A reaction method for preparing olefins by deacylation of ketones induced by visible light

Abstract

The invention discloses a reaction method for preparing an olefin by deacylation of a ketone induced by visible light, comprising: (1) dissolving a ketone and 2-pyridylhydrazoneamide in a solvent, adding an activation additive, and heating under an inert gas atmosphere for an activation reaction to obtain a dihydrotriazole aromatization precursor; and (2) mixing the product of step (1) with an olefin with or without purification, and performing a photocatalytic reaction under a photocatalyst, a cobalt catalyst, a base, an additive, a solvent, and illumination conditions to obtain a deacylated olefin product of the ketone. The reaction method for preparing an olefin by deacylation of a ketone of the present invention has the advantages of simple and readily available raw materials, mild reaction conditions, and wide substrate applicability, and meets the requirements for developing green and environmentally friendly chemistry.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and in particular to a reaction method for preparing olefins by deacylation of ketones induced by visible light. Background Art

[0002] Olefins are important building blocks for organic synthesis, enabling easy structural transformations of compounds such as alkyl halides, ethers, alcohols, and carbonyl compounds. Furthermore, as important chemical raw materials, olefins are widely used in the production of polymers, detergents, and synthetic lubricants, making their preparation crucial. Ketones, among the most common organic compounds, are found in natural products and pharmaceutical molecules. Furthermore, as one of the most commonly used functional groups in organic synthesis, they can be easily converted from other functional groups. Therefore, achieving efficient deacylation of ketones to produce olefins is crucial.

[0003] Among classical organic transformations, only a handful of reactions are known to convert ketones to alkenes, including the Wittig reaction, the Shapiro reaction, and the Bamford-Stevens reaction. However, these approaches are limited by the applicable scope of substrates, the configurational selectivity of products, and the limitations of reaction conditions.

[0004] Free radicals play an important role in many fields such as organic chemistry, materials science, and biochemistry. As a key intermediate, they can be used in the synthesis and transformation of a variety of valuable compounds in organic chemical reactions. Among the many transformation schemes of ketones, there are many cases of using transition metal catalysis to activate the carbon-carbon bond of ketones. However, there are few reports on strategies to generate free radicals through the activation of the carbon-carbon bond of ketones. The main limiting factors are insufficient driving force for the reaction and the instability of the generated free radical precursors. With the continuous deepening of research on free radical precursors, strategies to generate free radicals using aromatization as the driving force have begun to attract attention.

[0005] Among them, in 2021, the research group of Professor Dong Guangbin of the University of Chicago reported a case of aromatization-driven CC bond activation of ketones (J.Am.Chem.Soc.2021,143,20042). They used 2-pyridylhydrazoneamide (MPHA) as a ketone activation reagent to achieve copper-mediated deacylation alkenylation of methyl ketones. This reaction provides new ideas and methods for the efficient synthesis of alkenes. However, this transformation requires an equivalent amount of transition metal copper as an oxidant, which limits the substrate range and synthetic applications of the reaction.

[0006] Considering the application of alkenes in human daily production and life, developing an efficient and mild method to achieve the deacylation of ketones to prepare alkenes has important practical significance. Summary of the Invention

[0007] The present invention provides a reaction method for preparing olefins by deacylation of ketones induced by visible light, which is the application of a dihydrotriazole aromatization precursor in the deacylation Heck reaction of ketones, and can achieve the deacylation conversion of ketones efficiently and mildly.

[0008] The technical solutions of the present invention are as follows:

[0009] The present invention provides a reaction method for preparing olefins by deacylation of ketones induced by visible light, comprising:

[0010] (1) dissolving a ketone and 2-pyridylhydrazoneamide in a solvent, adding an activation additive, and heating under an inert gas atmosphere to perform an activation reaction to obtain a dihydrotriazole aromatization precursor;

[0011] (2) The product of step (1) is mixed with an olefin with or without purification, and subjected to a photocatalytic reaction under the conditions of a photocatalyst, a cobalt catalyst, a base, an additive, a solvent and light to obtain a deacylated olefin product of the ketone.

[0012] Preferably, the ketone is represented by formula (i) or formula (ii); the olefin is represented by formula (iii) to (v); the deacylated olefin product of the ketone is represented by formula (vi) to (xi);

[0013]

[0014] in:

[0015] R1 and R2 are independently selected from optionally substituted alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkoxy, and alkyl ester groups;

[0016] Cy1 is selected from an optionally substituted 5- to 8-membered cycloalkyl group, a heterocyclic group containing one or more nitrogen, oxygen or sulfur atoms as ring members;

[0017] Ar is selected from an optionally substituted aromatic group or a heteroaryl group;

[0018] R3 is selected from hydrogen, alkyl, aromatic, and heteroaryl;

[0019] R4 and R5 are independently selected from hydrogen, optionally substituted sulfonyl, carbonyl, or ester; R4 and R5 are not simultaneously hydrogen;

[0020] Cy2 is selected from an optionally substituted 5- to 8-membered cycloalkenyl, a heterocycloalkenyl containing one or more nitrogen, oxygen or sulfur atoms as ring members;

[0021] R6 is a substituent formed by ring opening of Cy1.

[0022] The reaction route is as follows:

[0023]

[0024] Preferably, R1 and R2 are independently selected from:

[0025] optionally substituted C1-C6 alkyl, optionally substituted C3-C6 cycloalkyl, optionally substituted C1-C6 alkoxy, aryl, heteroaryl, alkyl ester group.

[0026] Further preferably, R1 and R2 are independently selected from:

[0027]

[0028] Preferably, Cy1 is selected from:

[0029]

[0030] In Cy1, * indicates the position of the C=O bond.

[0031] Preferably, the ketone is 2-acetyl indane (S1), acetyl cyclohexane (S2), cyclopentyl ethyl ketone (S3), cyclobutyl methyl ketone (S4), 1-BOC-3-acetyl acridine (S5), 1-N-Ts-4-acetyl piperidine (S6), 1,4-diacetyl piperidine (S7), 4-(3,4-dimethoxyphenyl) butane-2-one (S8), 4-(benzyloxy) butane-2-one (S9), 6-methyl-2-heptanone (S10), methyl 4-acetobutyrate (S11), ethyl levulinate (S12), 4-(acetoxyphenyl)-2-butanone (S13), diethyl acetonosuccinate (S14), BETA-dihydroionone (S15) , 4-(4-methoxyphenyl)-2-butanone (S16), phenoxyacetone (S17), cyclohexylacetone (S18), nabumetone (S19), 1-(tetrahydro-2H-pyran-4-yl)ethanone (S20), 2-(5-oxohexyl)-1H-isoindole-1,3(2H)-dione (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-cyclopentaphenanthrene-17-one (S23), 4, cyclopentaphenanthrene-17-one (S24), 4, cyclopentaphenanthrene-17-one (S25), 4, cyclopentaphenanthrene-17-one (S26), 4, cyclopentaphenanthrene-17-one (S27), 4, cyclopentaphenanthrene-17-one (S28), 4, cyclopentaphenanthrene-17-one (S29), 4, cyclopentaphenanthrene-17-one (S30), 4, cyclopentaphenanthrene-17-one (S31), 4, cyclopentaphenanthrene-17-one (S32), 4, cyclopentaphenanthrene-17-one (S33), 4, cyclopentaphenanthrene-17-one (S34), 4, cyclopentaphenanthrene-17-one (S35), 4, cyclopentaphenanthrene-17- Hexanone (S24), tetrahydropyrone (S25), 4-propylcyclohexane-1-one (S26), 4-phenylcyclohexane-1-one (S27), 2-(4-oxocyclohexyl)isoindoline-1,3-dione (S28), N-tert-butyloxycarbonyl-4-piperidone (S29), 4(4'-benzonitrile)cyclohexanone (S30), 1,4-cyclohexanedione monoethylene glycol ketal (S31), 3,3-dimethyl-1,5-dioxaspiro[5.5]undecan-9-one (S32), adamantanone (S33), N-BOC-3-methyl-4-piperidone (S34), 4-N-benzyloxycarbonylaminocyclohexanone (S35), N-tert-butyloxycarbonyl-nortropine (S36), At least one of tert-butyl cis-5-oxohexahydrocyclopenta[C]pyrrole-2(1H)-carboxylate (S37), tert-butyl 2-((4-oxocyclohexyl)carbamoyl)pyrrolidine-1-carboxylate (S38), (S)-2-(6-methoxynaphthalen-2-yl)-N-(4-oxocyclohexyl)propionamide (S39), 5-(2,5-dimethylphenoxy)-2,2-dimethyl-N-(4-oxocyclohexyl)pentanamide (S40), 2-(3-benzoylphenyl)-N-(4-oxocyclohexyl)propionamide (S41), and 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-N-(4-oxocyclohexyl)thiazole-5-carboxamide (S42).

[0032]

[0033]

[0034] Preferably, the olefin is selected from:

[0035]

[0036] The dihydrotriazole aromatization precursor is shown in formula (I) or formula (II):

[0037]

[0038] Preferably, the preparation method of the dihydrotriazole aromatization precursor comprises: dissolving ketone and 2-pyridylhydrazoneamide in a solvent, adding an activation additive, and heating to 60-100° C. under an inert gas atmosphere to perform an activation reaction.

[0039] In step (1), the activation additive is at least one of camphorsulfonic acid, p-toluenesulfonic acid, adamantanecarboxylic acid, basic alumina, neutral alumina and acidic alumina.

[0040] In step (1), the solvent is at least one of acetonitrile (MeCN), 1,4-dioxane (Dioxane), ethyl acetate (EA), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), methyl tert-butyl ether (MTBE), hexafluoroisopropanol (HFIP), dichloromethane (DCM), 1,2-dichloroethane (DCE), and N-methylpyrrolidone (NMP).

[0041] The photocatalyst is 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPAIPN);

[0042] [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridyl-KN,KN]bis[5-fluoro-2-(5-methyl-2-pyridyl-KN)phenyl KC]iridium hexafluorophosphate (Ir[F(CH3)ppy]2(dtbbpy)PF6); [2,2'-bi(4-tert-butylpyridine)]bis[2-(4-fluorophenyl)pyridyl]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)phenyl KC]iridium hexafluorophosphate (Ir[(FMeCF3ppy)2dtbbpy]PF6); 4,4'-bis(trifluoromethyl)-2,2'-bipyridyl At least one of pyridinebis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl)phenyl]iridium(III) hexafluorophosphate (Ir[(dFdCF3ppy)2dtbbpy]PF6); fac-tris(2-phenylpyridine)iridium (fac-Ir(ppy)3); (4,4'-di-tert-butyl-2,2'-bipyridyl)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)]iridium hexafluorophosphate (Ir[dF(CF3)ppy]2(dtbbpy)PF6); and 2,4,5,6-tetracarbazolyl-1,3-dicyanobenzene (4CzIPN).

[0043] Preferably, the photocatalyst is [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridyl-KN,KN]bis[5-fluoro-2-(5-methyl-2-pyridyl-KN)phenyl KC]iridium hexafluorophosphate. The olefin configuration prepared using this photocatalyst is mainly E-form.

[0044] Preferably, the photocatalyst is 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile. The olefin configuration prepared using this photocatalyst is mainly Z-configuration.

[0045] The cobalt catalyst is at least one of chloro(pyridine)bis(dimethylglyoxime)cobalt(III)oxime (Co(dmgH)2PyCl), dichlorobis(dimethylglyoxime)cobalt(II) (Co(dmgH)2Cl2), chlorobis(dimethylglyoxime)[4-(dimethylamino)pyridine]cobalt(III) (Co(dmgH)2(DMAP)Cl), dichlorobis(dimethylglyoxime)cobalt(III) (Co(dmgH)(dmgH2)Cl2), and chlorobis(dimethylglyoxime)[4-(methoxy)pyridine]cobalt(III) (Co(dmgH)2(OMe)PyCl).

[0046] In step (2), the solvent is at least one of dichloromethane (DCM), 1,2-dichloroethane (DCE), acetonitrile (MeCN), toluene, trifluorotoluene (PhCF3), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), 1,4-dioxane, acetone, chloroform (CHCl3), ethyl acetate (EA), and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP).

[0047] The base is at least one of 4-dimethylaminopyridine (DMAP), N,N-diisopropylethylamine (DIPEA), lithium carbonate (Li2CO3), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), tetramethylguanidine (TMG), 1,8-diazobisspiro[5.4.0]undec-7-ene (DBU), cesium carbonate (Cs2CO3), potassium tert-butoxide (t-BuOK), sodium methoxide (MeONa), lithium hydroxide (KOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium phosphate (K3PO4), dipotassium hydrogen phosphate (K2HPO4), and potassium dihydrogen phosphate (KH2PO4).

[0048] In step (2), the additive is at least one of indium bromide (InBr3), indium chloride (InCl3), aluminum fluoride (AlF3), silver fluoride (AgF), cerium chloride (CeCl3), chromium chloride (CrCl3), ferrous chloride (FeCl2), ferric acetate (Fe(OAc)3), aluminum acetate (Al(OAc)3), indium trifluoromethanesulfonate (In(OTf)3), cesium trifluoromethanesulfonate (Cs(OTf)3), and ferric trifluoromethanesulfonate (Fe(OTf)3).

[0049] Preferably, in step (1), based on the molar amount of 2-pyridylhydrazoneamide, the molar amount of ketone is 100-120%; and the molar amount of the activating additive is 2-10%.

[0050] Preferably, in step (2), based on the molar amount of 2-pyridylhydrazoneamide, the molar amount of the photocatalyst is 1-2%; the molar amount of the cobalt catalyst is 10-20%; the molar amount of the base is 20-40%; and the molar amount of the additive is 20-50%.

[0051] Preferably, in step (1), the temperature of the ketone activation reaction is 78 to 95° C., and the reaction time is 12 to 24 hours; in step (2), the temperature of the photocatalytic reaction is room temperature to 60° C., and the reaction time is 24 to 48 hours.

[0052] Preferably, the wavelength of the light is 390-467 nm. The light wavelength can be selected from 390, 427, 440, 456, 467 nm, etc.

[0053] In the reaction method for preparing olefins by visible light-induced deacylation of ketones disclosed in the present invention, under the conditions of a photocatalyst, an organic solvent, a cobalt catalyst, a base, an additive and light, the dihydrotriazole aromatization precursor after ketone activation driven by visible light-induced aromatization can efficiently generate alkyl radicals, which are then added to the olefins, and a β-H elimination reaction occurs under the action of the cobalt catalyst, thereby obtaining a series of ketone deacylated Heck products.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] (1) The present invention utilizes the dihydrotriazole aromatization precursor generated in situ by ketone and MPHA as the reaction substrate, which greatly broadens the source of alkyl radicals and also provides new ideas and guidance for the carbon-carbon bond activation of ketone.

[0056] (2) The deacylation reaction method of ketones to prepare alkenes of the present invention has the advantages of simple and readily available raw materials, mild reaction conditions, and wide substrate applicability. It meets the requirements of developing green and environmentally friendly chemistry and provides a reliable method for the preparation of alkenes.

[0057] (3) Triazole structures are widely present in drug molecules. The method of the present invention can achieve a ring-opening reaction on cyclic ketone derivatives and obtain a series of triazole compounds containing double bond structures. These compounds can undergo later functionalization reactions. Therefore, this method is expected to be widely used in the post-modification of drug molecules. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 1 is a reaction mechanism diagram of the preparation of olefins by deacylation mediated by a dihydrotriazole aromatization precursor in an embodiment of the present invention;

[0059] Figure 2 is the H NMR spectrum of the product of Example 1 of the present invention;

[0060] Figure 3 is the NMR carbon spectrum of the product of Example 1 of the present invention;

[0061] Figure 4 This is the H NMR spectrum of the product of Example 2 of the present invention;

[0062] Figure 5 This is the C NMR spectrum of the product of Example 2 of the present invention;

[0063] Figure 6 This is the H NMR spectrum of the product of Example 3 of the present invention;

[0064] Figure 7 This is the NMR carbon spectrum of the product of Example 3 of the present invention;

[0065] Figure 8 is the H NMR spectrum of the product of Example 4 of the present invention;

[0066] Figure 9 is the NMR carbon spectrum of the product of Example 4 of the present invention;

[0067] Figure 10 is the H NMR spectrum of the product of Example 5 of the present invention;

[0068] Figure 11 is the NMR carbon spectrum of the product of Example 5 of the present invention;

[0069] Figure 12 is the H NMR spectrum of the product of Example 6 of the present invention;

[0070] Figure 13 is the NMR carbon spectrum of the product of Example 6 of the present invention;

[0071] Figure 14 is the H NMR spectrum of the product of Example 7 of the present invention;

[0072] Figure 15 is the NMR carbon spectrum of the product of Example 7 of the present invention;

[0073] Figure 16 is the H NMR spectrum of the product of Example 8 of the present invention;

[0074] Figure 17 is the C NMR spectrum of the product of Example 8 of the present invention;

[0075] Figure 18 is the H NMR spectrum of the product of Example 9 of the present invention;

[0076] Figure 19 is the NMR carbon spectrum of the product of Example 9 of the present invention;

[0077] Figure 20 is the H NMR spectrum of the product of Example 10 of the present invention;

[0078] Figure 21 is the C NMR spectrum of the product of Example 10 of the present invention;

[0079] Figure 22 is the H NMR spectrum of the product of Example 11 of the present invention;

[0080] Figure 23 is the NMR carbon spectrum of the product of Example 11 of the present invention;

[0081] Figure 24 is the H NMR spectrum of the product of Example 12 of the present invention;

[0082] Figure 25 This is the NMR carbon spectrum of the product of Example 12 of the present invention. DETAILED DESCRIPTION

[0083] 1. Synthesis of Ketone Activator 2-Pyridylhydrazoneamide (MPHA)

[0084] The reaction route is as follows:

[0085]

[0086] General Procedure A:

[0087] Step 1: To a 500 mL eggplant-shaped flask equipped with a magnetic stirrer, add 2-cyanopyridine (80 mmol), methylhydrazine sulfate (200 mmol), potassium phosphate (400 mmol), and ethanol (200 mL) in this order. Heat under reflux under a nitrogen atmosphere for 48 hours. After completion of the reaction, filter, evaporate under reduced pressure, and recrystallize to obtain the product, the ketone activator 2-pyridylhydrazoneamide (MPHA).

[0088] General procedure A was followed to give a pale yellow solid (7.2 g, 60%). 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).

[0089] Heck reaction of ketone deacylation mediated by dihydrotriazole aromatization precursor

[0090] The reaction route is as follows:

[0091]

[0092]

[0093] The steps include:

[0094] (a) dissolving a ketone and 2-pyridylhydrazone amide (MPHA) in a solvent, adding an activating additive to the system, and heating under a nitrogen atmosphere for 12-24 hours to obtain a dihydrotriazole aromatization precursor;

[0095] (b) The aromatization precursor of dihydrotriazole generates alkyl radicals under the conditions of photocatalyst, base, additive, solvent and light. The radicals add to olefins and then undergo β-H elimination reaction under the action of cobalt catalyst to obtain a series of polysubstituted olefin products.

[0096] The reaction mechanism of deacylation of ketones to prepare alkenes is as follows Figure 1 As shown, taking 1-(tetrahydro-2H-pyran-4-yl)ethanone as an example, 1-(tetrahydro-2H-pyran-4-yl)ethanone and MPHA are first condensed to generate a dihydrotriazole intermediate in situ, which undergoes single electron transfer with the excited state photocatalyst to obtain intermediate A, which is then deprotonated to form a free radical B, which adds to the olefin to obtain a free radical C; C is then captured by divalent cobalt D to form a trivalent cobalt complex E, and finally undergoes reductive elimination to obtain the olefin product H and the trivalent cobalt hydrogen species F, which combines with protons to become trivalent cobalt G, which then undergoes single electron transfer with the photocatalyst to realize the photocatalytic cycle and the cobalt catalytic cycle.

[0097] The activation additive is at least one of camphorsulfonic acid, p-toluenesulfonic acid, adamantanecarboxylic acid, basic alumina, neutral alumina, and acidic alumina.

[0098] General Procedure B

[0099] Step 1: In a 25 mL reaction flask, add ketone activator MPHA (10 mmol), additive camphorsulfonic acid (0.1 mmol), raw material ketone (12 mmol) and solvent acetonitrile (10 mL) in sequence, heat to 78 ° C under nitrogen atmosphere, and react for 24 h.

[0100] Step 2: After step 1, the solvent in the reaction flask is dried by rotary evaporation, and then the dihydrotriazole intermediate is obtained by column chromatography separation or recrystallization.

[0101] General Procedure C

[0102] To an 8 mL reaction flask equipped with a magnetic stirrer, the dihydrotriazole intermediate (0.2 mmol), the photocatalyst Ir[F(CH3)ppy]2(dtbbpy)PF6 (0.004 mmol), the cobalt catalyst Co(dmgH)2Cl2 (0.02 mmol), the base DMAP (0.08 mmol), the additive indium tribromide (0.1 mmol), the olefin (0.6 mmol), and the solvent DCM (2 mL) were added in sequence. Under a nitrogen atmosphere, the reaction flask was illuminated with a 40 W, 440 nm LED blue light. The magnetic stirrer was turned on, the heat sink in the reactor was activated, and the reaction was allowed to react for 24 hours. The reaction product was primarily E-form.

[0103] General Procedure D

[0104] To an 8 mL reaction flask equipped with a magnetic stirrer, the dihydrotriazole intermediate (0.2 mmol), photocatalyst 4DPAIPN (0.004 mmol), cobalt catalyst Co(dmgH)2PyCl (0.02 mmol), base DMAP (0.08 mmol), additive indium tribromide (0.1 mmol), olefin (0.6 mmol), and solvent DCM (2 mL) were added in sequence. Under a nitrogen atmosphere, the flask was illuminated with a 40 W, 440 nm LED blue light. The magnetic stirrer was turned on, the heat sink in the reactor was activated, and the reaction was allowed to react for 24 hours. The reaction product exhibited a predominantly Z-configuration.

[0105] General Procedure E

[0106] To an 8 mL reaction flask equipped with a magnetic stirrer, the dihydrotriazole intermediate (0.2 mmol), the photocatalyst Ir[F(CH3)ppy]2(dtbbpy)PF6 (0.004 mmol), the cobalt catalyst Co(dmgH)2Cl2 (0.02 mmol), the base DMAP (0.08 mmol), the additive indium tribromide (0.1 mmol), the olefin (0.6 mmol), and the solvent DCM (2 mL) were added in sequence. Under a nitrogen atmosphere, the reaction flask was illuminated with a 40 W, 440 nm LED blue light. The magnetic stirrer was turned on, the heat sink in the reactor was turned off, and the reaction was allowed to react for 48 hours. The reaction product was primarily E-form.

[0107] The raw material ketone is selected from:

[0108]

[0109]

[0110] The olefin is selected from:

[0111]

[0112] Example 1: (E)-4-(3-chlorophenylvinyl)tetrahydro-2H-pyran

[0113]

[0114] Starting from ketone S20 and olefin S44, the product (E)-4-(3-chlorostyryl)tetrahydro-2H-pyran was obtained according to General Procedure C (64%). 1 H NMR (400MHz, CDCl3) δ7.27(t,J=7.6Hz,1H),7.24–7.19(m,2H),7.11(d,J=7.2Hz,1H),6.33(d,J=11.6Hz,1H),5 .53(dd,J=11.6,10.1Hz,1H),3.96(dt,2H),3.42(td,J=11.4,3.1Hz,2H),2.81–2.69(m,1H),1.60–1.49(m,4H). 13 C NMR (101MHz, CDCl3) δ139.42,138.17,134.25,129.67,128.63,127.05,126.94,126.71,67.41,34.27,32.79.

[0115] Figure 2 and Figure 3 They are the H NMR spectrum and C NMR spectrum of (E)-4-(3-chlorostyryl)tetrahydro-2H-pyran, respectively.

[0116] Example 2: (Z)-4-(2-chlorophenylvinyl)tetrahydro-2H-pyran

[0117]

[0118] Starting from ketone S20 and olefin S45, the product (Z)-4-(2-chlorostyryl)tetrahydro-2H-pyran was obtained according to General Procedure D (58%). 1 H NMR (400MHz, CDCl3) δ7.41–7.37(m,1H),7.25–7.19(m,3H),6.45(d,J=11.5Hz,1H),5.61(dd,J= 11.5,10.1Hz,1H),3.98–3.90(m,2H),3.40–3.32(m,2H),2.64–2.52(m,1H),1.61–1.48(m,4H). 13C NMR (101MHz, CDCl3) δ138.07,135.99,133.68,130.25,129.57,128.37,126.52,125.69,67.42,34.39,32.73.

[0119] Figure 4 and Figure 5 They are the H-NMR spectrum and C-NMR spectrum of (Z)-4-(2-chlorostyryl)tetrahydro-2H-pyran, respectively.

[0120] Example 3: (E)-4-(3-bromostyryl)tetrahydro-2H-pyran

[0121]

[0122] Starting from ketone S20 and olefin S47, the product (E)-4-(3-bromostyryl)tetrahydro-2H-pyran was obtained according to General Procedure C (58%). 1 H NMR (400MHz, CDCl3) δ7.50(s,1H),7.33(d,J=7.8Hz,1H),7.25(d,J=6.9Hz,1H),7.16(t,J=7.8Hz,1H),6.30(d,J=16.0Hz,1H) ,6.16(dd,J=16.0,6.7Hz,1H),4.06–3.98(m,2H),3.51–3.42(m,2H),2.44–2.33(m,1H),1.73–1.66(m,2H),1.62–1.49(m,2H). 13 C NMR (101MHz, CDCl3) δ139.82,136.31,130.15,130.04,128.98,127.06,124.89,122.86,67.79,38.48,32.57.

[0123] Figure 6 and Figure 7 They are the H NMR spectrum and C NMR spectrum of (E)-4-(3-bromostyryl)tetrahydro-2H-pyran, respectively.

[0124] Example 4: tert-Butyl (Z)-(4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)phenyl)carbonate

[0125]

[0126] Starting from ketone S20 and olefin S55, the product (Z)-tert-butyl (4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)phenyl)carbonate (75%) was obtained according to General Procedure D. 1H NMR (400MHz, CDCl3) δ7.27–7.21(m,2H),7.16–7.11(m,2H),6.36(d,J=11.6Hz,1H),5.48(dd,J=11.6,10.0Hz ,1H),3.95(dt,J=11.8,4.2,2.3Hz,2H),3.41(td,J=11.4,3.0Hz,2H),2.85–2.73(m,1H),1.67–1.50(m,13H). 13 CNMR (101MHz, CDCl3) δ152.10,149.85,137.19,135.29,129.56,128.49,127.39,121.22,83.74,67.44,34.14,32.91,27.84.

[0127] Figure 8 and Figure 9 They are the H NMR spectrum and C NMR spectrum of tert-butyl (Z)-(4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)phenyl)carbonate, respectively.

[0128] Example 5: 1-phenyl-3-(tetrahydro-2H-pyran-4-yl)-1H-pyrrole-2,5-dione

[0129]

[0130] Starting from ketone S20 and olefin S68, the product 1-phenyl-3-(tetrahydro-2H-pyran-4-yl)-1H-pyrrole-2,5-dione was obtained according to General Procedure C (46%). 1 H NMR (400MHz, CDCl3) δ7.50–7.43(m,2H),7.39–7.32(m,2H),6.41(s,1H),4.07(dt,2H), 3.55(td,J=11.9,2.0Hz,2H),2.93–2.83(m,1H),1.98–1.89(m,2H),1.76–1.63(m,2H). 13 C NMR (101MHz, CDCl3) δ169.88,169.56,152.77,131.57,129.24,127.94,126.08,125.66,67.61,32.60,31.05.

[0131] Figure 10 and Figure 11 They are the H NMR spectrum and C NMR spectrum of 1-phenyl-3-(tetrahydro-2H-pyran-4-yl)-1H-pyrrole-2,5-dione, respectively.

[0132] Example 6: (E)-2-(2-(tetrahydro-2H-pyran-4-yl)vinyl)isoindoline-1,3-dione

[0133]

[0134] Starting from ketone S6 and olefin S67, the product (E)-2-(2-(tetrahydro-2H-pyran-4-yl)vinyl)isoindoline-1,3-dione was obtained according to General Procedure C (39%). 1 H NMR (400MHz, CDCl3) δ7.89–7.83(m,2H),7.76–7.71(m,2H),6.68–6.56(m,2H),4.00(dt,2 H),3.46(td,J=11.7,2.3Hz,2H),2.41–2.30(m,1H),1.74–1.67(m,2H),1.64–1.59(m,2H). 13 C NMR (101MHz, Chloroform-d) δ166.81,134.52,131.83,126.10,123.66,117.05,67.79,37.27,32.83.

[0135] Figure 12 and Figure 13 These are the H NMR spectrum and C NMR spectrum of (E)-2-(2-(tetrahydro-2H-pyran-4-yl)vinyl)isoindoline-1,3-dione, respectively.

[0136] Example 7: (E)-benzyl 3-(tetrahydro-2H-pyran-4-yl)acrylate

[0137]

[0138] Starting from ketone S20 and olefin S71, the product (E)-3-(tetrahydro-2H-pyran-4-yl)acrylate was obtained according to General Procedure C (41%). 1 H NMR (400MHz, CDCl3) δ7.41–7.30(m,5H),6.95(dd,J=15.8,6.5Hz,1H),5.85(dd,J=15.8,1.5Hz,1H),5.18(s,2 H),4.03–3.95(m,2H),3.43(td,J=11.7,2.3Hz,2H),2.45–2.34(m,1H),1.71–1.63(m,2H),1.58–1.46(m,2H). 13C NMR (101MHz, CDCl3) δ166.68,152.66,136.17,128.72,128.42,128.38,119.71,67.52,66.35,37.79,31.46.

[0139] Figure 14 and Figure 15 They are the H NMR spectrum and C NMR spectrum of benzyl (E)-3-(tetrahydro-2H-pyran-4-yl)acrylate, respectively.

[0140] Example 8: (Z)-4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)benzonitrile

[0141]

[0142] Starting from ketone S20 and olefin S50, the product (Z)-4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)benzonitrile (60%) was obtained according to General Procedure D. 1 H NMR (400MHz, CDCl3) δ7.62(d,J=8.3Hz,2H),7.32(d,J=8.1Hz,2H),6.38(d,J=11.5Hz,1H),6.29-5.63(dd,J=16.0,6.5Hz, , (dd,J=11.7,10.1Hz,1H),4.06–3.92(m,2H),3.51–3.32(m,2H),2.79–2.66(m,1H),2.49–2.36(m,2H),1.64–1.51(m,2H). 13 C NMR (101MHz, CDCl3) δ142.34,139.79,132.49,132.27,129.20,126.86,126.67,119.03,110.46,67.30,34.46,32.64.

[0143] Figure 16 and Figure 17 They are the H NMR spectrum and C NMR spectrum of (Z)-4-(2-(tetrahydro-2H-pyran-4-yl)vinyl)benzonitrile, respectively.

[0144] Example 9: (E)-2-(6-(4-chlorophenyl)hex-5-en-1-yl)isoindoline-1,3-dione

[0145]

[0146] Starting from ketone S21 and olefin S43, the product (E)-2-(6-(4-chlorophenyl)hex-5-en-1-yl)isoindoline-1,3-dione was obtained according to General Procedure C (53%). 1 H NMR (400MHz, CDCl3) δ7.84(dd,J=5.4,3.0Hz,2H),7.71(dd,J=5.5,3.1Hz,2H),7.24(s,4H),6.32(dd,1H),6.16(dd,J =15.8,6.9Hz,1H),3.71(t,J=7.2Hz,2H),2.25(q,J=7.3Hz,2H),1.73(tt,J=7.5Hz,2H),1.54(tt,J=15.0,6.9Hz,2H). 13 CNMR (101MHz, CDCl3) δ168.61,136.30,134.04,132.53,132.27,131.04,129.31,128.71,127.30,123.33,37.94,32.63,28.27,26.58.

[0147] Figure 18 and Figure 19 These are the H NMR spectrum and C NMR spectrum of (E)-(2-(6-(4-chlorophenyl)hex-5-en-1-yl)isoindoline-1,3-dione, respectively.

[0148] Example 10: (E)-6-(4-chlorophenyl)hex-5-enoic acid methyl ester

[0149]

[0150] Starting from ketone S11 and olefin S43, the product (E)-6-(4-chlorophenyl)hex-5-enoic acid methyl ester (35%) was obtained according to General Procedure C. 1 H NMR (400MHz, CDCl3) δ7.36–7.30(m,4H),6.49–6.38(m,1H),6.22(dt,J=15.7,6.9 Hz,1H),3.73(s,3H),2.43(t,J=7.4Hz,2H),2.36–2.27(m,2H),1.95–1.83(m,2H). 13 C NMR (101MHz, Chloroform-d) δ174.13,136.15,132.65,130.40,129.72,128.75,127.30,51.71,33.50,32.44,24.50.

[0151] Figure 20 and Figure 21They are the H NMR spectrum and C NMR spectrum of methyl (E)-6-(4-chlorophenyl)hex-5-enoate, respectively.

[0152] Example 11: 4-(2,2-Diphenylvinyl)tetrahydro-2H-pyran

[0153]

[0154] Starting from ketone S6 and olefin S63, the product 4-(2,2-diphenylvinyl)tetrahydro-2H-pyran was obtained according to General Procedure C (66%). 1 H NMR (400MHz, CDCl3) δ7.40–7.30(m,2H),7.27–7.13(m,8H),5.87(d,J=9.8Hz,1H),3.89(dt, 2H),3.28(td,J=11.1,4.0Hz,2H),2.43–2.29(m,1H),1.65–1.49(m,4H),1.65–1.57(m,2H). 13 C NMR(101MHz,Chloroform-d)δ145.04,142.52,141.12,140.32,133.80,129.76,128 .63,128.43,128.25,127.93,127.30,127.20,127.18,126.31,67.48,35.75,33.05.

[0155] Figure 22 and Figure 23 These are the H-NMR spectrum and C-NMR spectrum of 4-(2,2-diphenylvinyl)tetrahydro-2H-pyran, respectively.

[0156] Example 12: (E)-2-(5-(7-(4-chlorostyryl)bicyclo[3.3.1]nonan-3-yl)-1-methyl-1H-1,2,4-triazol-3-yl)pyridine

[0157]

[0158] Starting from ketone S33 and olefin S43, the product (E)-2-(5-(7-(4-chlorostyryl)bicyclo[3.3.1]nonan-3-yl)-1-methyl-1H-1,2,4-triazol-3-yl)pyridine was obtained according to General Procedure E (39%). 1H NMR (400MHz, CDCl3) δ8.71(d,1H),8.11(d,J=22.4,7.9Hz,1H),7.87(t,1H),7.41–7.28(m,5H),6.35(dd,J=34.4,13.8Hz,1H),6.14-5.53 (dd,J=15.9,6.8Hz,dd,1H),3.90(s,3H),3.47–3.33(m,1H),3.12–2.97(m,1H),2.32–2.09(m,4H),1.94–1.60(m,7H),1.41–1.18(m,4H). 13 C NMR(101MHz,Chloroform-d)δ160.67,160.43,150.20,149.92,138.94,137.17,136.27,132.38,1 30.01,128.57,127.30,126.66,123.64,121.64,39.98,35.39,31.65,28.36,27.76,26.91,25.21.

[0159] Figure 24 and Figure 25 They are the H NMR spectrum and C NMR spectrum of (E)-2-(5-(7-(4-chlorostyryl)bicyclo[3.3.1]nonan-3-yl)-1-methyl-1H-1,2,4-triazol-3-yl)pyridine, respectively.

[0160] The embodiments described above provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements and equivalent substitutions made within the scope of the principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A reaction method for preparing olefins by deacylation of ketones induced by visible light, characterized in that: include: (1) A ketone and 2-pyridylhydrazone amide are dissolved in a solvent, an activation additive is added, and the mixture is heated under an inert gas atmosphere for activation reaction to obtain a dihydrotriazole aromatization precursor; (2) the product of step (1) is mixed with an olefin with or without purification, and subjected to a photocatalytic reaction in the presence of a photocatalyst, a cobalt catalyst, a base, an additive, a solvent and light to obtain a deacylated olefin product of the ketone; The ketone is represented by formula (i) or formula (ii); the olefin is represented by formula (iii) to (v); the deacylated olefin product of the ketone is represented by formula (vi) to (xi); ； ； in: R1 and R2 are independently selected from optionally substituted alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkoxy, and alkyl ester groups; Cy1 is selected from an optionally substituted 5- to 8-membered cycloalkyl group, a heterocyclic group containing one or more nitrogen, oxygen or sulfur atoms as ring members; Ar is selected from an optionally substituted aromatic group or a heteroaryl group; R3 is selected from hydrogen, alkyl, aromatic, and heteroaryl; R4 and R5 are independently selected from hydrogen, optionally substituted sulfonyl, carbonyl, or ester; R4 and R5 are not simultaneously hydrogen; Cy2 is selected from an optionally substituted 5- to 8-membered cycloalkenyl group, a heterocycloalkenyl group containing one or more nitrogen, oxygen or sulfur atoms as ring members; R6 is a substituent formed by the ring opening of Cy1; The activation additive is at least one of camphorsulfonic acid, p-toluenesulfonic acid, adamantanecarboxylic acid, basic alumina, neutral alumina and acidic alumina; The photocatalyst is 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile; [4,4'-bis(1,1-dimethylethyl)-2,2'-bipyridyl-KN,KN]bis[5-fluoro-2-(5-methyl-2-pyridyl-KN)phenyl KC]iridium hexafluorophosphate; [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)phenyl KC]iridium hexafluorophosphate; 4,4'-bis( At least one of (trifluoromethyl)-2,2'-bipyridylbis[3,5-difluoro-2-[5-trifluoromethyl-2-pyridyl)phenyl]iridium(III) hexafluorophosphate; fac-tris(2-phenylpyridine)iridium; (4,4'-di-tert-butyl-2,2'-bipyridyl)bis[(2-pyridyl)phenyl]iridium(III) hexafluorophosphate; bis[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bi(4-tert-butylpyridine)]iridium hexafluorophosphate; and 2,4,5,6-tetracarbazolyl-1,3-dicyanobenzene; The cobalt catalyst is at least one of chloro(pyridine)bis(dimethylglyoxime)cobalt(III)oxime, dichlorobis(dimethylglyoxime)cobalt(II), chlorobis(dimethylglyoxime)[4-(dimethylamino)pyridine]cobalt(III), dichlorobis(dimethylglyoxime)cobalt(III), and chlorobis(dimethylglyoxime)[4-(methoxy)pyridine]cobalt(III); The additive is at least one of indium tribromide, indium trichloride, aluminum trifluoride, silver fluoride, cerium trichloride, chromium trichloride, ferrous chloride, ferric acetate, aluminum acetate, indium trifluoromethanesulfonate, cesium trifluoromethanesulfonate, and ferric trifluoromethanesulfonate.

2. The method for producing olefins by visible light-induced deacylation of ketones according to claim 1, characterized in that: R1 and R2 are independently selected from: 。 3. The method for producing olefins by visible light-induced deacylation of ketones according to claim 1, wherein: Cy1 is selected from: ； In Cy1, * refers to the position of the C=O bond.

4. The method for producing olefins by visible light-induced deacylation of ketones according to claim 1, characterized in that: The dihydrotriazole aromatization precursor is represented by formula (I) or formula (II): 。 5. The method for producing olefins by visible light-induced deacylation of ketones according to claim 1, characterized in that: In step (1), the temperature of the ketone activation reaction is 78-95°C, and the reaction time is 12-24 hours; in step (2), the temperature of the photocatalytic reaction is room temperature to 60°C, and the reaction time is 24-48 hours.

Images