions without separation.

[0049] (2) The deacylation reaction method of ketones of the present invention has the advantages of simple and readily available raw materials, mild reaction conditions and wide applicability of substrates, which meets the requirements for the development of green and environmentally friendly chemistry.

[0050] (3) The method of the present invention can perform ring-opening reaction on cyclic ketones to obtain a series of triazole compounds, wherein the triazole structure is widely present in drug molecules, so the method is expected to be widely used in drug molecule modification. Attached Figure Description

[0051] Figure 1 This is a diagram illustrating the deacylation reaction mechanism mediated by the dihydrotriazole aromatylation precursor in the embodiments of the present invention;

[0052] Figure 2 This is the hydrogen NMR spectrum of the product of Example 1 of the present invention;

[0053] Figure 3 This is the carbon NMR spectrum of the product of Example 1 of the present invention;

[0054] Figure 4 This is the hydrogen NMR spectrum of the product of Example 2 of the present invention;

[0055] Figure 5 This is the carbon NMR spectrum of the product of Example 2 of the present invention;

[0056] Figure 6 This is the hydrogen NMR spectrum of the product of Example 3 of the present invention;

[0057] Figure 7 This is the carbon NMR spectrum of the product of Example 3 of the present invention;

[0058] Figure 8 This is the 1H NMR spectrum of the product of Example 4 of the present invention;

[0059] Figure 9 This is the carbon NMR spectrum of the product of Example 4 of the present invention;

[0060] Figure 10 This is the hydrogen NMR spectrum of the product of Example 5 of the present invention;

[0061] Figure 11 This is the carbon NMR spectrum of the product of Example 5 of the present invention;

[0062] Figure 12 This is the 1H NMR spectrum of the product of Example 6 of the present invention;

[0063] Figure 13 This is the carbon NMR spectrum of the product of Example 6 of the present invention;

[0064] Figure 14 This is the hydrogen NMR spectrum of the product of Example 7 of the present invention;

[0065] Figure 15 This is the carbon NMR spectrum of the product of Example 7 of the present invention;

[0066] Figure 16 This is the 1H NMR spectrum of the product of Example 8 of the present invention;

[0067] Figure 17 This is the carbon NMR spectrum of the product of Example 8 of the present invention;

[0068] Figure 18 This is the 1H NMR spectrum of the product of Example 9 of the present invention;

[0069] Figure 19 This is the carbon NMR spectrum of the product of Example 9 of the present invention;

[0070] Figure 20 This is the hydrogen NMR spectrum of the product of Example 10 of the present invention;

[0071] Figure 21 This is the carbon NMR spectrum of the product of Example 10 of the present invention;

[0072] Figure 22 This is the hydrogen NMR spectrum of the product of Example 11 of the present invention;

[0073] Figure 23 This is the carbon NMR spectrum of the product of Example 11 of the present invention;

[0074] Figure 24 This is the hydrogen NMR spectrum of the product of Example 12 of the present invention;

[0075] Figure 25 This is the carbon NMR spectrum of the product of Example 12 of the present invention;

[0076] Figure 26 This is the hydrogen NMR spectrum of the product of Example 13 of the present invention;

[0077] Figure 27 This is the carbon NMR spectrum of the product of Example 13 of the present invention;

[0078] Figure 28 This is the 1H NMR spectrum of the product of Example 14 of this invention;

[0079] Figure 29 This is the carbon NMR spectrum of the product of Example 14 of the present invention;

[0080] Figure 30This is the hydrogen NMR spectrum of the product of Example 15 of the present invention;

[0081] Figure 31 This is the carbon NMR spectrum of the product of Example 15 of the present invention. Detailed Implementation

[0082] I. Synthesis of ketone activator 2-pyridylhydrazone (MPHA)

[0083] The reaction route is as follows:

[0084]

[0085] General Procedure A:

[0086] Step 1: In a 500 mL round-bottom flask equipped with a magnetic stirrer, add 2-cyanopyridine (80 mmol), methylhydrazine sulfate (200 mmol), potassium phosphate (400 mmol), and ethanol (200 mL) sequentially. Then, heat under reflux for 48 h at a nitrogen atmosphere. After the reaction is complete, filter, distill under reduced pressure, and recrystallize to obtain the product, ketone activator 2-pyridylhydrazoneamide (MPHA).

[0087] Following standard procedure A, a pale yellow solid (7.2 g, 60%) was obtained. 1 H NMR (400MHz, CD3CN) δ8.51–8.43(m,1H),7.98(dd,J=8.1,1.1Hz,1H),7.75–7.69(m,1H),7.28(ddt,J=7.3,4.9,1.1Hz,1H),5.26(s,2H),2.85(s,3H).

[0088] II. Deacylation method mediated by dihydrotriazole aromatization precursor

[0089] The reaction route is as follows:

[0090]

[0091] or:

[0092]

[0093] R3 is a substituent formed by the ring opening of Cy.

[0094] Includes the following steps:

[0095] (a) Dissolve the ketone and 2-pyridylhydrazone (MPHA) in a solvent, add an activating additive to the system, and heat under a nitrogen atmosphere for 12-24 hours to obtain the dihydrotriazole aromatization precursor;

[0096] (b) Using aryl halides as arylizing agents, the dihydrotriazole aromatization precursor generates alkyl radicals under photocatalyst, base, solvent and light conditions. Subsequently, the radicals are captured by divalent nickel complexes to form trivalent nickel intermediates, and finally carbon-carbon bond reduction and elimination occur to obtain the deacylated aryl product.

[0097] The mechanism of deacylation of ketones is as follows: Figure 1 As shown, taking cyclopentanone as an example, cyclopentanone and MPHA first condense in situ to generate a dihydrotriazole intermediate. This intermediate undergoes a single-electron transfer with an excited-state photocatalyst to obtain intermediate A, which is then deprotonated to form a free radical B. Zero-valent nickel D and an aryl halide undergo oxidative addition to obtain intermediate E. Free radical B is captured by E to form a trivalent nickel complex F, which then undergoes reductive elimination to obtain an arylated product G and a monovalent nickel C. C undergoes a single-electron transfer with the photocatalyst to achieve photocatalytic cycling and nickel catalytic cycling.

[0098] The activating additive is at least one of camphor sulfonic acid, p-toluene sulfonic acid, adamantane carboxylic acid, basic alumina, neutral alumina, and basic alumina.

[0099] General Procedure B

[0100] Step 1: Add the ketone activator MPHA (0.60 mmol), the additive camphor sulfonic acid (0.06 mmol), the starting ketone (0.72 mmol), and the solvent acetonitrile (1 mL) to an 8 mL reaction flask in sequence. Heat to 78 °C under a nitrogen atmosphere and react for 24 h.

[0101] Step 2: After Step 1, add the photocatalyst Ir[(dFCF3)ppy]2dtbbpyPF6 (0.002 mmol), nickel catalyst Ni(dppf)Cl2 (0.04 mmol), base K3PO4 (0.8 mmol), aryl bromide (0.2 mmol), and solvent acetonitrile (3 mL) to the reaction flask in sequence. Irradiate the reaction flask with a 40 W LED blue light with a wavelength of 440 nm under a nitrogen atmosphere and react for 36 h.

[0102] General procedure C

[0103] Step 1: Add the ketone activator MPHA (0.60 mmol), the additive camphor sulfonic acid (0.06 mmol), the starting ketone (0.72 mmol), and the solvent acetonitrile (1 mL) to an 8 mL reaction flask in sequence. Heat to 78 °C under a nitrogen atmosphere and react for 24 h.

[0104] Step 2: After Step 1, add the photocatalyst Ir[(dFCF3)ppy]2dtbbpyPF6 (0.002 mmol), nickel catalyst Ni(dppf)Cl2 (0.04 mmol), base K3PO4 (0.8 mmol), aryl bromide (0.2 mmol), and solvent acetonitrile (3 mL) to the reaction flask in sequence. Irradiate the reaction flask with a 40 W LED blue light with a wavelength of 440 nm under a nitrogen atmosphere. Turn off the heat dissipation device in the reaction apparatus and react for 24 h.

[0105] General Procedure D

[0106] Step 1: Add the ketone activator MPHA (0.60 mmol), the additive camphor sulfonic acid (0.06 mmol), the starting ketone (0.72 mmol), and the solvent acetonitrile (1 mL) to an 8 mL reaction flask in sequence. Heat to 78 °C under a nitrogen atmosphere and react for 12–24 h.

[0107] Step 2: After Step 1, add the photocatalyst 4DPAIPN (0.004 mmol), nickel catalyst Ni(PBu3)2Br2 (0.04 mmol), base K3PO4 (0.6 mmol), aryl bromide (0.2 mmol), and solvent acetonitrile (3 mL) to the reaction flask in sequence. Irradiate the reaction flask with a 40 W LED blue light with a wavelength of 440 nm under a nitrogen atmosphere. Turn off the heat dissipation device of the photoreaction chamber and react for 48 h.

[0108] The raw material ketone is selected from:

[0109]

[0110] Aryl halogenated compounds are selected from:

[0111]

[0112] Example 1: 1-(3-(tetrahydro-2H-pyran-4-yl)phenyl)ethane-1-one

[0113]

[0114] Using ketone S21 and aryl halide S48 as starting materials, the product 1-(3-(tetrahydro-2H-pyran-4-yl)phenyl)ethane-1-one (94%) was obtained by following general procedure B. 1H NMR (400MHz, CDCl3) δ7.86–7.76(m,2H),7.47–7.37(m,2H),4.19–3.98(m,2H),3.53( td,J=11.5,2.7Hz,2H),2.83(tt,J=11.6,4.3Hz,1H),2.60(s,3H),1.96–1.66(m,4H). 13 C NMR(101MHz, CDCl3)δ198.39,146.48,137.48,131.66,128.90,126.71,126.66,68.37,41.57,33.88,26.84.HRMS(ESI-TOF)m / z calcd.forC 13 H 17 O2([M+H)) + )205.1223,found:205.1224.

[0115] Figure 2 and Figure 3 The images show the 1H NMR and 1C NMR spectra of 1-(3-(tetrahydro-2H-pyran-4-yl)phenyl)ethane-1-one, respectively.

[0116] Example 2: 2-Methoxy-4-tetrahydropyran-4-ylpyridine

[0117]

[0118] Using ketone S21 and aryl halide S60 as starting materials, the product 2-methoxy-4-tetrahydropyran-4-ylpyridine (72%) was obtained by following the general procedure C. 1 H NMR (400MHz, CDCl3) δ8.07(d,J=5.4Hz,1H),6.73(dd,J=5.4,1.5Hz,1H),6.58(d,J=1.5Hz,1H),4.06(dt, J=11.5,3.5Hz,2H),3.91(s,3H),3.57–3.42(m,2H),2.69(td,J=10.4,9.8,4.7Hz,1H),1.85–1.67(m,4H). 13 C NMR(101MHz, CDCl3)δ164.73,157.43,146.93,115.92,108.79,68.12,53.50,40.86,32.96.HRMS(ESI-TOF)m / zcalcd.forC 11 H 16 NO2([M+H] + )194.1176,found:194.1175.

[0119] Figure 4 and Figure 5 The images show the 1H and 1C NMR spectra of 2-methoxy-4-tetrahydropyran-4-ylpyridine, respectively.

[0120] Example 3: 1-(3-cyclopentylphenyl)ethane-1-one

[0121]

[0122] Using ketone S3 and aryl halide S48 as starting materials, the product 1-(3-cyclopentylphenyl)ethane-1-one (62%) was obtained by following general procedure B. 1 H NMR (400MHz, CDCl3) δ7.84(t,J=1.9Hz,1H),7.76(dt,J=7.6,1.5Hz,1H),7.45(dt,J=7.7,1.6Hz,1H),7.37(t,J=7.6Hz,1H),3.18–2.93(m, 1H),2.60(s,3H),2.10(dddt,J=11.0,8.7,6.1,1.2Hz,2H),1.83(qddd,J=9.4,7.3,4.3,3.1Hz,2H),1.77–1.67(m,2H),1.68–1.53(m,2H). 13 C NMR(101MHz, CDCl3)δ198.64,147.23,137.28,132.15,128.57,126.96,126.11,45.95,34.75,26.85,25.63.HRMS(ESI-TOF)m / z calcd.forC 13 H 17 O([M+H] + )189.1274,found:189.1272.

[0123] Figure 6 and Figure 7 The images show the 1H NMR spectrum and 1C NMR spectrum of 1-(3-cyclopentylphenyl)ethane-1-one, respectively.

[0124] Example 4: (4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)(phenyl)methyl ketone

[0125]

[0126] Using ketone S26 and aryl halide S47 as starting materials, the product (4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)(phenyl)methyl ketone (38%) was obtained according to the general procedure D. 1 H NMR (400MHz, CDCl3) δ8.63–8.58(m,1H),7.97(dd,J=8.0,1.3Hz,1H),7.72–7.60(m,5H),7.53–7.45(m,1H),7.39(td,J=7.6,7.2,1.5H z,2H),7.18(td,J=7.5,2.0Hz,3H),3.89–3.72(m,5H),3.62(td,J=6.6,1.3Hz,2H),2.99(td,J=6.3,1.3Hz,2H),2.83(t,J=6.6Hz,2H). 13 CNMR (101MHz, CDCl3) δ196.48, 160.36, 155.07, 149.93 (d, J = 5.0Hz), 144.11, 137.85, 136.74, 135.71, 132. 32,130.38,130.03,128.77,128.31,123.67,121.29,71.43,68.98,36.20,35.77,27.22.HRMS(ESI-TOF)m / z calcd.for C 25 H 25 N4O2([M+H)) + )413.1972,found:413.1964.

[0127] Figure 8 and Figure 9 The images show the 1H and 1C NMR spectra of (4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)(phenyl)methyl ketone, respectively.

[0128] Example 5: 1-(4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one

[0129]

[0130] Using ketone S26 and aryl halide S44 as starting materials, the product 1-(4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one (46%) was obtained by following general procedure D. 1H NMR (400MHz, CDCl3) δ8.65(dd,J=5.0,1.6Hz,1H),8.00(dd,J=7.9,1.2Hz,1H),7.79–7.66(m,3H),7.28–7.19(m,1H),7.14( d,J=7.9Hz,2H),3.84–3.70(m,5H),3.66–3.52(m,2H),2.98(t,J=6.1Hz,2H),2.80(t,J=6.6Hz,2H),2.46(d,J=1.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ197.91,160.13,155.09,149.85,149.75,144.75,136.94,135.39,129 .00,128.53,123.74,121.34,71.30,68.96,36.13,35.77,27.18,26.60.HRMS(ESI-TOF)m / z calcd.forC 20 H 23 N4O2([M+H)) + )351.1816,found:351.1810.

[0131] Figure 10 and Figure 11 The images show the 1H and 1C NMR spectra of 1-(4-(2-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one, respectively.

[0132] Example 6: 1-(2-methoxy-4-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one

[0133]

[0134] Using ketone S26 and aryl halide S53 as starting materials, the product 1-(2-methoxy-4-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one (39%) was obtained by following general procedure D. 1HNMR (400MHz, CDCl3) δ8.74–8.63(m,1H),8.06(d,J=8.0Hz,1H),7.76(td,J =7.7,1.8Hz,1H),7.63(d,J=8.0Hz,1H),7.33–7.16(m,1H),6.77(dd,J=7.9 ,1.5Hz,1H),6.73–6.70(m,1H),3.87–3.82(m,4H),3.65(t,J=6.8Hz,2H),3 .04(t,J=6.1Hz,2H),2.83(t,J=6.7Hz,2H),2.55(s,2H).HRMS(ESI-TOF)m / z calcd.for C 21 H 25 N4O3([M+H)) + )381.1921,found:381.1914.

[0135] Figure 12 and Figure 13 The images show the 1H and 1C NMR spectra of 1-(2-methoxy-4-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)phenyl)ethyl-1-one, respectively.

[0136] Example 7: 1-(2-methoxy-5-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)ethyl)phenyl)ethyl-1-one

[0137]

[0138] Using ketone S26 and aryl halide S64 as starting materials, the product 1-(2-methoxy-5-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)ethyl)phenyl)ethyl-1-one (41%) was obtained by following general procedure D. 1H NMR (400MHz, CDCl3) δ8.64(d,J=4.7Hz,1H),8.00(d,J=7.8Hz,1H),7.69(tt,J=7.9, 2.0Hz,1H),7.47(d,J=2.4Hz,1H),7.21(q,J=5.7,4.8Hz,1H),7.12(dd,J=8.6,2.5H z,1H),6.74(dd,J=8.4,1.9Hz,1H),3.80(s,3H),3.78–3.72(m,5H),3.53(td,J=6.7 ,1.9Hz,2H),2.98(td,J=6.3,2.0Hz,2H),2.76–2.64(m,2H),2.51(d,J=1.9Hz,3H). 13 C NMR (101MHz, CDCl3) δ199.94,160.15,157.63,155.14,149.87,136.81,134.09,131.00,130.47,12 7.85,123.65,121.31,111.72,71.84,68.91,55.56,35.81,35.01,31.94,27.21.HRMS(ESI-TOF)m / z calcd.for C 21 H 25 N4O3([M+H)) + )381.1921,found:381.1916.

[0139] Figure 14 and Figure 15 The images show the 1H and 1C NMR spectra of 1-(2-methoxy-5-(2-(1-methyl-3-pyridin-2-yl)-1H-1,2,4-triazol-5-yl)ethoxy)ethyl)ethyl)phenyl)ethyl-1-one, respectively.

[0140] Example 8: (3R,4S)-3-(3-acetylbenzyl)-4-((1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester

[0141]

[0142] Using ketone S38 and aryl halide S48 as starting materials, the product (3R,4S)-3-(3-acetylbenzyl)-4-((1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester (68%) was obtained according to the general procedure D. 1H NMR (400MHz, CDCl3) δ8.72–8.63(m,1H),8.10–8.02(m,1H),7.83–7.68(m,3H),7.46–7.32(m,2H),7.28–7.22(m, 1H),3.88–3.79(m,3H),3.56–3.11(m,4H),3.01–2.85(m,3H),2.84–2.56(m,3H),2.54(s,3H),1.46–1.34(m,9H). 13 C NMR (101MHz, CDCl3) δ198.14,160.54,155.33,155.15,154.76,149.97,149.8 2,140.49,140.34,137.57,136.81,133.46,128.96,128.34,128.28,126.73,1 23.78,121.47,79.68,79.61,50.38,49.80,49.49,49.15,42.48,42.05,40.0 2,39.24,35.43,34.25,33.85,29.73,28.55,26.69,24.43.HRMS(ESI-TOF)m / z calcd.for C 27 H 34 N5O3([M+H)) + )476.2656,found:476.2647.

[0143] Figure 16 and Figure 17 The images show the 1H and 1C NMR spectra of (3R,4S)-3-(3-acetylbenzyl)-4-((1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester, respectively.

[0144] Example 9: (2S)-N-(1-(3-acetylphenyl)-5-(1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)pent-3-yl)-2-(6-methoxynaphth-2-yl)propionamide

[0145]

[0146] Using ketone S40 and aryl halide S48 as starting materials, the product (2S)-N-(1-(3-acetylphenyl)-5-(1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)pent-3-yl)-2-(6-methoxynaphth-2-yl)propionamide (30%) was obtained according to general procedure D. 1H NMR (400MHz, CDCl3) δ8.72(ddd,J=4.8,1.9,1.0Hz,1H),8.03(dt,J=7.9,1.1Hz,1H),7.75(td,J=7.7,1.8Hz,1H),7.72– 7.65(m,2H),7.60–7.52(m,3H),7.34(dd,J=8.5,1.9Hz,1H),7.29(ddd,J=7.6,4.8,1.2Hz,1H),7.23(t,J=7.7Hz,1H),7 .13–7.05(m,3H),5.60(d,J=9.2Hz,1H),4.18–3.96(m,1H),3.88(s,3H),3.79(s,3H),3.56(q,J=7.1Hz,1H),2.84–2.70 (m,2H),2.50(s,3H),2.47–2.39(m,2H),2.04–1.94(m,2H),1.80–1.69(m,1H),1.63–1.55(m,1H),1.52(d,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ198.37,174.43,160.22,157.83,156.78,150.03,149.8 8,142.00,137.31,136.81,136.77,133.81,133.24,129.23,129.02,128.66,1 28.09,127.68,126.14,126.00,123.76,121.36,119.30,105.73,55.39,49.1 9,47.14,37.44,35.41,32.46,31.98,26.73,23.04,18.32.HRMS(ESI-TOF)m / z calcd.for C 35 H 38 N5O3([M+H)) + )576.2969,found:576.2961.

[0147] Figure 18 and Figure 19 The images show the 1H and 1C NMR spectra of ((2S)-N-(1-(3-acetylphenyl)-5-(1-methyl-3-(pyridin-2-yl)-1H-1,2,4-triazol-5-yl)pent-3-yl)-2-(6-methoxynaphth-2-yl)propionamide, respectively.

[0148] Example 10: 4-(3-acetylphenyl)piperidine-1-carboxylic acid tert-butyl ester

[0149]

[0150] Using ketone S6 and aryl halide S48 as starting materials, tert-butyl 4-(3-acetylphenyl)piperidine-1-carboxylic acid was obtained by following general procedure B. 1 H NMR (400MHz, CDCl3) δ7.84–7.72(m,2H),7.45–7.38(m,2H),4.25(d,J=12.8Hz,2H),2.87–2.75(m,2H),2 .71(tt,J=12.2,3.6Hz,1H),2.59(s,3H),1.89–1.75(m,2H),1.64(qd,J=12.6,4.4Hz,2H),1.47(s,9H). 13 C NMR(101MHz, CDCl3)δ198.29,154.91,146.45,137.53,131.69,128.88,126.73,126.65,79.64,44.38,42.75,33.19,28.59,26.78.HRMS(ESI-TOF)m / z calcd.for C 14 H 18 NO3([M+H)) + )248.1281,found:248.1282.

[0151] Figure 20 and Figure 21 The images show the 1H and 1C NMR spectra of 4-(3-acetylphenyl)piperidine-1-carboxylic acid tert-butyl ester, respectively.

[0152] Example 11: 3-(3-acetylphenyl)azacyclobutane-1-carboxylic acid tert-butyl ester

[0153]

[0154] Using ketone S5 and aryl halide S48 as raw materials, the product 3-(3-acetylphenyl)azacyclobutane-1-carboxylic acid tert-butyl ester (36%) was obtained by following general procedure C. 1 H NMR (400MHz, CDCl3) δ7.87(d,J=1.9Hz,1H),7.83(dt,J=7.6,1.5Hz,1H),7.54(dt,J=7.7,1.6Hz,1H),7.45(t, J=7.7Hz,1H),4.35(t,J=8.7Hz,2H),3.98(dd,J=8.6,6.0Hz,2H),3.85–3.69(m,1H),2.61(s,3H),1.46(s,9H). 13C NMR (101MHz, CDCl3) δ198.06,156.48,143.01,137.69,131.51,129.20,127.29,126.66,79.82,56.47,33.51,28.54,26.82.HRMS(ESI-TOF)m / z calcd.for C 12 H 14 NO3([M+H)) + )220.0968,found:220.0974.

[0155] Figure 22 and Figure 23 The images show the 1H and 1C NMR spectra of 3-(3-acetylphenyl)azacyclobutane-1-carboxylic acid tert-butyl ester, respectively.

[0156] Example 12: 1-(3-(3,4-dimethoxyphenethyl)phenyl)ethyl-1-one

[0157]

[0158] Using ketone S8 and aryl halide S48 as starting materials, the product 1-(3-(3,4-dimethoxyphenethyl)phenyl)ethyl-1-one (68%) was obtained by following general procedure C. 1 H NMR (400MHz, CDCl3) δ7.77(dd,J=6.3,2.0Hz,2H),7.39–7.31(m,2H),6.78(d,J=8.2Hz,1H),6.69(dd,J=8.1,2 .0Hz,1H),6.64(d,J=2.0Hz,1H),3.84(s,3H),3.82(s,3H),3.00–2.92(m,2H),2.90–2.83(m,2H),2.56(s,3H). 13 C NMR (101MHz, CDCl3) δ198.37,148.88,147.46,142.30,137.31,133.93,133.48,128.57,128 .34,126.21,120.42,112.02,111.39,56.00,55.88,38.01,37.40,26.71.HRMS(ESI-TOF)m / z calcd.for C 18 H 21 O3([M+H)) + )285.1485,found:285.1484.

[0159] Figure 24 and Figure 25The images show the 1H NMR and 1C NMR spectra of 1-(3-(3,4-dimethoxyphenylethyl)phenyl)ethyl-1-one, respectively.

[0160] Example 13: Ethyl 3-(3-acetylphenyl)propionate

[0161]

[0162] Using ketone S14 and aryl halide S48 as starting materials, ethyl 3-(3-acetylphenyl)propionate (51%) was obtained by following general procedure C. 1 H NMR (400MHz, CDCl3) δ7.96–7.64(m,2H),7.44–7.34(m,2H),4.12(q,J=7.1Hz,2H),3. 01(t,J=7.7Hz,2H),2.64(dd,J=8.1,7.3Hz,2H),2.59(s,3H),1.23(t,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ198.26,172.70,141.29,137.55,133.30,128.86,128.22,126.59,60.66,35.83,30.91,26.78,14.33.HRMS(ESI-TOF)m / z calcd.for C 13 H 17 O3([M+H)) + )221.1172,found:221.1174.

[0163] Figure 26 and Figure 27 The images show the 1H and 1C NMR spectra of ethyl 3-(3-acetylphenyl)propionate, respectively.

[0164] Example 14: 1-(3-(phenoxymethyl)phenyl)ethyl-1-one

[0165]

[0166] Using ketone S7 and aryl halide S48 as starting materials, the product 1-(3-(phenoxymethyl)phenyl)ethyl-1-one (85%) was obtained by following general procedure B. 1H NMR (400MHz, CDCl3) δ8.04(t,J=2.1Hz,1H),7.92(dt,J=7.8,1.5Hz,1H),7.66(dt,J=7.6,1.4H z,1H),7.49(t,J=7.7Hz,1H),7.36–7.26(m,2H),7.05–6.94(m,3H),5.12(s,2H),2.62(s,3H). 13 C NMR(101MHz, CDCl3)δ198.06,158.60,137.86,137.51,132.17,129.68,129.02,128.05,127.30,69.46,26.83.HRMS(ESI-TOF)m / zcalcd.for C 15 H 15 O2([M+H)) + )227.1067,found:227.1067.

[0167] Figure 28 and Figure 29 The images show the 1H NMR and 1C NMR spectra of 1-(3-(phenoxymethyl)phenyl)ethyl-1-one, respectively.

[0168] Example 15: N,N-Dimethyl-3-(tetrahydro-2H-pyran-4-yl)aniline

[0169]

[0170] Using ketone S21 and aryl halide S55 as raw materials, N,N-dimethyl-3-(tetrahydro-2H-pyran-4-yl)aniline (86%) was obtained by following general procedure B. 1 H NMR (400MHz, CDCl3) δ7.23–7.14(m,1H),6.64–6.56(m,3H),4.14–3.98(m,2H),3 .51(td,J=11.7,2.4Hz,2H),2.93(s,6H),2.74–2.60(m,1H),1.92–1.67(m,4H). 13 C NMR(101MHz, CDCl3)δ150.79,146.87,129.22,115.11,111.18,110.78,68.52,42.14,40.70,34.07.HRMS(ESI-TOF)m / z calcd.for C 13 H 20 NO([M+H] + )206.1539,found:206.1539.

[0171] Figure 30 and Figure 31 The images show the 1H NMR and 1C NMR spectra of N,N-dimethyl-3-(tetrahydro-2H-pyran-4-yl)aniline, respectively.

[0172] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for deacylation of ketones driven by visible light-induced aromatization, characterized in that, include: (1) Dissolve the ketone and MPHA in a solvent, add an activating additive, and heat under an inert gas atmosphere to activate the reaction to obtain the dihydrotriazole aromatization precursor. (2) The product of step (1) is mixed with an aryl halide, with or without purification, and photocatalytically reacted under the conditions of photocatalyst, nickel catalyst, base, solvent and light to obtain the deacylated aryl product of the ketone. The structural formula of the dihydrotriazole aromatized precursor is shown in formula (I) or formula (II): R1, R2, and Cy are derived from the raw material ketone; The aryl halide is selected from at least one of the following groups of compounds: ； The ketones mentioned are 2-acetylindane, acetylcyclohexane, cyclopentyl ethyl ketone, cyclobutylmethyl ketone, 1-BOC-3-acetyl acridine, 1-N-BOC-4-acetylpiperidine, phenoxyethyl ketone, 4-(3,4-dimethoxyphenyl)butane-2-one, 4-(benzyloxy)butane-2-one, 6-methyl-2-heptanone, methyl 4-acetylbutyrate, ethyl acetylpropionate, 4-acetylbutyl ethyl ester, n-propyl acetylpropionate, methyl 5-acetylvalerate, 4-(4-methoxyphenyl)-2-butanone, 6-methyl-5-hepten-2-ethylheptanone. - Ketones, Cyclohexylacetone, Naphthylbutyrone, BETA-dihydroionone, 1-(tetrahydro-2H-pyran-4-yl)ethyl ketone, 3,7-dimethyl-1-(5-oxohexyl)-3,7-dihydro-1H-purine-2,6-dione, 8R,9S,13S,14S)-13-methyl-3-(5-oxohexyl)oxy)-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopentanphenanthrene-17-one, 5-nonanone, Cyclohexanone, Tetrahydropyranone, 4-propylcyclohexane Alkyl-1-one, 4-phenylcyclohexane-1-one, 2-(4-oxocyclohexyl)isoindoline-1,3-dione, N-tert-butoxycarbonyl-4-piperidinone, 4(4'-benzonitrile)cyclohexanone, 1,4-cyclohexanedione monoethylene glycol ketal, ethyl p-cyclohexanone formate, 1-tert-butoxycarbonyl-2-methyl-piperidinone, N-BOC-3-methyl-4-piperidinone, 4-N-benzyloxycarbonylaminocyclohexanone, N-tert-butoxycarbonyl-nortropinone, cis-5-oxohexahydrocyclopentadien[C]pyrrole-2(1H)-carboxylic acid tert- At least one of the following: butyl ester, 2-((4-oxocyclohexyl)carbamoyl)pyrrolidine-1-carboxylic acid tert-butyl ester, (S)-2-(6-methoxynaphthyl-2-yl)-N-(4-oxocyclohexyl)propionamide, 5-(2,5-dimethylphenoxy)-2,2-dimethyl-N-(4-oxocyclohexyl)pentanamide, 2-(3-benzoylphenyl)-N-(4-oxocyclohexyl)propionamide, and 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-N-(4-oxocyclohexyl)thiazole-5-carboxamide; The activating additive is at least one of camphor sulfonic acid, p-toluene sulfonic acid, and acidic alumina; The photocatalysts are 2,4,5,6-tetra(diphenylamino)isophthalonitrile, [2,2'-bi(4-tert-butylpyridine)]bis[2-(4-fluorophenyl)pyridine]iridium(III)hexafluorophosphate, [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridyl-KN,KN]bis[5-fluoro-2-(5-methyl-2-pyridyl-KN)phenylKC]iridiumhexafluorophosphate, and 4,4'-bis(tri... At least one of the following: (4,4'-di-tert-butyl-2,2'-bipyridine bis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl)phenyl]iridium(III) hexafluorophosphate, (4,4'-di-tert-butyl-2,2'-bipyridine)bis[(2-pyridyl)phenyl]iridium(III) hexafluorophosphate, and bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium hexafluorophosphate; The nickel catalyst is at least one of (1,1'-bis(diphenylphosphine)ferrocene) nickel chloride, dibromobis(tributylphosphine) nickel(II), dibromobis(triphenylphosphine) nickel, and 1,3-bis(diphenylphosphine propane) nickel chloride; The reaction route is as follows: or: R3 is a triazole substituent formed by the ring opening of Cy and linked to MPHA residues.

2. The method for visible light-induced aromatization-driven deacylation of ketones according to claim 1, characterized in that, In step (1), the molar amount of ketone is 100-120% of the molar amount of MPHA; the molar amount of activating additive is 2-10% of the molar amount of MPHA. In step (2), the molar amount of photocatalyst is 1 to 2% of the molar amount of MPHA; the molar amount of nickel catalyst is 10 to 20% of the molar amount of MPHA; and the molar amount of alkali is 300 to 400% of the molar amount of MPHA.

3. The method for visible light-induced aromatization-driven deacylation of ketones according to claim 1, characterized in that, In step (1), the temperature of the ketone activation reaction is 78~95℃ and the reaction time is 12~24h; in step (2), the temperature of the photocatalytic reaction is room temperature to 80℃ and the reaction time is 24~48h.

Images