Method for synthesizing benzyl alkyl ketone compound through visible light catalysis

Abstract

The invention discloses a method for synthesizing a benzyl alkyl ketone compound through visible light catalysis. The method for synthesizing the benzyl alkyl ketone compound through visible light catalysis comprises the following steps: in an inert atmosphere, adding an olefin compound, an anhydride compound or an acyl imidazole compound and a tertiary amine compound into an organic solvent of a photocatalyst, mixing, and carrying out a photoreaction under a visible light irradiation condition to obtain the benzyl alkyl ketone compound. According to the method, tertiary amine is oxidized into alpha-site free radical species of nitrogen under the mild photooxidation condition, so that fracture of olefin carbon-carbon pi bonds is induced, meanwhile, anhydride (or an acylimidazole compound) is used as an acyl source, fracture of carbon-carbon sigma bonds is promoted by using a visible light catalyzed oxidation-reduction strategy, and the olefin is synthesized. Therefore, the process of obtaining the benzyl alkyl ketone compound through the carbon-carbon bond breakage acylation reaction of olefin is realized. The synthesis method is mild, efficient and simple to operate, and has atom economy.

Description

Technical Field

[0001] The present invention belongs to the field of photocatalytic synthesis, relates to the synthesis of benzyl alkyl ketone compounds, and particularly relates to a method for synthesizing benzyl alkyl ketone compounds by visible light catalysis. Background Art

[0002] The carbon-carbon bond is one of the basic skeleton units constituting organic compounds, and the cleavage functionalization of the carbon-carbon bond is of great significance in organic synthesis. At the end of the 19th century, Wallach first realized the cleavage of the carbon-carbon bond (Justus Liebigs Ann. Chem. 1890, 259, 309 - 331.). Subsequently, the cleavage of the carbon-carbon bond has been widely used in organic synthesis. For example, in the first total synthesis route of paclitaxel achieved by Holton, the ring expansion process was realized by the cleavage of the carbon-carbon bond of cycloalcohol catalyzed by Lewis acid to further obtain paclitaxel (J. Am. Chem. Soc. 1994, 116, 1597 - 1598.). Since the rapid development of visible light catalysis in 2008, compared with the relatively high transition state energy barrier required for thermal reactions, the chemical reactions initiated by the singlet or triplet states excited by visible light hardly require a transition state energy barrier, which enables visible light catalysis to achieve carbon-carbon bond cleavage as a mild method. Currently, the methods of photocatalytic carbon-carbon bond cleavage have been developed rapidly and diversely. For example, the cleavage of carbon-carbon single bonds is promoted by the oxidation of cyclobutanone oxime derivatives to generate imine radicals, and the cleavage of carbon-carbon single bonds is induced by the oxidative aromatization of Hantzsch ester derivatives. For another example, the cleavage of carbon-carbon single bonds is realized by the oxidation of alkyl alcohol derivatives to generate alkoxy radicals, and the cleavage of carbon-carbon single bonds is promoted by the oxidation of carboxylic acids and derivatives or the reduction of organic peroxides using unstable peroxide bonds. In addition, the release of cyclopropane ring strain can also be used as a driving force to induce the cleavage of carbon-carbon single bonds (Chem. Rev. 2021, 121, 506 - 561.). However, there are few current methods for photocatalytic carbon-carbon double bond cleavage. For example, the Wu Jie research group has developed a selective cleavage and dihalogenation reaction of trisubstituted olefins (Nat. Commun. 2020, 11, 4462.). The Xiao Jianliang research group has developed a class of enzyme-mimicking non-heme manganese complexes, and through the strategy of photo-assisted oxygen activation, an aerobic oxidation cleavage reaction of unactivated olefins under mild conditions has been realized (J. Am. Chem. Soc. 2021, 143, 10005 - 10013.). On the other hand, the benzyl alkyl ketone skeleton exists in many active molecules, and the study of its chemical synthesis has important scientific significance..

[0003] Up to now, there has been no patent or literature report on the synthesis of benzyl alkyl ketone compounds by the means of visible light catalysis to achieve the acylative cleavage of the carbon-carbon double bond of olefins. Summary of the Invention

[0004] The object of the present invention is to provide a method for the visible light-catalyzed synthesis of benzyl alkyl ketone compounds.

[0005] Under mild photo-oxidation conditions, the method of the present invention oxidizes tertiary amines into α-position radical species of nitrogen, induces the cleavage of the carbon-carbon π bond of alkenes, and uses acid anhydrides (or acyl imidazole compounds) as acyl sources to promote the cleavage of carbon-carbon σ bonds by means of a visible light-catalyzed redox strategy, thereby realizing the process of acylating the carbon-carbon bond cleavage of alkenes to obtain benzyl alkyl ketone compounds. The synthesis method of the present invention is mild, efficient, simple to operate, and has atom economy.

[0006] A method for the visible light-catalyzed synthesis of benzyl alkyl ketone compounds provided by the present invention includes the following steps: in an inert atmosphere, an alkene compound, an acid anhydride compound or an acyl imidazole compound, and a tertiary amine compound are added to an organic solvent of a photocatalyst and mixed, and a photoreaction is carried out under visible light irradiation conditions to obtain benzyl alkyl ketone compounds.

[0007] In the above method, the structural formula of the alkene compound is as shown in Formula I below:

[0008]

[0009] In Formula I, R 1 is H or Me, R 2 is H, Me, OMe, OAc, OPh, Ph, F, Cl or COOMe, R 3 is H, Me, t Bu, OMe, OAc, Ph, Me 3 Si, 1-pyrazolyl or SMe, R 4 is H, Me or OMe, R 5 is H or Me.

[0010] In the present invention, the structural formula of the 1-pyrazolyl is as follows, and the dotted line is the site connected to the benzene ring in Formula I:

[0011]

[0012] In the present invention, the groups in Formula I may specifically be as follows:

[0013] 1) R 1 is H, R 2 is H, R 4 is H, R 5 is H, R 3 is H, Me, t Bu, OAc, Ph, TMS, 1-pyrazolyl or SMe;

[0014] 2) R 1 is H, R 3 is H, R 4 is H, R 5 is H, R 2 is Me, OMe, OAc, OPh, Ph, F, Cl or COOMe;

[0015] 3) R 1 is Me, R 2 is H, R 3 is H, R 4 is H, R 5 is H;

[0016] 4) R 1 is H, R 2 is F, R 3 is H, R 4 is Me or OMe, R 5 is H;

[0017] 5) R 1 is H, R 2 is OMe, R 3 is H, R 4 is Me or OMe, R 5 is H;

[0018] 6) R 1 is H, R 2 is Me, R 3 is H, R 4 is Me, R 5 is H;

[0019] 7) R 1 is H, R 2 is OMe, R 3 is OMe, R 4 is H or OMe, R 5 is H;

[0020] 8) R 1 is H, R 2 is H or OPh, R 3 is H, R 4 is H, R 5 is Me.

[0021] In the above method, the structural formula of the acid anhydride compound is shown as Formula II below:

[0022]

[0023] In Formula II, R is Et, Me, i Bu, iPr (isopropyl), cyclopropyl.

[0024] In the above method, the structure of the acyl imidazole compound is shown as the following formula Ⅲ:

[0025]

[0026] In formula Ⅲ, R' is -CH 2 CH 2 CH=CH 2 (4-(1-butylene)-yl in English), -CH 2 CH 2 CH 2 CH 2 Cl (4-(1-chlorobutane)-yl in English), -CH 2 CH 2 Ph (2-(1-ethylbenzene)-yl in English), -(CH 2 ) 7 CH=CH(CH 2 ) 7 CH 3 (1-(8Z-heptadecene)-yl in English).

[0027] In the present invention, the structural formula of formula Ⅲ is specifically as follows:

[0028]

[0029] In the above method, the tertiary amine compound is at least one of N,N-dicyclohexylmethylamine (MeN(cycloheptyl) 2 ), N,N-cyclohexyl-tert-butylmethylamine (MeN(cycloheptyl) 2 t (Bu)), N,N-isopropyl-tert-butylmethylamine (MeN( i Pr) t (Bu)) and N,N-cycloheptyl-tert-butylmethylamine (MeN(cycloheptyl) 2 t (Bu)), and their structural formulas are shown as follows in sequence:

[0030]

[0031] In the above method, the photocatalyst is selected from 4CzIPN, 4DPAIPN, 3DPA2FBN, 3DPAFIPN and Ir(ppy) 2(dtbbpy)PF 6 At least one of them has the following structural formula:

[0032]

[0033] In the above method, the organic solvent is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and N,N-dimethylacetamide;

[0034] The inert atmosphere includes a nitrogen atmosphere.

[0035] In the above method, the concentration of the olefin compound can be 0.033 mol / L to 0.1 mol / L, and preferably can be 0.03, 0.05, or 1 mol / L;

[0036] The concentration of the acid anhydride compound or the acyl imidazole compound can be 0.033 mol / L to 0.4 mol / L;

[0037] The concentration of the tertiary amine compound can be 0.033 mol / L to 0.3 mol / L. This concentration range is the optimal concentration range. Below or above this concentration range, the reaction yield of the system is low.

[0038] In the above method, the concentration of the photocatalyst can be 0.001 mol / L to 0.004 mol / L.

[0039] In the above method, the molar ratio of the olefin compound to the acid anhydride compound or the acyl imidazole compound can be 0.25 to 1:1, and preferably can be 0.5:1, 0.5 to 1:1, or 0.25 to 0.5:1.

[0040] In the above method, the molar ratio of the olefin compound to the tertiary amine compound can be 0.33 to 1:1. Below this ratio, the reaction yield is very low and has no practical application value.

[0041] In the above method, the light source used for the visible light irradiation is LED blue light;

[0042] The time of the photoreaction can be 6 h to 24 h. When the time is shortened to 6 h, the yield decreases significantly. When the time is extended to 24 h, the yield does not change significantly. Therefore, the above is the preferred photoreaction time range.

[0043] The present invention has the following beneficial effects:

[0044] 1. The present invention uses an organic photocatalyst to achieve a photooxidation-reduction cycle, making up for the defects of previous synthesis methods such as the use of transition precious metals and limited substrates;

[0045] 2. The present invention synthesizes a basic structural unit widely present in active molecules, namely benzyl alkyl ketone compounds, through a visible light catalysis method in one step. The entire synthesis method is mild, efficient, and simple to operate.

[0046] 3. The present invention realizes for the first time the acylation reaction of carbon-carbon double bond cleavage of olefins through visible light catalysis.

[0047] 4. The present invention uses LED blue light as a visible light source, which is simple to operate. Description of the Drawings

[0048] Figure 1 It is the hydrogen spectrum of the product 1-phenyl-2-butanone.

[0049] Figure 2 It is the carbon spectrum of the product 1-phenyl-2-butanone.

[0050] Figure 3 It is the reaction mechanism diagram of the present invention. Detailed Description of the Invention

[0051] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0052] The materials, reagents, etc. used in the following examples can all be obtained from commercial channels unless otherwise specified.

[0053] The present invention will be described in detail below through specific examples and drawings, but it is not a specific limitation of the present invention.

[0054] A method for synthesizing benzyl alkyl ketone compounds by visible light catalysis provided by the present invention includes the following steps: in an inert atmosphere, an olefin compound, an acid anhydride compound or an acyl imidazole compound, and a tertiary amine compound are added to an organic solvent of a photocatalyst and mixed, and a photoreaction is carried out under visible light irradiation conditions to obtain benzyl alkyl ketone compounds.

[0055] The structural general formula of the benzyl alkyl ketone compounds of the present invention is shown as the following formula VI:

[0056]

[0057] In formula VI, R 1 , R 2 , R 3 , R 4 , R 5 are the same as those in formula I, R is the same as that in formula II or R' is the same as that in formula III;

[0058] The reaction mechanism of the present invention is as Figure 3As shown, the photo-catalyst 4 in the excited state undergoes single-electron oxidation of the amine 2, followed by deprotonation to generate the N-α radical 2'. Subsequently, radical addition to the alkene 1 gives the intermediate 6. The benzyl radical intermediate 6 is reduced by a single electron of the photo-catalyst anion radical in the ground state and undergoes an electrophilic addition reaction with propanoic anhydride (acyl source) to form the intermediate product 7. The intermediate product 7 is oxidized by a single electron of the photo-catalyst 4 in the excited state and deprotonated to obtain the radical intermediate 7', which induces the cleavage of the carbon-carbon single bonds connected to the β and γ positions of nitrogen to generate the alkyl radical 9' and the enamine 8. The alkyl radical 9' is reduced by a single electron of the photo-catalyst anion radical 5 in the ground state and protonated, finally obtaining the target product 9'.

[0059] In Examples 26 to 51 below, R or R' in the target compound of Formula VI is ethyl, and the specific structural formula is as shown in Formula IV. The reaction equation is specifically as follows:

[0060]

[0061] In Examples 52 to 59 below, R 1 , R 2 , R 3 , R 4 , R 5 are H, OPh, H, H, H respectively, and the specific structural formula is as shown in Formula V. The reaction equation is specifically as follows:

[0062]

[0063] Example 1

[0064] In a transparent vial with a capacity of 7 mL, 0.004 mmol of 4DPAIPN was added, and then transferred to a nitrogen glove box. 2 mL of ultra-dry dimethyl sulfoxide (dimethyl sulfoxide was dried with calcium oxide and then obtained by vacuum distillation to get anhydrous dimethyl sulfoxide) was added. The vial was sealed and taken out of the glove box. Using a microsyringe, 0.2 mmol of styrene, 0.4 mmol of N,N-dicyclohexylmethylamine, and 0.4 mmol of propanoic anhydride were successively added to the reaction system. The reaction solution was irradiated with LED (blue light, the specific wavelength could be 456 nm, the same below) for 12 h. Then, 2 mL of water and 2 mL of 1 M hydrochloric acid solution were successively added to the reaction solution, mixed evenly, extracted with ethyl acetate (3×10 mL), the organic phase was collected, washed with water (3×10 mL), washed with saturated sodium chloride (3×10 mL), an appropriate amount of anhydrous sodium sulfate was added to the organic phase, left standing for 30 min, the organic solvent was removed by vacuum distillation, and an appropriate amount of 1,3,5-trimethoxybenzene was added as an internal standard. According to the gas-phase standard curve, the gas-phase yield of the product was 46%. The product was identified by GC-MS as 1-phenyl-2-butanone.

[0065] Example 2

[0066] Same as Example 1, except that 4CzIPN was used as the visible light catalyst, and the gas-phase yield of the product was 19%.

[0067] Example 3

[0068] Same as Example 1, except that 3DPA2FBN was used as the visible light catalyst, and the gas-phase yield of the product was 45%.

[0069] Example 4

[0070] Same as Example 1, except that 3DPAFIPN was used as the visible light catalyst, and the gas-phase yield of the product was 34%.

[0071] Example 5

[0072] Same as Example 1, except that Ir(ppy) 2 (dtbbpy)PF 6 was used as the visible light catalyst, and the gas-phase yield of the product was 4%.

[0073] Example 6

[0074] Same as Example 1, except that N,N-dimethylformamide was used as the reaction solvent, and the gas-phase yield of the product was 31%.

[0075] Example 7

[0076] Same as Example 1, except that N-methylpyrrolidone was used as the reaction solvent, and the gas-phase yield of the product was 32%.

[0077] Example 8

[0078] Same as Example 1, except that N,N-dimethylacetamide was used as the reaction solvent, and the gas-phase yield of the product was 28%.

[0079] Example 9

[0080] Same as Example 1, except that the amounts of N,N-dicyclohexylmethylamine and propionic anhydride were adjusted from 0.4 mmol and 0.4 mmol to 0.2 mmol and 0.2 mmol respectively, and the gas-phase yield of the product was 17%.

[0081] Example 10

[0082] Same as Example 1, except that the amounts of N,N-dicyclohexylmethylamine and propionic anhydride were adjusted from 0.4 mmol and 0.4 mmol to 0.3 mmol and 0.3 mmol respectively, and the gas-phase yield of the product was 26%.

[0083] Example 11

[0084] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.3 mmol and 0.4 mmol respectively, and the gas-phase yield of the product obtained is 32%.

[0085] Example 12

[0086] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.6 mmol and 0.4 mmol respectively, and the gas-phase yield of the product obtained is 34%.

[0087] Example 13

[0088] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.6 mmol and 0.6 mmol respectively, and the gas-phase yield of the product obtained is 34%.

[0089] Example 14

[0090] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.4 mmol and 0.3 mmol respectively, and the gas-phase yield of the product obtained is 27%.

[0091] Example 15

[0092] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.4 mmol and 0.6 mmol respectively, and the gas-phase yield of the product obtained is 43%.

[0093] Example 16

[0094] Same as Example 1, except that the amounts of substance of N,N-dicyclohexylmethylamine and propionic anhydride are adjusted from 0.4 mmol and 0.4 mmol to 0.4 mmol and 0.8 mmol respectively, and the gas-phase yield of the product obtained is 45%.

[0095] Example 17

[0096] Same as Example 1, except that N,N-cycloheptyl-tert-butylmethylamine is added instead of N,N-dicyclohexylmethylamine, and the gas-phase yield of the product obtained is 49%.

[0097] Example 18

[0098] Same as Example 1, except that N,N-isopropyl-tert-butylmethylamine is added instead of N,N-dicyclohexylmethylamine, and the gas-phase yield of the product obtained is 53%.

[0099] Example 19

[0100] Same as Example 1, except that N,N-cyclohexyl-tert-butylmethylamine is added instead of N,N-dicyclohexylmethylamine, and the gas-phase yield of the product obtained is 57%.

[0101] Example 20

[0102] Same as Example 19, except that the reaction solution is irradiated with LED (blue light) for 6 h, and the gas-phase yield of the product obtained is 49%.

[0103] Example 21

[0104] Same as Example 19, except that the reaction solution is irradiated with LED (blue light) for 24 h, and the gas-phase yield of the product obtained is 57%.

[0105] Example 22

[0106] Same as Example 19, except that the amount of substance of the visible-light catalyst 4DPAIPN is adjusted from 0.004 mmol to 0.006 mmol, and the gas-phase yield of the product obtained is 66%.

[0107] Example 23

[0108] Same as Example 19, except that the amount of substance of the visible-light catalyst 4DPAIPN is adjusted from 0.004 mmol to 0.008 mmol, and the gas-phase yield of the product obtained is 59%.

[0109] Example 24

[0110] Same as Example 22, except that the volume of ultradry dimethyl sulfoxide is adjusted from 2 mL to 4 mL, and the gas-phase yield of the product obtained is 64%.

[0111] Example 25

[0112] Same as Example 22, except that the volume of ultradry dimethyl sulfoxide is adjusted from 2 mL to 6 mL, and the gas-phase yield of the product obtained is 62%.

[0113] Example 26

[0114] In a 7 mL transparent vial, 0.006 mmol of 4DPAIPN was added. It was transferred to a nitrogen glove box, and 2 mL of ultra-dry dimethyl sulfoxide was added. The vial was sealed and taken out of the glove box. 0.2 mmol of styrene, 0.4 mmol of N,N-cyclohexyl-tert-butylmethylamine, and 0.4 mmol of propionic anhydride were successively added to the reaction system using a micro syringe. After irradiating the reaction solution with LED (blue light) for 12 h, 2 mL of water and 2 mL of 1 M hydrochloric acid solution were successively added to the reaction solution. After mixing evenly, it was extracted with ethyl acetate (3×10 mL). The organic phase was collected, washed with water (3×10 mL), and washed with saturated sodium chloride (3×10 mL). An appropriate amount of anhydrous sodium sulfate was added to the organic phase, and it was allowed to stand for 30 min. After removing the organic solvent by distillation under reduced pressure, the pure product was obtained by column chromatography separation, and the product yield was 61%.

[0115] The structure was confirmed as follows:

[0116] 1 H NMR (400 MHz, CDCl 3 ) δ 7.32 - 7.12 (m, 5H), 3.64 (s, 2H), 2.43 (q, J = 7.3 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H).

[0117] 13 C NMR (101 MHz, CDCl 3 ) δ 209.14, 134.60, 129.50, 128.82, 127.07, 49.95, 35.33, 7.89.

[0118] HRMS (ESI, m / z) Calcd. for C 10 H 11 O [M - H] - : 147.0815, found: 147.0808.

[0119] The 1H NMR (as Figure 1 shown), 13C NMR (as Figure 2 shown), and high-resolution mass spectrometry identified the product as 1-phenylbutan-2-one.

[0120] Example 27

[0121] Same as Example 26, except that 4-methylstyrene was added instead of styrene, and the product yield was 54%. The 1H NMR, 13C NMR, and high-resolution mass spectrometry identified the product as 1-(4-methylphenyl)butan-2-one.

[0122] The structure was confirmed as follows:

[0123] 11H NMR (400 MHz, CDCl 3 ) δ 7.12 (q, J = 8.0 Hz, 4H), 3.64 (s, 2H), 2.46 (q, J = 7.3 Hz, 2H), 2.33 (s, 3H), 1.02 (t, J = 7.3 Hz, 3H).

[0124] 13 13C NMR (101 MHz, CDCl 3 ) δ 209.42, 136.67, 131.53, 129.51, 129.35, 49.55, 35.19, 21.16, 7.90.

[0125] HRMS (ESI, m / z) Calcd. for C 11 H 13 O [M-H] - : 161.0972, found: 161.0967.

[0126] Example 28

[0127] Same as Example 26, except that 4-tert-butylstyrene was added instead of styrene, and the product yield was 51%. The product was identified as 1-(4-tert-butylphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0128] The structure was confirmed as follows:

[0129] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.41 - 7.29 (m, 2H), 7.21 - 7.07 (m, 2H), 3.65 (s, 2H), 2.48 (q, J = 7.3 Hz, 2H), 1.31 (s, 9H), 1.03 (t, J = 7.3 Hz, 3H).

[0130] 13 13C NMR (101 MHz, CDCl 3 ) δ 209.44, 149.95, 131.54, 129.16, 125.77, 49.45, 35.33, 34.59, 31.48, 7.91.

[0131] HRMS (ESI, m / z) Calcd. for C 14 H 19 O [M-H] - : 203.1441, found: 203.1438.

[0132] Example 29

[0133] Same as Example 26, except that 4-acetoxystyrene is added instead of styrene, and the product yield is 54%. The product is identified as 1-(4-acetoxyphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0134] The structure was confirmed as follows:

[0135] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, J = 8.5 Hz, 2H), 7.08 (d, J = 8.5 Hz, 2H), 3.71 (s, 2H), 2.52 (q, J = 7.3 Hz, 2H), 2.32 (s, 3H), 1.07 (t, J = 7.3 Hz, 3H).

[0136] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.71, 169.55, 149.74, 132.07, 130.46, 121.85, 49.04, 35.42, 21.20, 7.81.

[0137] HRMS (ESI, m / z) Calcd. for C 12 12 13 14 3 [M-H] - : 205.0870, found: 205.0866.

[0138] Example 30

[0139] Same as Example 26, except that 4-phenylstyrene is added instead of styrene, and the product yield is 55%. The product is identified as 1-[4-(1,1'-biphenyl)]butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0140] The structure was confirmed as follows:

[0141] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.61 - 7.51 (m, 4H), 7.42 (dd, J = 8.3, 6.9 Hz, 2H), 7.37 - 7.21 (m, 3H), 3.72 (s, 2H), 2.51 (q, J = 7.3 Hz, 2H), 1.05 (t, J = 7.3 Hz, 3H).

[0142] 13 13C NMR (101 MHz, CDCl 3)δ209.01,140.83,140.00,133.58,129.91,128.87,127.51,127.37,127.13,49.46,35.43,7.90.

[0143] HRMS(ESI,m / z)Calcd.for C 16 H 15 O[M-H] - :223.1128,found:223.1125.

[0144] Example 31

[0145] Same as Example 26, except that 4-trimethylsilylstyrene was added instead of styrene, and the product yield was 53%. The product was identified as 1-(4-trimethylsilylphenyl)butan-2-one by 1H NMR, 13C NMR, and HRMS.

[0146] The structure was confirmed as follows:

[0147] 1 H NMR(400MHz,CDCl 3 )δ7.53(d,J=7.7Hz,2H),7.25(d,J=7.6Hz,2H),3.73(s,2H),2.53(q,J=7.3Hz,2H),1.08(t,J=7.3Hz,3H),0.31(s,9H).

[0148] 13 C NMR(101MHz,CDCl 3 )δ209.01,138.99,135.07,133.84,128.87,49.88,35.39,7.86,-1.02.

[0149] HRMS(ESI,m / z)Calcd.for C 13 H 19 OSi[M-H] - :219.1211,found:219.1208.

[0150] Example 32

[0151] Same as Example 26, except that 4-(1-pyrazolyl)styrene was added instead of styrene, and the product yield was 70%. The product was identified as 1-[4-(1-pyrazolyl)phenyl]butan-2-one by 1H NMR, 13C NMR, and HRMS.

[0152] The structure was confirmed as follows:

[0153] 11H NMR (400 MHz, CDCl 3 ) δ 7.89 (d, J = 2.5 Hz, 1H), 7.69 (s, 1H), 7.63 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 8.2 Hz, 2H), 6.43 (s, 1H), 3.69 (s, 2H), 2.48 (q, J = 7.3 Hz, 2H), 1.02 (t, J = 7.3 Hz, 3H).

[0154] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.63, 141.10, 139.18, 132.69, 130.47, 126.78, 119.45, 107.66, 49.01, 35.42, 7.82.

[0155] HRMS (ESI, m / z) Calcd. for C 13 H 15 N 2 O [M+H] + : 215.1179, found: 215.1179.

[0156] Example 33

[0157] Same as Example 26, except that 4-(methylthio)styrene was added instead of styrene, and the product yield was 41%. The product was identified as 1-(4-(methylthio)phenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0158] Structure confirmation is as follows:

[0159] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.35 (d, J = 8.2 Hz, 2H), 7.29 - 7.19 (m, 2H), 3.77 (s, 2H), 2.59 (d, J = 4.0 Hz, 5H), 1.15 (t, J = 7.3 Hz, 3H).

[0160] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.93, 137.14, 131.37, 129.94, 127.10, 49.24, 35.31, 16.04, 7.86.

[0161] HRMS (ESI, m / z) Calcd. for C 11 H 13 SO [M-H] -: 193.0693, found: 193.0689.

[0162] Example 34

[0163] Same as Example 26, except that 3-methylstyrene was added instead of styrene, and the product yield was 55%. The product was identified as 1-(3-methylphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0164] The structure was confirmed as follows:

[0165] 1 H NMR (400 MHz, CDCl 3 ) δ 7.21 (t, J = 7.5 Hz, 1H), 7.12 - 6.94 (m, 3H), 3.65 (s, 2H), 2.47 (q, J = 7.3 Hz, 2H), 2.34 (s, 3H), 1.03 (t, J = 7.3 Hz, 3H).

[0166] 13 C NMR (101 MHz, CDCl 3 ) δ 209.32, 138.48, 134.51, 130.25, 128.71, 127.83, 126.51, 49.94, 35.28, 21.47, 7.90.

[0167] HRMS (ESI, m / z) Calcd. for C 11 H 13 O [M-H] - : 161.0972, found: 161.0966.

[0168] Example 35

[0169] Same as Example 26, except that 3-methoxystyrene was added instead of styrene, and the product yield was 70%. The product was identified as 1-(3-methoxyphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0170] The structure was confirmed as follows:

[0171] 1 H NMR (400 MHz, CDCl 3 ) δ 7.26 (t, J = 7.9 Hz, 1H), 6.88 - 6.72 (m, 3H), 3.82 (s, 3H), 3.67 (s, 2H), 2.50 (q, J = 7.3 Hz, 2H), 1.05 (t, J = 7.3 Hz, 3H).

[0172] 1313C NMR (101 MHz, CDCl 3 ) δ 209.00, 159.93, 136.04, 129.78, 121.84, 115.10, 112.54, 55.28, 49.98, 35.22, 7.86.

[0173] HRMS (ESI, m / z) Calcd. for C 11 H 13 O 2 [M - H] - : 177.0921, found: 177.0915.

[0174] Example 36

[0175] Same as Example 26, except that 3 - acetoxystyrene was added instead of styrene, and the product yield was 51%. The product was identified as 1 - (3 - acetoxyphenyl)butan - 2 - one by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0176] The structure was confirmed as follows:

[0177] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.32 (t, J = 7.9 Hz, 1H), 7.07 (d, J = 7.7 Hz, 1H), 7.04 - 6.82 (m, 2H), 3.68 (s, 2H), 2.47 (q, J = 7.3 Hz, 2H), 2.28 (s, 3H), 1.02 (t, J = 7.3 Hz, 3H).

[0178] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.44, 169.50, 150.94, 136.06, 129.68, 126.97, 122.68, 120.27, 49.41, 35.48, 21.20, 7.81.

[0179] HRMS (ESI, m / z) Calcd. for C 12 H 15 O 3 [M + H] + : 207.1016, found: 207.1016.

[0180] Example 37

[0181] Same as Example 26, except that 3-phenoxystyrene is added instead of styrene, and the product yield is 71%. The product is identified as 1-(3-phenoxyphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0182] The structure was confirmed as follows:

[0183] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.32 - 7.15 (m, 3H), 7.03 (t, J = 7.4 Hz, 1H), 6.94 (d, J = 7.7 Hz, 2H), 6.89 - 6.70 (m, 3H), 3.58 (s, 2H), 2.40 (q, J = 7.3 Hz, 2H), 0.96 (t, J = 7.3 Hz, 3H).

[0184] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.52, 157.61, 157.07, 136.41, 129.98, 129.85, 124.29, 123.45, 119.89, 119.06, 117.29, 49.58, 35.36, 7.83.

[0185] HRMS (ESI, m / z) Calcd. for C 16 15 15 10 2 [M - H] - : 239.1078, found: 239.1077.

[0186] Example 38

[0187] Same as Example 26, except that 3-phenylstyrene is added instead of styrene, and the product yield is 65%. The product is identified as 1-[3-(1,1'-biphenyl)]butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0188] The structure was confirmed as follows:

[0189] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.46 - 7.36 (m, 2H), 7.37 - 7.10 (m, 6H), 7.02 (dt, J = 7.6, 1.4 Hz, 1H), 3.57 (s, 2H), 2.33 (q, J = 7.3 Hz, 2H), 0.87 (t, J = 7.3 Hz, 3H).

[0190] 13 13C NMR (101 MHz, CDCl3 ) δ 208.93, 141.76, 140.94, 135.03, 129.19, 128.84, 128.36, 128.32, 127.48, 127.26, 125.89, 49.90, 35.37, 7.87.

[0191] HRMS(ESI, m / z) Calcd. for C 16 H 15 O[M - H] - : 223.1128, found: 223.1124.

[0192] Example 39

[0193] Same as Example 26, except that 3 - fluorostyrene was added instead of styrene, and the product yield was 65%. The product was identified as 1 - (3 - fluorophenyl)butan - 2 - one by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0194] The structure was confirmed as follows:

[0195] 1 H NMR(400 MHz, CDCl 3 ) δ 7.35 - 7.21(m, 1H), 6.94(ddt, J = 19.3, 9.9, 1.9 Hz, 3H), 3.68(s, 2H), 2.48(q, J = 7.3 Hz, 2H), 1.04(t, J = 7.3 Hz, 3H).

[0196] 13 C NMR(101 MHz, CDCl 3 ) δ 208.26, 164.24, 161.79, 136.86, 136.79, 130.25, 130.17, 125.24, 125.21, 116.63, 116.41, 114.15, 113.94, 49.35, 49.33, 35.57, 7.84.

[0197] HRMS(ESI, m / z) Calcd. for C 11 H 10 FO[M - H] - : 165.0721, found: 165.0716.

[0198] Example 40

[0199] Same as Example 26, except that 3 - chlorostyrene was added instead of styrene, and the product yield was 45%. The product was identified as 1 - (3 - chlorophenyl)butan - 2 - one by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0200] The structural confirmation is as follows:

[0201] 1 H NMR (400 MHz, CDCl 3 ) δ 7.29 - 7.17 (m, 3H), 7.13 - 7.00 (m, 1H), 3.66 (s, 2H), 2.48 (q, J = 7.3 Hz, 2H), 1.04 (t, J = 7.3 Hz, 3H).

[0202] 13 C NMR (101 MHz, CDCl 3 ) δ 208.13, 136.39, 134.54, 129.98, 129.66, 127.74, 127.30, 49.20, 35.62, 7.84.

[0203] HRMS (ESI, m / z) Calcd. for C 10 H 10 ClO [M - H] - : 181.0426, found: 181.0419.

[0204] Example 41

[0205] Same as Example 26, except that methyl 3 - vinylbenzoate is added instead of styrene, and the product yield is 46%. The product is identified as methyl 3 - [1 - (2 - butanone)yl]benzoate by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0206] The structural confirmation is as follows:

[0207] 1 H NMR (500 MHz, CDCl 3 ) δ 8.03 - 7.77 (m, 2H), 7.40 (dd, J = 5.1, 1.0 Hz, 2H), 3.91 (s, 3H), 3.74 (s, 2H), 2.49 (q, J = 7.3 Hz, 2H), 1.04 (t, J = 7.3 Hz, 3H).

[0208] 13 C NMR (126 MHz, CDCl 3 ) δ 208.30, 167.01, 134.86, 134.11, 130.67, 129.00, 128.84, 128.35, 52.27, 49.35, 35.66, 7.86.

[0209] HRMS (ESI, m / z) Calcd. for C 12 H 14 NaO3 [M+Na] + : 185.0573, found: 185.0573.

[0210] Example 42

[0211] Same as Example 26, except that 2-methylstyrene was added instead of styrene, and the product yield was 40%. The product was identified as 1-(2-methylphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0212] The structure was confirmed as follows:

[0213] 1 H NMR (400 MHz, CDCl 3 ) δ 7.21 - 7.11 (m, 4H), 3.70 (s, 2H), 2.45 (q, J = 7.3 Hz, 2H), 2.25 (s, 3H), 1.04 (t, J = 7.3 Hz, 3H).

[0214] 13 C NMR (101 MHz, CDCl 3 ) δ 209.17, 136.94, 133.49, 130.58, 130.49, 127.39, 126.35, 48.08, 35.27, 19.80, 7.96.

[0215] HRMS (ESI, m / z) Calcd. for C 11 H 13 O [M-H] - : 161.0972, found: 161.0966.

[0216] Example 43

[0217] Same as Example 26, except that 3-fluoro-5-methylstyrene was added instead of styrene, and the product yield was 48%. The product was identified as 1-(3-fluoro-5-methylphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0218] The structure was confirmed as follows:

[0219] 1 H NMR (400 MHz, CDCl 3 ) δ 6.84 - 6.64 (m, 3H), 3.63 (s, 2H), 2.51 (s, 2H), 2.32 (s, 3H), 1.04 (t, J = 7.3 Hz, 3H).

[0220] 13 C NMR (101 MHz, CDCl3 ) δ 208.46, 164.22, 161.79, 140.76, 140.68, 136.44, 136.36, 126.00, 125.98, 114.78, 114.58, 113.58, 113.37, 49.42, 49.40, 35.49, 21.39, 21.37, 7.86.

[0221] HRMS(ESI, m / z) Calcd. for C 11 H 12 FO[M - H] - : 179.0878, found: 179.0869.

[0222] Example 44

[0223] Same as Example 26, except that 3 - fluoro - 5 - methoxystyrene was added instead of styrene, and the product yield was 39%. The product was identified as 1 - (3 - fluoro - 5 - methoxyphenyl)butan - 2 - one by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0224] The structure confirmation is as follows:

[0225] 1 1H NMR (400 MHz, CDCl 3 ) δ 6.52 (d, J = 9.1 Hz, 3H), 3.78 (s, 3H), 3.62 (s, 2H), 2.48 (q, J = 7.3 Hz, 2H), 1.03 (t, J = 7.3 Hz, 3H).

[0226] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.21, 164.98, 162.55, 161.20, 161.09, 137.32, 137.22, 111.19, 111.17, 108.86, 108.65, 100.46, 100.21, 55.64, 49.66, 49.64, 35.46, 7.85.

[0227] HRMS(ESI, m / z) Calcd. for C 11 H 14 FO 2 [M + H] + : 197.0972, found: 197.0972.

[0228] Example 45

[0229] Same as Example 26, except that 3,5-dimethoxystyrene is added instead of styrene, and the product yield is 62%. The product was identified as 1-(3,5-dimethoxyphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0230] The structure was confirmed as follows:

[0231] 1 1H NMR (400 MHz, CDCl 3 ) δ 6.35 (s, 3H), 3.77 (s, 6H), 3.60 (s, 2H), 2.47 (q, J = 7.3 Hz, 2H), 1.01 (t, J = 7.3 Hz, 3H).

[0232] 13 13C NMR (101 MHz, CDCl 3 ) δ 208.94, 161.08, 136.72, 107.52, 99.06, 55.39, 50.24, 35.10, 7.86.

[0233] HRMS (ESI, m / z) Calcd. for C 12 11 17 H 3 2 + O

[0234] [M + H]

[0235] : 209.1172, found: 209.1172.

[0236] The structure was confirmed as follows:

[0237] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.26 (s, 2H), 7.20 (s, 1H), 4.42 (s, 3H), 4.25 (s, 2H), 3.11 (q, J = 7.3 Hz, 2H), 2.95 (s, 3H), 1.66 (t, J = 7.3 Hz, 3H).

[0238] 13 13C NMR (101 MHz, CDCl 3)δ209.16,159.94,139.87,135.77,122.74,113.38,112.10,55.26,50.00,35.16,21.57,7.87.

[0239] HRMS(ESI,m / z)Calcd.for C 12 H 17 O 2 [M+H] + :193.1223,found:193.1223.

[0240] Example 47

[0241] Same as Example 26, except that 3,5-dimethylstyrene was added instead of styrene, and the product yield was 48%. The product was identified as 1-(3,5-dimethylphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0242] The structure was confirmed as follows:

[0243] 1 H NMR(400MHz,CDCl 3 )δ6.90(s,1H),6.83(s,2H),3.61(s,2H),2.48(q,J=7.3Hz,2H),2.31(s,6H),1.04(t,J=7.3Hz,3H).

[0244] 13 C NMR(101MHz,CDCl 3 )δ209.44,138.32,134.41,128.69,127.27,49.87,35.20,21.32,7.88.

[0245] HRMS(ESI,m / z)Calcd.for C 12 H 17 O[M+H] + :177.1274,found:177.1273.

[0246] Example 48

[0247] Same as Example 26, except that 3,4-dimethoxystyrene was added instead of styrene, and the product yield was 42%. The product was identified as 1-(3,4-dimethoxyphenyl)butan-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0248] The structure was confirmed as follows:

[0249] 11H NMR (400 MHz, CDCl 3 ) δ 6.80 (d, J = 8.1 Hz, 1H), 6.76 - 6.64 (m, 2H), 3.84 (s, 6H), 3.60 (s, 2H), 2.45 (q, J = 7.3 Hz, 2H), 1.01 (t, J = 7.3 Hz, 3H).

[0250] 13 13C NMR (101 MHz, CDCl 3 ) δ 209.45, 149.12, 148.14, 127.03, 121.59, 112.48, 111.42, 55.95, 55.92, 49.42, 35.05, 7.86.

[0251] HRMS (ESI, m / z) Calcd. for C 12 13 17 2 3 [M + H] + : 209.1172, found: 209.1178.

[0252] Example 49

[0253] Same as Example 26, except that 3,4,5 - trimethoxystyrene was added instead of styrene, and the product yield was 61%. The product was identified as 1 - (3,4,5 - trimethoxyphenyl)butan - 2 - one by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0254] Structure confirmation is as follows:

[0255] 1 1H NMR (400 MHz, CDCl 3 ) δ 6.39 (s, 2H), 3.81 (d, J = 6.5 Hz, 9H), 3.59 (s, 2H), 2.47 (q, J = 7.3 Hz, 2H), 1.02 (t, J = 7.3 Hz, 3H).

[0256] 13 13C NMR (101 MHz, CDCl 3 ) δ 209.02, 153.41, 137.09, 130.09, 106.48, 60.88, 56.18, 50.05, 35.18, 7.85.

[0257] HRMS (ESI, m / z) Calcd. for C 13 13 19 2 4 [M + H] +: 239.1278, found: 239.1276.

[0258] Example 50

[0259] Same as Example 26, except that 1-methyl-1-styrene is added instead of styrene, and the product yield is 60%. The product is identified as 2-phenylpentan-3-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0260] The structure confirmation is as follows:

[0261] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.28 - 7.10 (m, 5H), 3.68 (q, J = 7.0 Hz, 1H), 2.41 - 2.19 (m, 2H), 1.32 (d, J = 7.0 Hz, 3H), 0.89 (t, J = 7.3 Hz, 3H).

[0262] 13 13C NMR (101 MHz, CDCl 3 ) δ 211.67, 141.04, 128.99, 127.95, 127.18, 52.82, 34.37, 17.64, 8.09.

[0263] HRMS (ESI, m / z) Calcd. for C 11 H 15 O [M + H] + : 163.1117, found: 163.1121.

[0264] Example 51

[0265] Same as Example 26, except that 1-methyl-1-(3-phenoxyphenyl)styrene is added instead of styrene, and the product yield is 76%. The product is identified as 2-(3-phenoxyphenyl)pentan-3-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0266] The structure confirmation is as follows:

[0267] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.35 - 7.22 (m, 2H), 7.19 (t, J = 7.9 Hz, 1H), 7.08 - 6.99 (m, 1H), 6.99 - 6.70 (m, 5H), 3.66 (q, J = 7.0 Hz, 1H), 2.42 - 2.22 (m, 2H), 1.31 (d, J = 7.0 Hz, 3H), 0.90 (t, J = 7.3 Hz, 3H).

[0268] 13 C NMR (101 MHz, CDCl 3 ) δ 211.12, 157.75, 157.04, 142.98, 130.17, 129.87, 123.48, 122.64, 118.98, 118.46, 117.31, 52.58, 34.33, 17.49, 8.06.

[0269] HRMS (ESI, m / z) Calcd. for C 17 H 17 O 2 [M - H] - : 253.1234, found: 253.1233.

[0270] Example 52

[0271] Same as Example 37, except that acetic anhydride was added instead of propionic anhydride, and the product yield was 65%. The product was identified as 1-(3-phenoxyphenyl)propanone by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0272] The structure was confirmed as follows:

[0273] 1 1H NMR (500 MHz, CDCl 3 ) δ 7.23 (dt, J = 25.4, 7.9 Hz, 3H), 7.03 (t, J = 7.4 Hz, 1H), 6.94 (d, J = 8.0 Hz, 2H), 6.90 - 6.75 (m, 3H), 3.58 (s, 2H), 2.07 (s, 3H).

[0274] 13 13C NMR (126 MHz, CDCl 3 ) δ 205.92, 157.67, 157.00, 136.18, 130.06, 129.86, 124.28, 123.50, 119.84, 119.10, 117.38, 50.78, 29.40.

[0275] HRMS (ESI, m / z) Calcd. for C 15 H 13 O 2 [M - H] - : 225.0921, found: 225.0920.

[0276] Example 53

[0277] Same as Example 37, except that isovaleric anhydride is added instead of propionic anhydride, and the product yield is 62%. The product was identified as 4-methyl-1-(3-phenoxyphenyl)-2-pentanone by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0278] The structure was confirmed as follows:

[0279] 1 H NMR(500MHz,CDCl 3 )δ7.30-7.17(m,3H),7.03(tt,J=7.2,1.1Hz,1H),6.94(dt,J=7.8,1.1Hz,2H),6.88-6.81(m,2H),6.79(t,J=2.1Hz,1H),3.55(s,2H),2.25(d,J=6.9Hz,2H),2.06(dq,J=13.5,6.7Hz,1H),0.81(d,J=6.7Hz,6H).

[0280] 13 C NMR(126MHz,CDCl 3 )δ207.69,157.60,157.15,136.24,130.01,129.87,124.41,123.45,119.99,119.05,117.41,51.08,50.43,24.54,22.60.

[0281] HRMS(ESI,m / z)Calcd.for C 18 H 21 O 2 [M+H] + :269.1536,found:269.1533.

[0282] Example 54

[0283] Same as Example 37, except that isobutyric anhydride is added instead of propionic anhydride, and the product yield is 53%. The product was identified as 3-methyl-1-(3-phenoxyphenyl)-2-butanone by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0284] The structure was confirmed as follows:

[0285] 1 H NMR(500MHz,CDCl 3) δ 7.39 - 7.31 (m, 2H), 7.28 (t, J = 7.8 Hz, 1H), 7.14 - 7.07 (m, 1H), 7.02 (dt, J = 7.8, 1.1 Hz, 2H), 6.97 - 6.83 (m, 3H), 3.72 (s, 2H), 2.73 (hept, J = 6.9 Hz, 1H), 1.11 (d, J = 6.9 Hz, 6H).

[0286] 13 C NMR (126 MHz, CDCl 3 ) δ 211.57, 157.52, 157.18, 136.44, 129.92, 129.86, 124.44, 123.41, 120.08, 119.03, 117.32, 47.52, 40.30, 18.41.

[0287] HRMS (ESI, m / z) Calcd. for C 17 H 19 O 2 [M + H] + : 255.1380, found: 255.1378.

[0288] Example 55

[0289] Same as Example 37, except that cyclopropanecarboxylic anhydride was added instead of propionic anhydride, and the product yield was 35%. The product was identified as 1 - cyclopropyl - 2-(3 - phenoxyphenyl)ethanone by 1H NMR, 13C NMR, and high - resolution mass spectrometry.

[0290] The structure was confirmed as follows:

[0291] 1 1H NMR (400 MHz, CDCl 3 ) δ 7.30 - 7.17 (m, 3H), 7.03 (tt, J = 7.2, 1.1 Hz, 1H), 6.94 (dt, J = 7.8, 1.1 Hz, 2H), 6.91 - 6.87 (m, 1H), 6.83 (dd, J = 7.7, 1.2 Hz, 2H), 3.72 (s, 2H), 1.89 (tt, J = 7.8, 4.5 Hz, 1H), 1.01 - 0.91 (m, 2H), 0.78 (dq, J = 7.4, 3.6 Hz, 2H).

[0292] 13 13C NMR (101 MHz, CDCl 3)δ208.02,157.61,157.15,136.43,130.00,129.86,124.48,123.44,120.04,119.07,117.36,50.53,20.23,11.49.

[0293] HRMS(ESI,m / z)Calcd.for C 17 H 15 O 2 [M-H] - :251.1078,found:251.1079.

[0294] Example 56

[0295] Same as Example 37, except that 1-(1-imidazolyl)-1-one-4-pentene was added instead of propionic anhydride, and the product yield was 45%. The product was identified as 1-(3-phenoxy)phenyl-2-one-5-hexene by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0296] The structure was confirmed as follows:

[0297] 1 H NMR(400MHz,CDCl 3 )δ7.30(dt,J=22.2,8.1Hz,3H),7.10(t,J=7.4Hz,1H),7.06-6.75(m,5H),5.76(ddt,J=17.0,10.4,6.5Hz,1H),4.97(t,J=13.6Hz,2H),3.65(s,2H),2.54(t,J=7.4Hz,2H),2.30(q,J=7.1Hz,2H).

[0298] 13 C NMR(101MHz,CDCl 3 )δ207.16,157.69,157.10,137.03,136.17,130.08,129.90,124.36,123.52,119.95,119.12,117.45,115.44,50.07,41.20,27.78.

[0299] HRMS(ESI,m / z)Calcd.for C 18 H 19 O 2 [M+H] + :267.1380,found:267.1386.

[0300] Example 57

[0301] Same as Example 37, except that 1-(1-imidazolyl)-5-chloropentanone is added instead of propionic anhydride, and the product yield is 41%. The product is identified as 1-(3-phenoxy)phenyl-6-chloro-2-hexanone by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0302] The structure confirmation is as follows:

[0303] 1 H NMR(400MHz,CDCl 3 )δ7.31-7.16(m,3H),7.08-6.99(m,1H),6.99-6.89(m,2H),6.89-6.61(m,3H),3.57(s,2H),3.49-3.29(m,2H),2.49-2.32(m,2H),1.63(t,J=3.3Hz,4H).

[0304] 13 C NMR(101MHz,CDCl 3 )δ207.35,157.74,157.05,136.12,130.11,129.91,124.28,123.56,119.85,119.14,117.46,50.03,44.68,41.02,31.88,21.03.

[0305] HRMS(ESI,m / z)Calcd.for C 18 H 20 ClO 2 [M+H] + :303.1146,found:303.1155.

[0306] Example 58

[0307] Same as Example 37, except that 1-(1-imidazolyl)-3-phenylacetone is added instead of propionic anhydride, and the product yield is 72%. The product is identified as 1-(3-phenoxy)phenyl-4-phenyl-2-butanone by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0308] The structure confirmation is as follows:

[0309] 1 H NMR(500MHz,CDCl 3)δ 7.32 - 7.02 (m, 9H), 6.99 - 6.91 (m, 2H), 6.90 - 6.81 (m, 2H), 6.78 (d, J = 2.2 Hz, 1H), 3.56 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.71 (t, J = 7.6 Hz, 2H).

[0310] 13 C NMR(126 MHz, CDCl 3 )δ 207.02, 157.65, 157.05, 140.93, 136.04, 130.05, 129.87, 128.57, 128.39, 126.23, 124.32, 123.49, 119.90, 119.10, 117.41, 50.18, 43.60, 29.85.

[0311] HRMS(ESI, m / z) Calcd. for C 22 H 19 O 2 [M - H] - : 315.1391, found: 315.1395.

[0312] Example 59

[0313] Same as Example 37, except that (9Z)-octadecene-1-(1-imidazolyl)-1-one was added instead of propionic anhydride, and the product yield was 63%. The product was identified as 1-(3-phenoxy)phenyl-(10Z)-nonadecen-2-one by 1H NMR, 13C NMR, and high-resolution mass spectrometry.

[0314] The structure was confirmed as follows:

[0315] 1 1H NMR(500 MHz, CDCl 3 )δ 7.22 (dt, J = 28.3, 7.8 Hz, 3H), 7.05 - 6.97 (m, 1H), 6.92 (d, J = 8.0 Hz, 2H), 6.88 - 6.70 (m, 3H), 5.37 - 5.16 (m, 2H), 3.55 (s, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.89 (tt, J = 12.2, 5.6 Hz, 4H), 1.46 (p, J = 7.2 Hz, 2H), 1.19 (q, J = 13.3 Hz, 20H), 0.80 (t, J = 6.8 Hz, 3H).

[0316] 13 13C NMR(126 MHz, CDCl 3)δ208.17,157.64,157.13,136.37,130.57,130.32,130.01,129.87,124.35,123.46,119.95,119.08,117.38,49.98,42.17,32.73,32.67,32.02,29.77,29.67,29.61,29.44,29.34,29.30,29.19,29.06,23.82,22.80,14.24.

[0317] HRMS(ESI,m / z)Calcd.for C 31 H 45 O 2 [M+H] + :449.3414,found:449.3421.

[0318] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to enumerate all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A method for synthesizing benzyl alkyl ketone compounds by visible light catalysis, comprising the following steps: In an inert atmosphere, an olefin compound, an acid anhydride compound or an acyl imidazole compound and a tertiary amine compound are added to an organic solvent of a photocatalyst and mixed, and a photoreaction is carried out under visible light irradiation conditions to obtain a benzyl alkyl ketone compound.

2. The method according to claim 1, characterized in that The structural formula of the olefin compound is shown in the following formula I: In Formula I, R 1 H or Me, R 2 is H, Me, OMe, OAc, OPh, Ph, F, Cl or COOMe, R 3 H, Me, t Bu, OMe, OAc, Ph, Me3Si, 1-pyrazolyl or SMe, R 4 is H, Me or OMe, R 5 It is H or Me.

3. The method according to claim 1 or 2, characterized in that: The structural formula of the acid anhydride compound is shown in Formula II below: In formula II, R is Et, Me, i Bu, i Pr, cyclopropyl.

4. The method according to any one of claims 1 to 3, characterized in that The structure of the acyl imidazole compound is shown in the following formula III: In formula III, R' is -CH2CH2CH=CH2, -CH2CH2CH2CH2Cl, -CH2CH2Ph, -(CH2)7CH=CH(CH2)7CH3.

5. The method according to any one of claims 1 to 4, characterized in that The tertiary amine compound is at least one of N,N-dicyclohexylmethylamine, N,N-cyclohexyl tert-butylmethylamine, N,N-isopropyl tert-butylmethylamine and N,N-cycloheptyl tert-butylmethylamine, and the structural formulas thereof are shown below:

6. The method according to any one of claims 1 to 5, characterized in that The photocatalyst is selected from at least one of 4CzIPN, 4DPAIPN, 3DPA2FBN, 3DPAFIPN and Ir(ppy)2(dtbbpy)PF6, and its structural formula is as follows:

7. The method according to any one of claims 1 to 6, characterized in that The organic solvent is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone and N,N-dimethylacetamide; The inert atmosphere includes a nitrogen atmosphere.

8. The method according to any one of claims 1 to 7, characterized in that In the organic solvent, the final concentrations of the following compounds are as follows: The concentration of the olefin compound is 0.033 mol / L to 0.1 mol / L; The concentration of the acid anhydride compound or the acyl imidazole compound is 0.033 mol / L to 0.4 mol / L; The concentration of the tertiary amine compound is 0.033 mol / L to 0.3 mol / L; The concentration of the photocatalyst is 0.001 mol / L to 0.004 mol / L.

9. The method according to any one of claims 1 to 8, characterized in that The molar ratio of the olefin compound to the acid anhydride compound or the acyl imidazole compound is 0.25 to 1:1; The molar ratio of the olefin compound to the tertiary amine compound is 0.33 to 1:

1.

10. The method according to any one of claims 1 to 9, characterized in that The light source used for the visible light irradiation is LED blue light; The light reaction time is 6h to 24h.

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