A method for the reaction of an unactivated ketone with diiodobenzene

Abstract

The invention discloses a reaction method of an unactivated ketone and diiodobenzene. In the presence of sodium hydride, the unactivated ketone and diiodobenzene are reacted in a solvent to complete the reaction of the unactivated ketone and diiodobenzene. In the presence of sodium hydride, the unactivated ketone and diiodobenzene are reacted in a solvent to obtain an aryl ketone compound. The method of the invention is carried out under simple operation and mild reaction conditions, and can be easily scaled up without any metal additives or anhydrous conditions. The method is a general method for rearranged complex o-alkyl aryl ketone products, and the yield is as high as 91%, which is difficult to obtain by traditional methods.

Description

Technical Field

[0001] The invention belongs to organic synthesis technology, and specifically relates to a reaction method of unactivated ketone and diiodobenzene. Background Art

[0002] As an important compound, aromatic ketones are widely used in organic synthesis, medicinal chemistry, agricultural science and other fields. For example, they show pharmacological effects such as antibacterial, pain inhibition, and nerve inhibition. The carbon palladium reaction of nitriles provides a new idea for the synthesis of aromatic ketones, because this method is costly and the catalyst is difficult to recover. The prior art uses aromatic ketones and bromoaryl hydrocarbons as raw materials and mesoporous molecular sieve MCM-41 supported clamp-shaped palladium complex as a catalyst to study a method for preparing aromatic ketone compounds. The results show that under the conditions of a catalyst dosage of 1.0% and a reaction temperature of 81°C, the supported palladium catalyst can catalyze the generation of aromatic ketone compounds; there is also the problem of high reaction cost. Simple alkyl ketones (unactivated ketones) with intrinsically low reactivity can only react with aryl groups generated by halogenated (pseudohalogenated) aromatic hydrocarbons using strong bases (Tripathy, S., Reddy, R. and Durst, T. (2003). Preparation of benzocyclobutenols by low temperature reaction of ketone enolates with benzynes. Can. J. Chem. 81, 997−1002; Zouaoui, MA, Mouaddib, A., Jamart-Gregoire, B., Ianelli, S., Nardelli, M. and Caubere, P. (1991). Synthesis of strained aromatic polycyclic compounds via the reaction of arynes with enolates of cyclic ketones. J. Org. Chem. 56, 4078–4081). Therefore, it is necessary to develop a new method to prepare diaryl ketone compounds and alkyl aryl ketone compounds using unactivated ketones as raw materials through simple reactions. Summary of the invention

[0003] The present invention discloses a novel strategy for generating diaryl ketone compounds and alkyl aryl ketone compounds from o-diiodinated aromatic hydrocarbons and unactivated ketones, which are activated by a 60% NaH dispersion in commercially available mineral oil; the method of the present invention is carried out under simple and mild reaction conditions and can be easily scaled up without any metal additives or anhydrous conditions. The method is a general method for rearranged complex o-alkyl aryl ketone products with a yield of up to 91%, which is difficult to obtain by traditional methods.

[0004] The present invention adopts the following technical solution:

[0005] A method for reacting an unactivated ketone with diiodobenzene comprises reacting the unactivated ketone with diiodobenzene in a solvent in the presence of sodium hydride to complete the reaction of the unactivated ketone with diiodobenzene.

[0006] A method for preparing an aryl ketone compound by reacting an unactivated ketone with diiodobenzene, wherein the unactivated ketone and diiodobenzene are reacted in a solvent in the presence of sodium hydride to obtain an aryl ketone compound. The aryl ketone compound includes a diaryl ketone compound and an alkyl aryl ketone compound.

[0007] In the present invention, the molar ratio of unactivated ketone, diiodobenzene and sodium hydride is 1:(1-6):(2-8), preferably 1:(2-5):(3-6).

[0008] In the present invention, the reaction temperature is room temperature to 60° C., and the reaction time is 1 to 24 hours; preferably, the reaction temperature is 30 to 50° C., and the reaction time is 2 to 6 hours.

[0009] In the present invention, the solvent is tetrahydrofuran or DMA.

[0010] In the present invention, the chemical structural formula of the unactivated ketone is as follows: .

[0011] The chemical structure of diiodobenzene is as follows:

[0012] The chemical structure of the product diaryl ketone compound is as follows:

[0013] The chemical structure of the product alkyl aryl ketone compound is as follows:

[0014] The dotted line indicates ring formation or non-ring formation, Ar indicates phenyl or substituted phenyl, and sub-Ar indicates phenyl or substituted phenyl; R 1 , R 2 , R 3 None of them is hydrogen; Alkyl is an alkyl group, such as a C1-C20 straight chain or straight chain alkyl group; R is an alkyl group or a3 R', R'' are independently selected from alkyl, halogen or alkoxy.

[0015] The prior art uses a classic method of using a strong base such as NaNH2, alkyl lithium or Grignard reagent to prepare diaryl ketone compounds and alkyl aryl ketone compounds, which has the disadvantages of a narrow functional group range and complex side reactions. The present invention discloses a reaction method of an unactivated ketone with diiodobenzene using sodium hydride as an activator for the first time to obtain a variety of diaryl ketone compounds and alkyl aryl ketone compounds. The method of the present invention is carried out under simple operation and mild reaction conditions, and can be easily scaled up without the need for any metal additives or anhydrous conditions. As a general method for rearranged complex o-alkyl aryl ketone products, the method has a yield of up to 91%, which is difficult to obtain with traditional methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The figure shows the reaction diagram of unactivated ketone and the NMR image of the product.

[0017] Figure 2 Schematic diagram of the reaction of unactivated ketone.

[0018] Figure 3 Schematic diagram of the reaction of unactivated ketone.

[0019] Figure 4 Schematic diagram of the reaction of substituted diiodobenzene compounds, furan substrates, and azide substrates.

[0020] Figure 5 Schematic diagram of NMR characterization of the reaction products of furan substrate and azide substrate.

[0021] Figure 6 The chemical structure diagram of the product of Example 2 is shown in FIG.

[0022] Figure 7 The chemical structure diagram of the product of Example 2 is shown in FIG.

[0023] Figure 8 Schematic diagram of the chemical structure of the product of Example 3.

[0024] Fig. 9 Schematic diagram of the chemical structure of the product of Example 4.

[0025] Fig.10 Schematic diagram of the chemical structure of the product of the extended example. DETAILED DESCRIPTION

[0026] The raw materials used in the present invention are commercially available products or obtained according to conventional methods, and the specific preparation operations and testing methods involved are conventional techniques.

[0027] Unless otherwise stated, all reactions were performed under nitrogen atmosphere and all reagents were used as received from commercial suppliers. The progress of the reactions was monitored by thin layer chromatography (TLC) performed on glass plates coated with 0.2 mm thick silica gel GF254. Chromatograms were visualized by fluorescence quenching with UV light at 254 nm or by staining with potassium permanganate. Flash column chromatography was performed using silica gel 60 (200-300 mesh). Mass spectra were obtained using a TOF MS instrument with EI or ESI source. All 1 H NMR, 13 C NMR, 19 F NMR spectra were recorded on a Bruker AV-400, AV-500 or AV-600, and chemical shifts are expressed in parts per million (ppm) referenced to the solvent peak of CDCl3.

[0028] Unless otherwise stated, all reactions were performed under nitrogen atmosphere and all reagents were used as received from commercial suppliers. The progress of the reactions was monitored by thin layer chromatography (TLC) performed on glass plates coated with 0.2 mm thick silica gel GF254. Chromatograms were visualized by fluorescence quenching with UV light at 254 nm or by staining with potassium permanganate. Flash column chromatography was performed using silica gel 60 (200-300 mesh). Mass spectra were obtained using a TOF MS instrument with EI or ESI source. All 1 H NMR, 13 C NMR, 19 F NMR spectra were recorded on a Bruker AV-400, AV-500 or AV-600, and chemical shifts are expressed in parts per million (ppm) referenced to the solvent peak of CDCl3.

[0029] Synthesis example

[0030] See also Figure 1 , to a solution of Weinreb amide in anhydrous THF (25 mL) was added Grignard reagent (15 mmol) at 0°C. After stirring for 30 min, the mixture was warmed to room temperature. After 3 h, the mixture was quenched with saturated aqueous NH4Cl (30 mL) and the resulting mixture was extracted with EtOAc (30 mL×3); the combined extracts were dried over Na2SO4, concentrated in vacuo and purified by silica gel chromatography using an eluent (PE / EtOAc) to give the corresponding unactivated ketone compound 2.

[0031] As an example, compound 2h was used as an example to obtain a white solid, 1.23 g, 97% yield, and NMR characterization was shown in Figure 1 .

[0032] See also Figure 2 , Figure 3 , which is a schematic diagram of the reaction of some unactivated ketone compounds 2, and the specific reaction operation is conventional technology.

[0033] 1-(4-(phenylthio)phenyl)propan-1-one (2k): 1 H NMR (400 MHz, CDCl3): δ7.83 (d, J = 8.4 Hz, 2H), 7.53 – 7.45 (m, 2H), 7.44 – 7.35 (m, 3H), 7.21 (d, J =8.4 Hz, 2H), 2.94 (q, J = 7.2 Hz, 2H), 1.20 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 200.0, 144.6, 134.4, 133.9, 132.4, 129.8, 128.9, 128.7, 127.7, 31.8, 8.4.

[0034] 1-(4-((trifluoromethyl)thio)phenyl)propan-1-one (2l): 1 H NMR (400 MHz, CDCl3): δ 8.05 – 7.92 (m, 2H), 7.78 – 7.68 (m, 2H), 3.01 (q, J = 7.2 Hz, 2H),1.23 (t, J = 7.2 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 199.9, 138.5, 135.9, 129.9,129.4 (q, 308.1 Hz), 128.9, 32.2, 8.2. 19 F NMR (565 MHz, CDCl3): δ -41.82.HRMS(EI-TOF): calculated for [C 10 H9F3OS (M)] + : 234.0326, found: 234.0329.

[0035] 1-(4-tosylphenyl)propan-1-one (2n): 1H NMR (400 MHz, CDCl3): δ 8.06 –7.97 (m, 4H), 7.82 (d, J = 8.2 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 2.98 (q, J = 7.2Hz, 2H), 2.39 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ199.6, 145.7, 144.9, 140.2, 137.9, 130.2, 128.8, 128.0, 127.9, 32.4, 21.7,8.1.HRMS (EI-TOF): calculated for [C 16 H 16 O3S (M)] + : 288.0820, found: 288.0817。

[0036] 1-(4-(phenylethynyl)phenyl)propan-1-one (2v): 1 H NMR (400 MHz, CDCl3):δ 7.98 – 7.90 (m, 2H), 7.63 – 7.58 (m, 2H), 7.58 – 7.52 (m, 1H), 7.41 – 7.33(m, 3H), 3.00 (q, J = 7.2 Hz, 2H), 1.23 (t, J = 7.2 Hz, 3H). 13 C NMR (151 MHz,CDCl3): δ 200.1, 136.1, 131.84, 131.79, 128.9, 128.6, 128.1, 122.8, 92.6,88.8, 31.9, 8.3。

[0037] 6-((tetrahydro-2 H -pyran-2-yl)oxy)-1-( p -tolyl)hexan-1-one (2ba): 1 H NMR(400 MHz, CDCl3): δ 7.85 (d, J= 8.2 Hz, 2H), 7.24 (d, J = 7.9 Hz, 2H), 4.56 (dd, J = 4.4, 2.8 Hz, 1H), 3.90 – 3.81 (m, 1H), 3.79 – 3.70 (m, 1H), 3.52 – 3.45 (m,1H), 3.44 – 3.34 (m, 1H), 2.97 – 2.92 (t, J = 7.4 Hz, 2H), 2.40 (s, 3H) 1.86 –1.62 (m, 6H), 1.60 – 1.40 (m, 6H). 13C NMR (151 MHz, CDCl 3): δ 200.2, 143.7, 134.7,129.3, 128.3, 99.0, 67.5, 62.5, 38.5, 30.9, 29.7, 26.2, 25.6, 24.4, 21.7,19.8.HRMS (ESI-TOF): calculated for [C 18 H 26 O3Na (M + Na)] + : 313.1780, found:313.1781。

[0038] 3-(1,3-dioxan-2-yl)-1-( p -tolyl)propan-1-one (2bb): 1 H NMR (400 MHz,CDCl3): δ 7.88 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 4.66 (t, J = 5.0 Hz,1H), 4.09 (dd, J = 10.6, 5.0 Hz, 2H), 3.81 – 3.71 (m, 2H), 3.08 (t, J = 7.3 Hz,2H), 2.40 (s, 3H), 2.14 – 1.99 (m, 3H), 1.37 – 1.29 (m, 1H). 13C NMR (151 MHz, CDCl3): δ 199.4, 143.8, 134.6, 129.3, 128.3, 101.2, 67.0, 32.6, 29.5, 25.9,21.8.HRMS (EI-TOF): calculated for [C 14 H 18 O3(M)] + : 234.1256, found: 234.1255.

[0039] (4-fluorophenyl)(1-tosylpiperidin-4-yl)methanone (2bw): 1 H NMR (400MHz, CDCl3): δ 7.92 – 7.83 (m, 2H), 7.66 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.0Hz, 2H), 7.17 – 7.04 (m, 2H), 3.81 – 3.73 (m, 2H), 3.19 – 3.10 (m, 1H), 2.56– 2.47 (m, 2H), 2.45 (s, 3H), 1.96 – 1.81 (m, 4H). 13 C NMR (151 MHz, CDCl3): δ199.9, 165.9 (d, J = 255.4 Hz), 143.8, 133.2, 132.1 (d, J = 2.6 Hz), 131.0 (d, J =9.6 Hz), 129.8, 127.9, 116.0 (d, J = 21.8 Hz), 45.7, 42.4, 28.0, 21.7. 19 F NMR (565 MHz, CDCl3): δ -104.69 – -104.75 (m).

[0040] See also Figure 4 , which is a schematic diagram of the reaction of partially replacing the diiodobenzene compound 1, and the specific reaction operation is conventional technology.

[0041] 2,3-diiodo-5-methyl-1,1'-biphenyl (1g): 1H NMR (400 MHz, CDCl3): δ 7.77(d, J = 1.5 Hz, 1H), 7.47 – 7.36 (m, 3H), 7.30 – 7.23 (m, 2H), 7.06 (d, J = 1.5Hz, 1H), 2.29 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ 149.3, 146.7, 139.6, 139.3,129.9, 129.0, 128.0, 127.9, 110.1, 108.5, 20.5。

[0042] 1,2-diiodo-3,5-dimethylbenzene (1h): 1 H NMR (400 MHz, CDCl3): δ 7.56(s, 1H), 6.99 (s, 1H), 2.55 (s, 3H), 2.20 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ144.1, 139.6, 137.8, 129.8, 110.3, 109.8, 32.6, 20.5.HRMS (EI-TOF):calculated for [C8H8I2(M)] + : 357.8715, found: 357.8712。

[0043] 1,2-diiodo-3-methyl-5-(trifluoromethoxy)benzene (1i): 1 H NMR (400 MHz,CDCl3): δ 7.59 (s, 1H), 7.07 (s, 1H), 2.61 (s, 3H). 13 C NMR (151 MHz, CDCl3):δ149.0, 146.0, 129.3, 121.2, 120.3 (q, J = 258.9 Hz), 112.3, 109.9, 33.1. 19 F NMR(565 MHz, CDCl3): δ -57.89.HRMS (EI-TOF): calculated for [C8H5F3I2O (M)] + :427.8382, found: 427.8388。

[0044] Comparison Example

[0045] See also Figure 4 To a suspension of NaH (60% dispersed in mineral oil, 72.5 mg, 1.8 mmol) in anhydrous DMA (1 mL) were added furan (20.4 mg, 0.3 mmol) and o-diiodoaryl 1a (198.0 mg, 0.6 mmol), respectively, and stirred at 0°C for 5 minutes; then the mixture was heated to 50°C and stirred for 3 hours. After that, the reaction was quenched with a saturated aqueous solution of NH4Cl (3 mL) at 0°C, and then the mixture was extracted with EtOAc (3 mL×4). The combined extracts were dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography to obtain a colorless oily Diels-Alder adduct 9, 22.4 mg, with a yield of 52%. The NMR characterization was shown in Figure 5 .

[0046] See also Figure 4 Benzyl azide (27 mg, 0.2 mmol) was added to an oven-dried 10 mL round flask equipped with a stirring bar, and anhydrous THF (4 mL) was added. Subsequently, o-diiodoaryl 1a (134 mg, 0.4 mmol) and NaH (60% dispersed in mineral oil, 24 mg, 0.6 mmol) were added at room temperature. The resulting solution was stirred at 50 °C for 4 h. After that, the reaction was quenched with a saturated aqueous solution of NH4Cl (3 mL) at 0 °C, and then the mixture was extracted with EtOAc (3 mL×4). The combined extracts were dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography to obtain a light yellow solid product 10, 9.5 mg, with a yield of 23%. NMR characterization is shown in Figure 5 .

[0047] Embodiment 1

[0048] General procedure: Ketone and diiodobenzene were added to a solution of a designated base in anhydrous solvent under stirring at 0°C for 5 minutes. After that, the mixture was heated to the designated temperature and stirred for the designated time. The reaction was quenched with saturated NH4Cl (3 mL) aqueous solution at 0°C, and then the mixture was extracted with EtOAc (5 mL×4). The combined extracts were dried over Na2SO4, concentrated in vacuo, and prepared for NMR analysis using methylene as an internal standard. The reaction results under different operating conditions are as follows.

[0049]

[0050]

[0051] a Standard reaction conditions: A suspension of NaH (60% oil, 24 mg, 0.6 mmol, 3 eq.) in anhydrous THF (4 mL) was added under N2, ketone 2a (0.2 mmol) and o-diiodobenzene 1a (0.4 mmol, 2 eq.) were added, and the reaction mixture was stirred at 50 °C for 4 h. b, 1 H NMR yield. c Isolated yield based on using 0.5 mmol of 2a. d No reaction.

[0052] Embodiment 2

[0053] General procedure: To a suspension of NaH (60% dispersion in mineral oil, 60.5 mg, 1.5 mmol) in anhydrous THF (10 mL), ketone 2 (0.5 mmol) and o-diiodoaryl 1 (2.0 equiv.) were added separately and stirred at 0 °C for 5 min. The mixture was then heated to 50 °C for 4 h. Thereafter, the reaction was quenched with saturated aqueous NH4Cl (6 mL) at 0 °C. The mixture was then extracted with EtOAc (8 mL×4). The combined extracts were dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by silica gel chromatography to give o-alkylaryl ketone 3; the reaction results for different substrates are shown in Figure 6 and Figure 7 , where the yields are isolated yields, for products 3ar, 3bn-3bz, NaH (3.0 mmol, 6 equiv) and 1a (2.5 mmol, 5 equiv) were used, and for product 3cd, NaH (2.0 mmol, 4 equiv) and 1a (1.5 mmol, 3 equiv) were used.

[0054] Embodiment 3

[0055] General procedure: To a suspension of NaH (60% dispersion in mineral oil, 60.5 mg, 1.5 mmol) in anhydrous THF (10 mL), ketone 2 (0.5 mmol) and o-diiodoaryl 1 (2.0 equiv.) were added separately and stirred at 0 °C for 5 min. The mixture was then heated to 50 °C for 4 h. Thereafter, the reaction was quenched with saturated aqueous NH4Cl (6 mL) at 0 °C. The mixture was then extracted with EtOAc (8 mL×4). The combined extracts were dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by silica gel chromatography to give o-alkylaryl ketone 3; the reaction results for different substrates are shown in Figure 8 , where the yields are isolated yields, for products 3ci, 3cp, and 3cq, NaH (3.0 mmol, 6 equiv) and 1a (2.5 mmol, 5 equiv) were used.

[0056] Embodiment 4

[0057] General procedure: To a suspension of NaH (60% dispersion in mineral oil, 60.5 mg, 1.5 mmol) in anhydrous THF (10 mL), ketone 2 (0.5 mmol) and o-diiodoaryl 1 (2.0 equiv.) were added separately and stirred at 0 °C for 5 min. The mixture was then heated to 50 °C for 4 h. Thereafter, the reaction was quenched with saturated aqueous NH4Cl (6 mL) at 0 °C. The mixture was then extracted with EtOAc (8 mL×4). The combined extracts were dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by silica gel chromatography to give o-alkylaryl ketone 3; the reaction results for different substrates are shown in Fig. 9 , where yield is the isolated yield.

[0058] Amplification experiment

[0059] According to Example 2, when 2a (1.48 g, 10 mmol) and THF (100 mL) were used in the reaction, 1.78 g was obtained with a yield of 79%.

[0060] According to Example 2, when 2a (2.96 g, 20 mmol) and THF (200 ml) were used in the reaction, 3a (3.68 g) was obtained with a yield of 82%.

[0061] According to Example 2, when 2c (10 mmol) and THF (0.2 M) were used in the reaction, 3c was obtained in a yield of 65%.

[0062] According to Example 2, when 2 g (10 mmol) and THF (0.2 M) were used in the reaction, 3 g was obtained with a yield of 72%.

[0063] Extended Example

[0064] See also Fig.10 , to [Ph3PMe] at 0°C + [Br] ̶ To a suspension of (357.2 mg, 1.0 mmol) in anhydrous THF (4 mL) was added n-BuLi (0.4 mL, 2.5 M in hexane). After stirring for 30 min, a solution of ketone 3a (112.5 mg, 0.5 mL) in THF (1 mL) was added to the mixture at 0 °C. The resulting mixture was then heated to room temperature for 12 h. Thereafter, the mixture was treated with saturated aqueous NH4Cl solution (5 mL) and extracted with EtOAc (5 mL×3). The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography to give compound 5 as a colorless oil, 106.8 mg, 96% yield, HRMS (EI-TOF): calculated for [C 17 H 18O (M)] + : 222.1409, found: 222.1411.

[0065] See also Fig.10 , To a suspension of anhydrous AlCl3 (166.7 mg, 1.25 mmol) and NaBH4 (85.1 mg, 2.25 mmol) in anhydrous THF (4 mL) was added a solution of ketone 3a (112.5 mg, 0.5 mmol) in THF (1 mL) at 0°C. The resulting mixture was then heated to 60°C for 5 hours. Thereafter, the mixture was treated with a saturated aqueous Rochelle salt solution (5 mL) and extracted with EtOAc (5 mL×3). The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography to give a colorless oil compound 6, 78.2 mg, 74% yield, HRMS (EI-TOF): calculated for [C 16 H 18 O(M)] + : 210.1409, found: 210.1412.

[0066] See also Fig.10 , Step a: To a solution of ketone 3c (114.1 mg, 0.5 mmol) in MeOH (2.5 mL) was added NaBH4 (28.4 mg, 0.75 mmol) at 0 °C. After stirring for 10 min, the mixture was heated to room temperature for 4 h. The mixture was then treated with saturated aqueous NH4Cl (4 mL) and extracted with DCM (5 mL×3). The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography to give 7c as a colorless oil, 111.6 mg, 97% yield. Step b: To a solution of 7c (111.6 mg, 0.49 mmol) in HFIP (2.5 mL) was added TsONHMe (106.7 mg, 0.53 mmol) at room temperature and ambient atmosphere. The resulting mixture was stirred at room temperature for 12 h. The reactant was then diluted with DCM (3 mL) and basified with saturated aqueous NaHCO3 (3 mL). The aqueous layer was extracted with DCM (5 mL x 3), and the combined organic layers were washed with brine (5 mL), dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography to afford the title compound as a colorless oil, 47.3 mg, 72% yield.

[0067] The NMR characterizations of some products of the present invention are as follows.

[0068] (2-ethylphenyl)( p-tolyl)methanone (3a): 1 H NMR (400 MHz, CDCl3): δ 7.67– 7.60 (m, 2H), 7.36 – 7.30 (m, 1H), 7.27 – 7.23 (m, 1H), 7.19 – 7.13 (m,4H), 2.58 (q, J = 7.5 Hz, 2H), 2.34 (s, 3H), 1.07 (t, J = 7.6 Hz, 3H). 13 C NMR (101MHz, CDCl3): δ 198.6, 144.3, 142. 9, 138.9, 135.4, 130.5, 130.2 129.4, 129.3,128.2, 125.3, 26.5, 21.8, 16.0.HRMS (EI-TOF): calculated for [C 16 H 16 O (M)] + :224.1201, found: 224.1199。

[0069] [1,1'-biphenyl]-4-yl(2-ethylphenyl)methanone (3b): 1 H NMR (400 MHz,CDCl3): δ 7.82 – 7.75 (m, 2H), 7.59 – 7.49 (m, 4H), 7.39 – 7.23 (m, 5H), 7.22– 7.12 (m, 2H), 2.60 (q, J = 7.5 Hz, 2H), 1.08 (t, J = 7.6 Hz, 3H). 13 C NMR (151MHz, CDCl3): δ 198.4, 146.0, 143.0, 134.0, 138.6, 136.6, 130.9, 130.3, 129.5,129.1, 128.4, 128.3, 127.4, 127.2, 125.3, 26.5, 16.1.HRMS (EI-TOF):calculated for [C 21 H 18 O (M)] +: 286.1358, found: 286.1360。

[0070] (2-ethylphenyl)(4-fluorophenyl)methanone (3c): 1 H NMR (400 MHz, CDCl3):δ 7.78 – 7.71 (m, 2H), 7.37 – 7.30 (m, 1H), 7.27 – 7.23 (m, 1H), 7.18 – 7.14(m, 2H), 7.06 – 6.99 (m, 2H), 2.57 (q, J = 7.5 Hz, 2H), 1.07 (t, J = 7.6 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 197.2, 166.0 (d, J = 255.2 Hz), 143.0, 138.2, 134.3(d, J = 2.9 Hz), 132.9 (d, J = 9.3 Hz), 130.5, 129.6, 128.2, 125.4, 115.7 (d, J =21.9 Hz), 26.5, 16.0. 19 F NMR (377 MHz, CDCl3): δ -104.77 – -104.89 (m). HRMS(EI-TOF): calculated for [C 15 H 13 FO (M)] + : 228.0950, found: 228.0947。

[0071] (4-chlorophenyl)(2-ethylphenyl)methanone (3d): 1 H NMR (400 MHz, CDCl3):δ 7.68 – 7.63 (m, 2H), 7.37 – 7.30 (m, 3H), 7.27 – 7.23 (m, 1H), 7.17 – 7.13(m, 2H), 2.57 (q, J = 7.5 Hz, 2H), 1.06 (t, J = 7.6 Hz, 3H).13 C NMR (151 MHz,CDCl3): δ 197.5, 143.2, 139.8, 138.0, 136.3, 131.7, 130.6, 129.7, 128.9,128.3, 125.4, 26.5, 16.1.HRMS (EI-TOF): calculated for [C 15 H 13 ClO (M)] + :244.0655, found: 244.0650。

[0072] (4-bromophenyl)(2-ethylphenyl)methanone (3e): 1 H NMR (400 MHz, CDCl3):δ 7.61 – 7.55 (m, 2H), 7.53 – 7.46 (m, 2H), 7.37 – 7.31 (m, 1H), 7.27 – 7.23(m, 1H), 7.17 – 7.13 (m, 2H), 2.57 (q, J = 7.5 Hz, 2H), 1.06 (t, J = 7.6 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.7, 143.2, 137.9, 136.7, 131.9, 131.7, 130.7,129.7, 128.6, 128.3, 125.4, 26.5, 16.1.HRMS (EI-TOF): calculated for[C 15 H 13 BrO (M)] + : 288.0150, found: 288.0147。

[0073] (2-ethylphenyl)(4-iodophenyl)methanone (3f): 1 H NMR (400 MHz, CDCl3):δ 7.73 (d, J = 8.3 Hz, 2H), 7.42 (d, J = 8.3 Hz, 2H), 7.38 – 7.30 (m, 1H), 7.25(d, J= 7.7 Hz, 1H), 7.18 – 7.14 (m, 2H), 2.57 (q, J = 7.5 Hz, 2H), 1.06 (t, J =7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3):δ 198.0, 143.2, 137.9, 137.8, 137.2,131.6, 130.7, 129.7, 128.3, 125.4, 101.5, 26.5, 16.1.HRMS (EI-TOF):calculated for [C 15 H 13 IO (M)] + : 336.0011, found: 336.0014。

[0074] (2-ethylphenyl)(4-methoxyphenyl)methanone (3g): 1 H NMR (400 MHz,CDCl3): δ 7.71 – 7.65 (m, 2H), 7.31 – 7.25 (m, 1H), 7.23 – 7.18 (m, 1H), 7.15– 7.09 (m, 2H), 6.83 – 6.77 (m, 2H), 3.74 (s, 3H), 2.53 (q, J = 7.6 Hz, 2H),1.03 (t, J = 7.6 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.5, 163.8, 142.6, 139.0,132.6, 130.7, 129.9, 129.3, 127.8, 125.2, 113.7, 55.6, 26.4, 16.0.HRMS (EI-TOF): calculated for [C 16 H 16 O2(M)] + : 240.1150, found: 240.1148。

[0075] (2-ethylphenyl)(4-phenoxyphenyl)methanone (3h): 1H NMR (400 MHz,CDCl3): δ 7.72 – 7.63 (m, 2H), 7.31 – 7.23 (m, 3H), 7.22 – 7.18 (m, 1H), 7.16– 7.03 (m, 3H), 7.00 – 6.92 (m, 2H), 6.89 – 6.82 (m, 2H), 2.54 (q, J = 7.5 Hz,2H), 1.04 (t, J = 7.6 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.4, 162.3, 155.4,142.8, 138.7, 132.6, 132.3, 130.2, 130.1, 129.4, 128.0, 125.2, 124.8, 120.4,117.2, 26.5, 16.0.HRMS (EI-TOF): calculated for [C 21 H 18 O2(M)] + : 302.1307,found: 302.1302。

[0076] (2-ethylphenyl)(4-((tetrahydro-2 H -pyran-2-yl)oxy)phenyl)methanone(3i): 1 H NMR (400 MHz, CDCl3):δ 7.75 – 7.68 (m, 2H), 7.36 – 7.30 (m, 1H), 7.25(d, J = 7.6 Hz, 1H), 7.21 – 7.13 (m, 2H), 7.03 – 6.98 (m, 2H), 5.45 (t, J = 3.1Hz, 1H), 3.84 – 3.73 (m, 1H), 3.61 – 3.48 (m, 1H), 2.58 (q, J = 7.5 Hz, 2H),2.00 – 1.87 (m, 1H), 1.85 – 1.76 (m, 2H), 1.69 – 1.58 (m, 2H), 1.57 – 1.49(m, 1H), 1.08 (t, J = 7.6 Hz, 3H). 13C NMR (151 MHz, CDCl3): δ 197.6, 161.4, 142.6,139.0, 132.5, 131.3, 130.0, 129.3, 127.9, 125.2, 115.9, 96.1, 62.2, 30.2,26.4, 25.1, 18.6, 16.0. HRMS (EI-TOF): calculated for [C 20 H 22 O3(M)] + : 310.1569,found: 310.1575。

[0077] (2-ethylphenyl)(4-(trifluoromethoxy)phenyl)methanone (3j): 1 H NMR (400MHz, CDCl3): δ 7.81 – 7.73 (m, 2H), 7.36 – 7.31 (m, 1H), 7.25 (d, J = 7.7 Hz,1H), 7.20 – 7.12 (m, 4H), 2.57 (q, J = 7.5 Hz, 2H), 1.07 (t, J = 7.6 Hz, 3H). 13 CNMR (151 MHz, CDCl3): δ 197.1, 152.8, 143.3, 137.9, 136.2, 132.3, 130.7,129.7, 128.4, 125.3, 120.4 (q, J = 259.1 Hz), 120.3, 26.5, 16.0. 19 F NMR (565MHz, CDCl3): δ -57.61.HRMS (EI-TOF): calculated for [C 16 H 13 F3O2(M)] + : 294.0868,found: 294.0865。

[0078] (2-ethylphenyl)(4-(phenylthio)phenyl)methanone (3k): 1H NMR (400 MHz,CDCl3): δ 7.72 – 7.65 (m, 2H), 7.55 – 7.49 (m, 2H), 7.45 – 7.36 (m, 4H), 7.32(d, J = 7.8 Hz, 1H), 7.26 – 7.21 (m, 2H), 7.21 – 7.16 (m, 2H), 2.66 (q, J = 7.5Hz, 2H), 1.16 (t, J = 7.6 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.8, 145.6,142.9, 138.4, 135.0, 134.3, 131.8, 130.8, 130.3, 129.8, 129.5, 129.0, 128.1,127.0, 125.2, 26.5, 16.0.HRMS (EI-TOF): calculated for [C 21 H 18 OS (M)] + :318.1078, found: 318.1081。

[0079] (2-ethylphenyl)(4-((trifluoromethyl)thio)phenyl)methanone (3l): 1 H NMR(400 MHz, CDCl3): δ 7.77 – 7.69 (m, 2H), 7.66 – 7.57 (m, 2H), 7.38 – 7.30 (m,1H), 7.28 – 7.22 (m, 1H), 7.18 – 7.12 (m, 2H), 2.58 (q, J = 7.5 Hz, 2H), 1.06(t, J = 7.5 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.6, 143.6, 139.6, 137.5,135.6, 131.0, 130.12, 129.8, 129.4 (q, J = 308.8 Hz), 128.6, 125.4, 26.6,16.1. 19F NMR (565 MHz, CDCl3): δ -41.65.HRMS (EI-TOF):calculated for [C 16 H 13 F3OS(M)] + : 310.0639, found: 310.0644。

[0080] (2-ethylphenyl)(4-(trifluoromethyl)phenyl)methanone (3m): 1 H NMR (400MHz, CDCl3):δ 7.82 – 7.76 (m, 2H), 7.63 – 7.57 (m, 2H), 7.38 – 7.30 (m, 1H),7.28 – 7.22 (m, 1H), 7.17 – 7.12 (m, 2H), 2.57 (q, J = 7.5 Hz, 2H), 1.05 (t, J =7.5 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.6, 143.7, 140.9, 137.5, 134.5 (q, J = 32.2 Hz), 131.1, 130.5, 129.9, 128.7, 125.7 – 125.6 (m), 125.5, 123.8 (q, J =272.4 Hz), 26.6, 16.1. 19 F NMR (565 MHz, CDCl3): δ -63.07.HRMS (EI-TOF):calculated for [C 16 H 13 F3O (M)] + : 278.0918, found: 278.0915。

[0081] (2-ethylphenyl)(4-tosylphenyl)methanone (3n): 1H NMR (400 MHz, CDCl3):δ 8.04 – 7.98 m, 2H), 7.92 – 7.83 (m, 4H), 7.49 – 7.42 (m, 1H), 7.38 – 7.30(m, 3H), 7.28 – 7.18 (m, 2H), 2.67 (q, J = 7.5 Hz, 2H), 2.41 (s, 3H), 1.15 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3):δ 197.2, 145.8, 144.9, 143.8, 141.5,137.8, 137.1, 131.2, 130.8, 130.2, 129.9, 128.8, 128.0, 127.6, 125.4, 26.5,21.7, 16.1.HRMS (EI-TOF): calculated for [C 22 H 20 O3(M)] + : 364.1133, found:364.1129。

[0082] 4-(2-ethylbenzoyl)benzonitrile (3o): 1 H NMR (400 MHz, CDCl3): δ 7.94 –7.84 (m, 2H), 7.80 – 7.71 (m, 2H), 7.50 – 7.44 (m, 1H), 7.41 – 7.33 (m, 1H),7.30 – 7.22 (m, 2H), 2.68 (q, J = 7.5 Hz, 2H), 1.16 (t, J = 7.5 Hz, 3H). 13 C NMR(101 MHz, CDCl3): δ 197.1, 143.8, 141.3, 137.0 132.4, 131.3, 130.5, 130.0,128.7, 125.5, 118.1, 116.4, 26.6, 16.1.HRMS (EI-TOF): calculated for [C 16 H 13 NO(M)] + : 235.0997, found: 235.0994。

[0083] (2-ethylphenyl)(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone (3p): 1 H NMR (400 MHz, CDCl3): δ 7.82 – 7.78 (m, 2H), 7.72 –7.67 (m, 2H), 7.37 – 7.31 (m, 1H), 7.27 – 7.23 (m, 1H), 7.19 – 7.13 (m, 2H),2.58 (q, J = 7.5 Hz, 2H), 1.27 (s, 12H), 1.06 (t, J = 7.5 Hz, 3H). 13 C NMR (101MHz, CDCl3): δ 199.1, 143.3, 139.9, 138.4, 134.8, 130.5, 129.6, 129.2, 128.5,125.3, 84.3, 26.6, 25.0, 16.0. HRMS (EI-TOF): calculated for [C 21 H 25 BO3(M +Na)] + :336.1897, found: 336.1894。

[0084] (2-ethylphenyl)( m -tolyl)methanone (3q): 1 H NMR (400 MHz, CDCl3): δ 7.55(s, 1H), 7.48 – 7.43 (m, 1H), 7.33 – 7.25 (m, 2H), 7.23 – 7.17 (m, 2H), 7.17– 7.09 (m, 2H), 2.56 (q, J = 7.5 Hz, 2H), 2.27 (s, 3H), 1.05 (t, J = 7.6 Hz, 3H). 13C NMR (151 MHz, CDCl3):δ 199.0, 143.0, 138.7, 138.4, 137.9, 134.1, 130.5,130.3, 129.5, 128.4, 128.3, 127.7, 125.2, 26.5, 21.4, 16.0.HRMS (EI-TOF):calculated for [C 16 H 16 O (M)] + : 224.1201, found: 224.1204。

[0085] (2-ethylphenyl)(3-methoxyphenyl)methanone (3r): 1 H NMR (400 MHz,CDCl3): δ 7.38 – 7.30 (m, 2H), 7.27 – 7.12 (m, 5H), 7.06 – 7.01 (m, 1H), 3.75(s, 3H), 2.59 (q, J = 7.5 Hz, 2H), 1.08 (t, J = 7.6 Hz, 3H). 13 C NMR (101 MHz,CDCl3): δ 198.6, 159.8, 143.0, 139.2, 138.4, 130.3, 129.5, 129.4, 128.3,125.2, 123.5, 119.9, 113.8, 55.5, 26.5, 16.0.HRMS (EI-TOF): calculated for[C 16 H 16 O (M)] + : 240.1150, found: 240.1147。

[0086] (3-chlorophenyl)(2-ethylphenyl)methanone (3s): 1 H NMR (400 MHz, CDCl3):δ 7.72 (t, J = 1.6 Hz, 1H), 7.58 (d, J = 7.7 Hz, 1H), 7.46 (dd, J= 8.0, 1.0 Hz,1H), 7.39 – 7.34 (m, 1H), 7.33 – 7.25 (m, 2H), 7.18 (d, J = 4.1 Hz, 2H), 2.59(q, J = 7.5 Hz, 2H), 1.09 (t, J = 7.5 Hz, 3H). 13C NMR (101 MHz, CDCl 3): δ 197.3, 143.4,139.6, 137.7, 134.9, 133.2, 130.8, 130.1, 129.9, 129.7, 128.5, 128.4, 125.4,26.5, 16.1. HRMS (EI-TOF): calculated for [C 15 H 13 ClO (M)] + : 244.0655, found:244.0652。

[0087] (2-ethylphenyl)( o -tolyl)methanone (3t): 1 H NMR (400 MHz, CDCl3): δ 7.43– 7.34 (m, 2H), 7.33 – 7.23 (m, 4H), 7.20 – 7.14 (m, 2H), 2.79 (q, J = 7.5 Hz,2H), 2.48 (s, 3H), 1.20 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 200.9,144.3, 139.1, 138.8, 138.7, 131.6, 131.4, 131.1, 131.0, 130.1, 129.9, 125.5,125.4, 26.7, 21.0, 16.03。

[0088] (2-ethylphenyl)(2-methoxyphenyl)methanone (3u): 1 H NMR (400 MHz,CDCl3): δ 7.39 – 7.32 (m, 2H), 7.29 – 7.23 (m, 1H), 7.21 – 7.14 (m, 2H), 7.07– 7.00 (m, 1H), 6.91 – 6.82 (m, 2H), 3.56 (s, 3H), 2.75 (q, J = 7.5 Hz, 2H),1.11 (t, J = 7.5 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 198.5, 158.5, 144.0, 139.5,133.1, 131.1, 130.8, 129.7, 129.7, 129.5, 125.2, 120.4, 111.9, 55.7, 26.7,16.0.HRMS (EI-TOF): calculated for [C 16 H 16 O2(M)] + : 240.1150, found: 240.1145。

[0089] (2-ethylphenyl)(4-(phenylethynyl)phenyl)methanone (3v): 1 H NMR (400MHz, CDCl3): δ 7.69 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 8.2 Hz, 2H), 7.47 – 7.42(m, 2H), 7.36 – 7.30 (m, 1H), 7.28 – 7.22 (m, 4H), 7.19 – 7.12 (m, 2H), 2.57(q, J = 7.5 Hz, 2H), 1.07 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 198.0,143.1, 138.2, 137.0, 131.9, 131.7, 130.5, 130.2, 129.6, 128.9, 128.6, 128.4,128.3, 125.3, 122.7, 93.0, 88.8, 26.5, 16.0.HRMS (EI-TOF): calculated for[C 23 H18 O (M)] + : 310.1358, found: 310.1360。

[0090] benzo[ d ][1,3]dioxol-5-yl(2-ethylphenyl)methanone (3w): 1 H NMR (400MHz, CDCl3): δ 7.31 – 7.25 (m, 2H), 7.22 – 7.16 (m, 2H), 7.11 (d, J = 4.1 Hz,2H), 6.68 (d, J = 8.1 Hz, 1H), 5.93 (s, 2H), 2.52 (q, J = 7.5 Hz, 2H), 1.03 (t, J =7.6 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.1, 152.2, 148.2, 142.6, 138.8,132.6, 130.0, 129.3, 127.8, 127.5, 125.2, 109.3, 107.8, 102.0, 26.4,15.9.HRMS (EI-TOF): calculated for [C 16 H 14 O2(M)] + : 254.0943, found: 254.0947。

[0091] (2,4-dimethoxyphenyl)(2-ethylphenyl)methanone (3x): 1 H NMR (400 MHz,CDCl3): δ 7.40 (d, J = 8.5 Hz, 1H), 7.28 – 7.21 (m, 1H), 7.19 – 7.15 (m, 1H),7.12 (dd, J = 7.6, 1.4 Hz, 1H), 7.09 – 7.02 (m, 1H), 6.42 – 6.34 (m, 2H), 3.75(s, 3H), 3.58 (s, 3H), 2.65 (q, J = 7.5 Hz, 2H), 1.09 (t, J= 7.5 Hz, 3H). 13 C NMR(151 MHz, CDCl3): δ 197.2, 164.4, 161.2, 142.8, 140.9, 134.3, 129.9, 129.3,128.4, 125.1, 121.8, 104.7, 98.9, 55.7, 55.6, 26.4, 15.9.HRMS (EI-TOF):calculated for [C 17 H 18 O3(M)] + : 270.1256, found: 270.1251。

[0092] (2,4-dichlorophenyl)(2-ethylphenyl)methanone (3y): 1 H NMR (400 MHz,CDCl3): δ 7.41 – 7.34 (m, 2H), 7.33 – 7.22 (m, 3H), 7.20 – 7.17 (m, 1H), 7.14– 7.08 (m, 1H), 2.85 (q, J = 7.5 Hz, 2H), 1.18 (t, J = 7.5 Hz, 3H). 13 C NMR (101MHz, CDCl3): δ 196.3, 145.7, 137.9, 137.3, 136.7, 133.3, 132.4, 131.5, 131.1,130.6, 130.5, 127.2, 125.7, 27.0, 15.9.HRMS (EI-TOF): calculated for[C 15 H 12 Cl2O (M)] + : 278.0265, found: 278.0262。

[0093] (2-ethylphenyl)(naphthalen-1-yl)methanone (3z): 1 H NMR (400 MHz,CDCl3): δ 8.69 (d, J = 8.5 Hz, 1H), 8.02 (d, J= 8.2 Hz, 1H), 7.96 – 7.90 (m,1H), 7.66 – 7.54 (m, 3H), 7.49 – 7.41 (m, 2H), 7.40 – 7.32 (m, 2H), 7.25 –7.19 (m, 1H), 2.85 (q, J = 7.5 Hz, 2H), 1.25 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz,CDCl3): δ 200.5, 144.4, 139.7, 136.3, 134.0, 132.9, 131.2, 131.14, 131.08,130.2, 129.9, 128.6, 128.1, 126.6, 126.0, 125.4, 124.3, 26.8, 16.1.HRMS (EI-TOF): calculated for [C 19 H 16 O (M)] + : 260.1201, found: 260.1203。

[0094] (2-ethylphenyl)(6-methoxynaphthalen-2-yl)methanone (3aa): 1 H NMR (400MHz, CDCl3): δ 8.00 (s, 1H), 7.88 (dd, J = 8.6, 1.7 Hz, 1H), 7.69 – 7.60 (m,2H), 7.36 – 7.30 (m, 1H), 7.28 – 7.18 (m, 2H), 7.18 – 7.12 (m, 1H), 7.08 –7.02 (m, 2H), 3.81 (s, 3H), 2.58 (q, J = 7.5 Hz, 2H), 1.06 (t, J = 7.6 Hz, 3H). 13CNMR (151 MHz, CDCl3): δ 198.6, 160.0, 142.9, 138.9, 137.5, 133.2, 132.8,131.3, 130.2, 129.5, 128.2, 127.8, 127.2, 125.9, 125.3, 119.8, 105.9, 55.5,26.5, 16.0.HRMS (EI-TOF): calculated for [C 20 H 18 O2(M)] + : 290.1307, found:290.1305。

[0095] (2-ethylphenyl)(pyren-4-yl)methanone (3ab): 1 H NMR (400 MHz, CDCl3): δ8.92 (d, J = 9.3 Hz, 1H), 8.30 – 8.15 (m, 4H), 8.12 – 8.01 (m, 4H), 7.51 – 7.46(m, 1H), 7.45 – 7.34 (m, 2H), 7.25 – 7.20 (m, 1H), 2.87 (q, J = 7.5 Hz, 2H),1.27 (t, J = 7.5 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 201.0, 144.4, 140.2, 134.0,133.0, 131.22, 131.20, 130.7, 130.5, 130.4, 130.0, 129.8, 129.7, 129.2,127.3, 126.54, 126.46, 126.3, 125.5, 125.1, 125.0, 124.5, 123.9, 26.9,16.2.HRMS (EI-TOF): calculated for [C 25 H 18 O (M)] + : 334.1358, found: 334.1356。

[0096] (2-ethylphenyl)(pyridin-3-yl)methanone (3ac): 1H NMR (400 MHz, CDCl3):δ 8.76 (d, J = 2.0 Hz, 1H), 8.61 (dd, J = 4.8, 1.7 Hz, 1H), 7.98 – 7.93 (m, 1H),7.31 – 7.22 (m, 2H), 7.19 (d, J = 7.7 Hz, 1H), 7.11 – 7.06 (m, 2H), 2.52 (q, J =7.5 Hz, 2H), 0.99 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 197.2, 153.5,151.7, 143.7, 137.2, 137.2, 133.4, 131.2, 130.0, 128.7, 125.5, 123.6, 26.6,16.1. HRMS (EI-TOF): calculated for [C 14 H 13 NO (M)] + : 211.0997, found: 211.0993。

[0097] (2-ethylphenyl)(thiophen-2-yl)methanone (3ad): 1 H NMR (400 MHz, CDCl3):δ 7.63 (dd, J = 4.9, 0.8 Hz, 1H), 7.37 – 7.30 (m, 3H), 7.25 (d, J = 7.5 Hz, 1H),7.20 – 7.14 (m, 1H), 7.02 (dd, J = 4.7, 4.0 Hz, 1H), 2.64 (q, J = 7.5 Hz, 2H),1.10 (t, J = 7.5 Hz, 3H). 13C NMR (151 MHz, CDCl3): δ 190.7, 145.3, 142.9, 138.3,135.6, 135.0, 130.5, 129.6, 128.2, 128.1, 125.2, 26.4, 16.1.HRMS (EI-TOF):calculated for [C 13 H 12 OS (M)] + : 216.0609, found: 216.0605。

[0098] phenyl( o- tolyl)methanone (3ae): 1 H NMR (400 MHz, CDCl3): δ 7.86 – 7.78(m, 2H), 7.61 – 7.55 (m, 1H), 7.48 – 7.43 (m, 2H), 7.42 – 7.37 (m, 1H), 7.34– 7.28 (m, 2H), 7.27 – 7.22 (m, 1H), 2.34 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ198.7, 138.7, 137.8, 136.8, 133.2, 131.1, 130.3, 130.2, 128.6, 128.5, 125.3,20.1。

[0099] o -tolyl( p -tolyl)methanone (3af): 1 H NMR (400 MHz, CDCl3): δ 7.61 (d, J =8.2 Hz, 2H), 7.31 – 7.25 (m, 1H), 7.22 – 7.12 (m, 5H), 2.32 (s, 3H), 2.22 (s,3H). 13 C NMR (151 MHz, CDCl3): δ 198.5, 144.2, 139.1, 136.5, 135.2, 131.0,130.4, 130.1, 129.3, 128.3, 125.3, 21.8, 20.0。

[0100] [1,1'-biphenyl]-4-yl( o-tolyl)methanone (3ag): 1 H NMR (400 MHz, CDCl3):δ 7.92 – 7.86 (m, 2H), 7.70 – 7.66 (m, 2H), 7.66 – 7.62 (m, 2H), 7.51 – 7.45(m, 2H), 7.44 – 7.38 (m, 2H), 7.38 – 7.34 (m, 1H), 7.33 – 7.27 (m, 2H), 2.37(s, 3H). 13C NMR (151 MHz, CDCl 3): δ 198.4, 146.0, 140.0, 138.9, 136.8, 136.5, 131.2,130.9, 130.4, 129.1, 128.6, 128.4, 127.5, 127.3, 125.4, 20.12。

[0101] (4-fluorophenyl)( o -tolyl)methanone (3ah): 1 H NMR (400 MHz, CDCl3): δ7.90 – 7.77 (m, 2H), 7.43 – 7.36 (m, 1H), 7.32 – 7.22 (m, 3H), 7.15 – 7.09(m, 2H), 2.32 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ 197.2, 165.95 (d, J = 255.5Hz), 138.5, 136.7, 134.2 (d, J = 2.9 Hz), 132.9 (d, J = 9.4 Hz), 131.2, 130.5,128.4, 125.4, 115.8 (d, J = 22.0 Hz), 20.0. 19 F NMR (565 MHz, CDCl3): δ -104.86– -104.99 (m)。

[0102] (4-iodophenyl)( o- tolyl)methanone (3ai): 1H NMR (400 MHz, CDCl3): δ 7.87– 7.77 (m, 2H), 7.54 – 7.47 (m, 2H), 7.43 – 7.36 (m, 1H), 7.31 – 7.21 (m,3H), 2.33 (s, 3H). 13 C NMR (151 MHz, CDCl3): δ 197.9, 138.0, 137.9, 137.2,137.0, 131.6, 131.3, 130.6, 128.6, 125.4, 101.4, 20.1. HRMS (EI-TOF):calculated for [C 14 H 11 IO (M)] + : 321.9855, found: 321.9859。

[0103] (4-methoxyphenyl)( o -tolyl)methanone (3aj): 1 H NMR (400 MHz, CDCl3): δ7.73 – 7.67 (m, 2H), 7.31 – 7.25 (m, 1H), 7.22 – 7.12 (m, 3H), 6.87 – 6.82(m, 2H), 3.78 (s, 3H), 2.22 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ 197.5, 163.8,139.3, 136.2, 132.6, 130.9, 130.6, 129.9, 128.0, 125.3, 113.8, 55.6, 19.9。

[0104] (4-(phenylthio)phenyl)( o -tolyl)methanone (3ak): 1 H NMR (400 MHz,CDCl3): δ 7.71 – 7.64 (m, 2H), 7.57 – 7.48 (m, 2H), 7.44 – 7.33 (m, 4H), 7.29– 7.22 (m, 3H), 7.21 – 7.17 (m, 2H), 2.31 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 197.7,145.5, 138.7, 136.6, 135.0, 134.2, 131.9, 131.1, 130.8, 130.2, 129.8, 129.0,128.3, 127.2, 125.3, 20.0.HRMS (EI-TOF): calculated for [C 20 H 16 OS (M)] + :304.0922, found: 304.0919。

[0105] naphthalen-2-yl( o -tolyl)methanone (3al): 1 H NMR (400 MHz, CDCl3): δ8.20 (s, 1H), 8.03 (dd, J = 8.6, 1.6 Hz, 1H), 7.96 – 7.85 (m, 3H), 7.64 – 7.58(m, 1H), 7.56 – 7.51 (m, 1H), 7.47 – 7.37 (m, 2H), 7.37 – 7.27 (m, 2H), 2.38(s, 3H). 13 C NMR (151 MHz, CDCl3): δ 198.7, 139.0, 136.9, 135.7, 135.2, 132.8,132.5, 131.1, 130.3, 129.7, 128.7, 128.63, 128.58, 127.9, 126.9, 125.4,125.2, 20.1。

[0106] (2-butylphenyl)(phenyl)methanone (3am): 1 H NMR (400 MHz, CDCl3): δ 7.72– 7.64 (m, 2H), 7.47 – 7.41 (m, 1H), 7.35 – 7.25 (m, 3H), 7.21 – 7.17 (m,1H), 7.16 – 7.08 (m, 2H), 2.53 (t, J = 7.8 Hz, 2H), 1.45 – 1.35 (m, 2H), 1.19 –1.08 (m, 2H), 0.70 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 198.9, 141.8,138.6, 138.0, 133.2, 130.22, 130.20, 128.5, 125.2, 33.9, 33.1, 22.6, 13.9.HRMS (EI-TOF): calculated for [C 17 H 18 O (M)] + : 238.1358, found: 238.1354。

[0107] (2-hexylphenyl)(phenyl)methanone (3an): 1 H NMR (400 MHz, CDCl3): δ 7.71– 7.66 (m, 2H), 7.47 – 7.41 (m, 1H), 7.35 – 7.24 (m, 3H), 7.21 – 7.17 (m,1H), 7.16 – 7.07 (m, 2H), 2.56 – 2.48 (m, 2H), 1.46 – 1.35 (m, 2H), 1.16 –1.03 (m, 6H), 0.69 (t, J = 6.6 Hz, 3H). 13 C NMR (101 MHz, CDCl3): 198.8, 141.9,138.6, 138.0, 133.2, 130.23, 130.19, 128.47, 128.45, 125.2, 33.4, 31.7, 31.6,29.2, 22.6, 14.1。

[0108] (2-heptadecylphenyl)(phenyl)methanone (3ao): 1 H NMR (400 MHz, CDCl3): δ7.89 – 7.74 (m, 2H), 7.61 – 7.54 (m, 1H), 7.49 – 7.38 (m, 3H), 7.32 (d, J = 7.5Hz, 1H), 7.29 – 7.21 (m, 2H), 2.64 (t, J = 7.8 Hz, 2H), 1.57 – 1.48 (m, 2H),1.33 – 1.17 (m, 28H), 0.88 (t, J= 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ198.9, 142.0, 138.7, 138.1, 133.3, 130.3, 130.2, 128.52, 128.50, 125.2, 33.4,32.1, 31.8, 29.84, 29.81, 29.79, 29.76, 29.64, 29.59, 29.51, 29.46, 22.8,14.3. HRMS (ESI-TOF): calculated for [C 30 H 45 O (M + H)] + : 421.3470, found:421.3471。

[0109] (2-butylphenyl)( p -tolyl)methanone (3ap): 1 H NMR (400 MHz, CDCl3): δ7.69 – 7.60 (m, 2H), 7.36 – 7.31 (m, 1H), 7.27 – 7.23 (m, 1H), 7.22 – 7.14(m, 4H), 2.61 – 2.55 (m, 2H), 2.36 (s, 3H), 1.51 – 1.39 (m, 2H), 1.25 – 1.14(m, 2H), 0.76 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 198.6, 144.2,141.7, 139.0, 135.5, 130.4, 130.1, 130.0, 129.2, 128.3, 125.2, 33.9, 33.1,22.6, 21.8, 13.9.HRMS (EI-TOF): calculated for [C 18 H 20 O (M)] + : 252.1514, found:252.1516。

[0110] (2-isobutylphenyl)(phenyl)methanone (3aq): 1H NMR (400 MHz, CDCl3): δ7.71 – 7.64 (m, 2H), 7.45 (t, J = 7.4 Hz, 1H), 7.35 – 7.25 (m, 3H), 7.18 – 7.09(m, 3H), 2.45 (d, J = 7.3 Hz, 2H), 1.73 – 1.61 (m, 1H), 0.69 (d, J = 6.6 Hz, 6H). 13 C NMR (101 MHz, CDCl3): δ 198.9, 140.8, 138.9, 138.0, 133.2, 131.0, 130.2,130.0, 128.7, 128.5, 125.3, 42.4, 30.3, 22.5。

[0111] phenyl(2-(2-phenylpent-4-en-1-yl)phenyl)methanone (3av): 1 H NMR (400MHz, CDCl3): δ 7.86 (d, J = 7.5 Hz, 1H), 7.64 (d, J = 7.5 Hz, 1H), 7.54 – 7.44(m, 1H), 7.40 – 7.33 (m, 2H), 7.32 – 6.98 (m, 7H), 6.93 (d, J = 7.2 Hz, 1H),5.71 – 5.59 (m, 0.48H), 5.57 – 5.45 (m, 0.52H), 5.01 – 4.89 (m, 1H), 4.88 –4.78 (m, 1H), 3.50 – 3.41 (m, 0.48H), 3.32 – 3.19 (m, 1H), 3.12 – 3.04 (m,0.52H), 2.98 – 2.91 (m, 0.48H), 2.89 – 2.81 (m, 0.52H), 2.49 – 2.37 (m, 1H),2.31 (t, J = 7.0 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 199.0, 198.6, 144.4, 144.0,139.78, 138.75, 137.9, 137.3, 136.7, 136.3, 133.1, 133.0, 131.2, 130.3,129.9, 128.8, 128.6, 128.5, 128.4, 128.2, 128.1, 127.8, 127.6, 126.4, 126.2,125.2, 116.9, 116.2, 47.7, 44.6, 40.79, 40.76, 40.4, 39.8.HRMS (EI-TOF):calculated for [C 24 H 22 O (M)] + : 326.1671, found: 326.1673。

[0112] (2-cycloheptylphenyl)(phenyl)methanone (3bn): 1 H NMR (400 MHz, CDCl3):δ 7.84 – 7.77 (m, 2H), 7.61 – 7.55 (m, 1H), 7.48 – 7.38 (m, 4H), 7.24 – 7.19(m, 2H), 2.82 – 2.73 (m, 1H), 1.90 – 1.81 (m, 2H), 1.72 – 1.60 (m, 4H), 1.58– 1.46 (m, 4H), 1.37 – 1.26 (m, 2H). 13 C NMR (101 MHz, CDCl3): δ 199.3, 148.5,138.2, 137.7, 133.3, 130.4, 130.2, 128.5, 127.7, 127.0, 125.0, 42.6, 36.8,27.8, 27.4. HRMS (EI-TOF): calculated for [C 20 H 22 O (M)] + : 278.1671, found:278.1673。

[0113] (2-cyclohexylphenyl)(phenyl)methanone (3bo): 1H NMR (400 MHz, CDCl3): δ7.84 – 7.78 (m, 2H), 7.61 – 7.55 (m, 1H), 7.48 – 7.40 (m, 4H), 7.26 – 7.19(m, 2H), 2.71 – 2.61 (m, 1H), 1.84 – 1.64 (m, 5H), 1.49 – 1.37 (m, 2H), 1.27– 1.13 (m, 3H). 13 C NMR (101 MHz, CDCl3): δ 199.2, 146.5, 138.6, 138.2, 133.4130.3, 130.2, 128.5, 127.9, 126.9, 125.2, 40.8, 34.5, 26.8, 26.2.HRMS (EI-TOF): calculated for [C 19 H 20 O (M)] + : 264.1514, found: 264.1511。

[0114] (2-((1 R ,4 R )-bicyclo[2.2.1]hept-5-en-2-yl)phenyl)(phenyl)methanone(3br): 1 H NMR (400 MHz, CDCl3): δ 7.88 – 7.83 (m, 2H), 7.62 – 7.56 (m, 1H),7.49 – 7.44 (m, 2H), 7.36 – 7.30 (m, 1H), 7.23 – 7.16 (m, 3H), 6.29 (dd, J =5.6, 3.1 Hz, 1H), 5.84 (dd, J = 5.6, 2.8 Hz, 1H), 3.53 – 3.48 (m, 1H), 3.01 (s,1H), 2.88 (s, 1H), 2.10 – 2.02 (m, 1H), 1.43 – 1.38 (m, 1H), 1.33 – 1.29 (m,1H), 1.28 – 1.22 (m, 1H). 13C NMR (101 MHz, CDCl3): δ 199.5, 143.5, 139.9, 137.9,137.4, 133.5, 133.0, 130.4, 129.3, 128.6, 127.8, 127.4, 125.1, 50.7, 49.0,43.4, 40.3, 34.0.HRMS (EI-TOF): calculated for [C 20 H 18 O (M)] + : 274.1358, found:274.1361。

[0115] (2-(3,3-dimethoxycyclobutyl)phenyl)(phenyl)methanone (3bv): 1 H NMR(400 MHz, CDCl3): δ 7.82 – 7.77 (m, 2H), 7.60 – 7.55 (m, 1H), 7.50 – 7.42 (m,4H), 7.27 – 7.25 (m, 2H), 3.49 – 3.39 (m, 1H), 3.13 (s, 3H), 3.12 (s, 3H),2.56 – 2.46 (m, 2H), 2.20 – 2.11 (m, 2H). 13 C NMR (101 MHz, CDCl3): δ 198.7,143.8, 138.5, 137.6, 133.4, 130.5, 130.2, 128.5, 128.1, 126.8, 125.6, 99.8,48.8, 48.4, 39.5, 27.8.HRMS (EI-TOF): calculated for [C 19 H 20 O3(M)] + : 296.1412,found: 296.1414。

[0116] (2-((3 R )-3-((3 R ,5 R ,9 S ,10 S ,13 R ,14 S ,17 R )-3-(( tert-butyl-dimethylsilyl)oxy)-10,13-dimethylhexade cahydro-1 H -cyclopenta[ a ]phenanthren-17-yl) butyl)phenyl)(phenyl)-methanone (3cb): 1 H NMR (400 MHz, CDCl3): δ 7.76 (dd, J = 5.1,3.3 Hz, 2H), 7.56 – 7.50 (m, 1H), 7.42 – 7.33 (m, 3H), 7.27 – 7.16 (m, 3H),3.58 – 3.48 (m, 1H), 2.71 – 2.60 (m, 1H), 2.50 – 2.39 (m, 1H), 1.87 – 1.66(m, 4H), 1.64 – 1.40 (m, 4H), 1.38 – 1.10 (m, 11H), 1.09 – 0.83 (m, 19H),0.79 (d, J = 6.3 Hz, 3H), 0.52 (s, 3H), 0.01 (s, 6H). 13 C NMR (101 MHz, CDCl3): δ198.7, 142.4, 138.8, 138.1, 133.2, 130.3, 130.21, 130.19, 128.5, 128.4,125.1, 72.9, 56.5, 56.0, 42.8, 42.4, 40.4, 40.2, 38.5, 37.1, 36.01, 35.97,35.7, 34.7, 31.2, 30.2, 28.2, 27.4, 26.5, 26.1, 24.3, 23.5, 20.9, 18.6, 18.4,12.1, -4.5.HRMS (ESI-TOF): calculated for [C 42 H 62 O2SiK (M + K)] + : 665.4156,found: 665.4155。

[0117] (6-(3-((3 r ,5 r ,7 r)-adamantan-1-yl)-4-methoxy phenyl)naphthalen-2-yl)(2-pentylphenyl)met hanone (3cc): 1 H NMR (400 MHz, CDCl3): δ 8.21 (s, 1H), 8.10– 8.01 (m, 2H), 7.94 (dd, J = 19.5, 8.6 Hz, 2H), 7.80 (dd, J = 8.5, 1.7 Hz, 1H),7.63 (d, J = 2.3 Hz, 1H), 7.56 (dd, J = 8.4, 2.3 Hz, 1H), 7.50 – 7.44 (m, 1H),7.42 – 7.35 (m, 2H), 7.33 – 7.28 (m, 1H), 3.92 (s, 3H), 2.75 – 2.65 (m, 2H),2.25 – 2.17 (m, 6H), 2.16 – 2.1 (m, 3H), 1.88 – 1.78 (m, 6H), 1.64 – 1.55 (m,2H), 1.29 – 1.19 (m, 4H), 0.81 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ198.8, 159.1, 141.9, 139.1, 139.0, 136.2, 134.9, 132.7, 132.5, 131.2, 130.22,130.15, 130.1, 128.6, 128.5, 126.6, 126.1, 125.9, 125.6, 125.3, 124.9, 112.2,55.3, 40.7, 37.3, 37.2, 33.4, 31.8, 31.5, 29.2, 22.5, 14.1. HRMS (ESI-TOF):calculated for [C 39 H 43 O2(M + H)] + : 543.3263, found: 543.3262。

[0118] 5,6,7,8-tetrahydro-13 H -dibenzo[ a,d ][9 ]annulen-13-one (3ce): 1 H NMR(400 MHz, CDCl3): δ 7.47 (dd, J = 7.6, 1.2 Hz, 2H), 7.41 – 7.34 (m, 2H), 7.30 –7.25 (m, 2H), 7.17 (d, J = 7.5 Hz, 2H), 2.72 – 2.62 (m, 4H), 1.76 – 1.66 (m,4H). 13 C NMR (101 MHz, CDCl3): δ 203.5, 141.5, 141.2, 131.0, 130.7, 126.7,126.2, 33.0, 27.1.HRMS (EI-TOF): calculated for [C 17 H 16 O (M)] + : 236.1201,found: 236.1199。

[0119] 2,2-dimethyl-1-(2-propylphenyl)propan-1-one (3cf): 1 H NMR (400 MHz,CDCl3): δ 7.31 – 7.23 (m, 2H), 7.20 – 7.10 (m, 2H), 2.47 – 2.40 (m, 2H), 1.68– 1.56 (m, 2H), 1.25 (s, 9H), 0.94 (t, J = 7.3 Hz, 3H). 13 C NMR (151 MHz, CDCl3):δ 215.2, 140.8, 138.8, 129.6, 128.7, 125.0, 124.6, 45.0, 35.9, 27.6, 24.7,14.3.HRMS (EI-TOF): calculated for [C 14 H 20 O (M)] + : 204.1514, found: 204.1512。

[0120] adamantan-1-yl(2-ethylphenyl)methanone (3ch): 1H NMR (400 MHz, CDCl3):δ 7.33 – 7.25 (m, 2H), 7.20 – 7.13 (m, 1H), 7.11 – 7.06 (m, 1H), 2.48 (q, J =7.5 Hz, 2H), 2.07 – 2.00 (m, 3H), 1.92 (d, J = 2.7 Hz, 6H), 1.77 – 1.64 (m,6H), 1.21 (t, J = 7.5 Hz, 3H). 13 C NMR (151 MHz, CDCl3): δ 214.5, 140.31, 140.29,128.9, 128.7, 124.8, 124.7, 47.2, 38.8, 36.6, 28.1, 26.8, 15.8.HRMS (EI-TOF):calculated for [C 19 H 24 O (M)] + : 268.1827, found: 268.1830。

[0121] (2-ethylphenyl)((3a S ,5a R ,8a R ,8b S )-2,2,7,7-tetramethyltetrahydro-3a H -bis([1,3]dioxolo)[4,5- b :4',5'- d ]pyran-3a-yl)methanone (3ci): 1 H NMR (400 MHz,CDCl3): δ 7.92 (d, J = 7.7 Hz, 1H), 7.38 (t, J = 7.2 Hz, 1H), 7.27 (d, J = 6.8 Hz,1H), 7.21 (t, J = 7.6 Hz, 1H), 5.23 (d, J = 2.6 Hz, 1H), 4.69 (dd, J = 7.9, 2.6 Hz,1H), 4.23 (dd, J= 7.9, 1.5 Hz, 1H), 3.95 (dd, J = 12.9, 1.9 Hz, 1H), 3.76 (d, J =12.9 Hz, 1H), 2.80 – 2.65 (m, 2H), 1.59 (s, 3H), 1.41 (s, 3H), 1.32 (d, J = 8.5Hz, 6H), 1.24 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 197.2, 144.8,135.0, 131.1, 129.71, 129.66, 124.7, 110.0, 109.2, 102.6, 70.5, 70.42, 70.36,61.7, 26.9, 26.3, 26.0, 24.9, 24.3, 16.2.HRMS (ESI-TOF): calculated for[C 20 H 26 O6Na (M + Na)] + : 385.1627, found: 385.1625。

[0122] (6-methoxy-2,5,7,8-tetramethylchroman-2-yl)(2-pentylph enyl)-methanone (3cj): 1 H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 7.6 Hz, 1H), 7.26 (t, J =7.5 Hz, 1H), 7.16 – 7.09 (m, 2H), 3.58 (s, 3H), 2.65 (t, J = 6.7 Hz, 2H), 2.55– 2.46 (m, 1H), 2.46 – 2.35 (m, 2H), 2.11 (s, 3H), 2.07 (s, 3H), 2.05 – 1.96(m, 1H), 1.81 (s, 3H), 1.70 (s, 3H), 1.59 – 1.49 (m, 1H), 1.46 – 1.36 (m,1H), 1.33 – 1.22 (m, 4H), 0.88 (t, J = 6.8 Hz, 3H).13 C NMR (151 MHz, CDCl3): δ210.6, 150.2, 147.3, 141.4, 137.7, 129.8, 129.7, 128.1, 127.2, 125.9, 124.4,123.3, 117.6, 82.7, 60.5, 33.4, 32.1, 31.6, 30.5, 25.0, 22.6, 20.7, 14.2,12.5, 11.9, 11.7.HRMS (ESI-TOF): calculated for [C 26 H 34 O3Na (M + Na)] + :417.2406, found: 417.2408。

[0123] (6b S ,8a S ,15a S ,15b R )-4-methoxy-8a-methyl-1,2,6b,7,8,8a, 14,15, 15a,15b-decahydro-9 H -benzo[4,5]cyclohepta[1,2 a ] phenanthren-9-one (3ck): 1 H NMR(400 MHz, CDCl3): δ 7.44 – 7.37 (m, 1H), 7.35 – 7.28 (m, 2H), 7.21 – 7.12 (m,2H), 6.72 (dd, J = 8.6, 2.6 Hz, 1H), 6.63 (d, J = 2.5 Hz, 1H), 3.78 (s, 3H), 2.88– 2.69 (m, 4H), 2.38 – 2.29 (m, 1H), 2.24 – 2.08 (m, 3H), 2.01 – 1.92 (m,1H), 1.68 – 1.49 (m, 4H), 1.46 – 1.34 (m, 1H), 1.29 (s, 3H), 1.26 – 1.13 (m,1H). 13C NMR (101 MHz, CDCl3): δ 216.1, 157.7, 140.7, 137.8, 137.4, 132.4,131.1, 127.6, 126.8, 126.4, 126.3, 113.5, 111.8, 55.3, 49.1, 43.2, 42.8,40.7, 38.0, 30.6, 30.2, 28.1, 26.6, 26.2, 14.3.HRMS (ESI-TOF): calculated for[C 25 H 29 O2(M + H)] + : 361.2168, found: 361.2167。

[0124] cyclopropyl(2-phenethylphenyl)methanone (3cn): 1 H NMR (400 MHz, CDCl3):δ 7.72 (dd, J = 7.6, 1.3 Hz, 1H), 7.41 – 7.36 (m, 1H), 7.34 – 7.25 (m, 4H),7.24 – 7.18 (m, 3H), 3.15 – 3.08 (m, 2H), 2.95 – 2.87 (m, 2H), 2.45 – 2.34(m, 1H), 1.31 – 1.26 (m, 2H), 1.10 – 1.02 (m, 2H). 13 C NMR (151 MHz, CDCl3): δ205.4, 142.0, 140.6, 140.1, 130.9, 130.8, 128.7, 128.4, 128.4, 126.0, 126.0,38.5, 36.0, 21.1, 12.3.HRMS (EI-TOF): calculated for [C 18 H 18 O (M)] + : 250.1358,found: 250.1361。

[0125] cyclopropyl(2-(tetrahydro-2 H -pyran-4-yl)phenyl)methanone (3cp): 1H NMR(400 MHz, CDCl3): δ 7.61 (dd, J = 7.7, 1.0 Hz, 1H), 7.46 – 7.35 (m, 2H), 7.30 –7.24 (m, 1H), 4.03 (dd, J = 11.3, 3.9 Hz, 2H), 3.55 – 3.46 (m, 2H), 3.31 – 3.20(m, 1H), 2.43 – 2.33 (m, 1H), 1.91 – 1.70 (m, 4H), 1.30 – 1.22 (m, 2H), 1.10– 1.02 (m, 2H). 13 C NMR (101 MHz, CDCl3): δ 206.1, 144.0, 140.2, 130.9, 127.9,127.0, 126.0, 68.5, 37.4, 34.2, 21.6, 12.4.HRMS (EI-TOF): calculated for[C 15 H 18 O2(M)] + : 230.1307, found: 230.1309。

[0126] (2-ethyl-4,5-dimethoxyphenyl)( p -tolyl)methanone (4b): 1 H NMR (400 MHz,CDCl3): δ 7.70 (d, J = 8.1 Hz, 2H), 7.27 – 7.22 (m, 2H), 6.81 (d, J = 3.7 Hz,2H), 3.94 (s, 3H), 3.79 (s, 3H), 2.62 (q, J = 7.5 Hz, 2H), 2.42 (s, 3H), 1.15(t, J = 7.5 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 197.8, 150.6, 146.2, 143.9,137.3, 135.9, 130.5, 130.4, 129.2, 112.33, 112.31, 56.2, 56.0, 26.4, 21.8,16.4.HRMS (ESI-TOF): calculated for [C 18 H 21 O3(M + H)] + : 285.1491, found:285.1490。

[0127] (5-bromo-2-phenethylphenyl)(phenyl)methanone (4k) and (4-bromo-2-phenethylphenyl)(phenyl)me thanone (4k'): 1 H NMR (400 MHz, CDCl3), mixture of4k and 4k': δ 7.80 – 7.73 (m, 2H), 7.64 – 7.57 (m, 1H), 7.52 (dd, J = 8.2, 2.1Hz, 0.5H), 7.50 – 7.39 (m, 3.5H), 7.24 – 7.13 (m, 4H), 7.10 – 7.03 (m, 2H),2.97 – 2.81 (m, 4H). 13 C NMR (151 MHz, CDCl3), mixture of 4k and 4k': δ 197.6,197.0, 143.3, 141.13, 141.11, 140.6, 139.7, 137.6, 137.4, 137.3, 133.7,133.6, 133.5, 133.3, 132.2, 131.2, 130.5, 130.31, 130.25, 128.8, 128.7,128.6, 128.54, 128.50, 128.47, 126.22, 126.18, 124.8, 119.3, 38.0, 37.9,35.4, 35.0. One aromatic carbon peak is overlapped.HRMS (ESI-TOF): calculatedfor [C 21 H 18BrO (M + H)] + : 356.0541, found: 356.0540。

[0128] (2-ethyl-5-methoxyphenyl)( p -tolyl)meth-anone (4m) and (2-ethyl-4-methoxy-phen yl)( p -tolyl)methanone (4m'): 1 H NMR (400 MHz, CDCl3), mixture of4m and 4m': δ 7.74 – 7.65 (m, 2H), 7.26 – 7.19 (m, 3H), 6.94 (dd, J = 8.5, 2.7Hz, 0.38H), 6.85 (d, J = 2.4 Hz, 0.62H), 6.77 (d, J = 2.7 Hz, 0.38H), 6.72 (dd, J =8.5, 2.5 Hz, 0.62H), 3.83 (s, 1.87H), 3.75 (s, 1.13H), 2.72 (q, J = 7.5 Hz,1.25H), 2.54 (q, J = 7.5 Hz, 0.75H), 2.39 (s, 3H), 1.17 (t, J = 7.5 Hz, 1.87H),1.09 (t, J = 7.5 Hz, 1.13H). 13 C NMR (101 MHz, CDCl3), mixture of 4m and 4m': δ198.2, 197.8, 161.2, 157.0, 146.4, 144.3, 143.6, 139.7, 136.2, 135.0, 134.6,131.4, 130.9, 130.4, 130.3, 129.2, 129.1, 115.9, 115.3, 113.1, 110.0, 55.4,55.3, 26.8, 25.6, 21.8, 21.7, 16.1, 16.0. HRMS (ESI-TOF): calculated for[C 17 H 19O2(M + H)] + : 255.1385, found: 255.1384。

[0129] (2-ethyl-5-methylphenyl)( p -tolyl)methan-one (4n) and (2-ethyl-4-methylphenyl)( p -tolyl)methanone (4n'): 1 H NMR (400 MHz, CDCl3), mixture of 4nand 4n': δ 7.85– 7.74 (m, 2H), 7.35 – 7.28 (m, 3H), 7.25– 7.20 (m, 1H), 7.16– 7.10 (m, 1H), 2.77 – 2.65 (m, 2H), 2.49 (s, 3H), 2.47 (s, 1.74H), 2.40 (s,1.26H), 1.26– 1.18 (m, 3H). 13 C NMR (101 MHz, CDCl3), mixture of 4n and 4n': δ198.8, 198.6, 144.2, 143.9, 143.3, 140.4, 139.8, 138.8, 135.9, 135.7, 135.4,134.8, 130.9, 130.4, 130.3, 129.3, 129.23, 129.15, 128.8, 128.6, 128.2,125.8, 26.5, 26.1, 21.80, 21.78, 21.6, 21.0, 16.13, 16.09. HRMS (EI-TOF):calculated for [C 17 H 18 O (M)] + : 238.1358, found: 238.1355。

[0130] 1-ethyl-2-(1-( p -tolyl)vinyl)benzene (5): 1H NMR (400 MHz, CDCl3): δ7.36 – 7.30 (m, 1H), 7.29 – 7.25 (m, 1H), 7.25 – 7.18 (m, 4H), 7.14 – 7.09(m, 2H), 5.78 (d, J = 1.2 Hz, 1H), 5.18 (d, J = 1.2 Hz, 1H), 2.46 (q, J = 7.6 Hz,2H), 2.36 (s, 3H), 1.11 – 1.05 (m, 3H). 13 C NMR (101 MHz, CDCl3): δ 149.1,142.3, 141.4, 138.2, 137.5, 130.3, 129.1, 128.5, 127.7, 126.5, 125.7, 114.1,26.4, 21.3, 15.4.HRMS (EI-TOF): calculated for [C 17 H 18 O (M)] + : 222.1409, found:222.1411。

[0131] 1-ethyl-2-(4-methylbenzyl)benzene (6): 1 H NMR (400 MHz, CDCl3): δ 7.28– 7.22 (m, 2H), 7.22 – 7.17 (m, 1H), 7.16 – 7.11 (m, 3H), 7.09 – 7.05 (m,2H), 4.04 (s, 2H), 2.68 (q, J = 7.6 Hz, 2H), 2.37 (s, 3H), 1.22 (t, J = 7.6 Hz,3H). 13 C NMR (101 MHz, CDCl3): δ 142.5, 138.6, 138.0, 135.5, 130.4, 129.2,128.7, 128.5, 126.7, 126.0, 38.4, 25.9, 21.1, 15.0.HRMS (EI-TOF): calculatedfor [C 16 H 18 O (M)] +: 210.1409, found: 210.1412。

[0132] (2-ethylphenyl)(4-fluorophenyl)methanol (7c): 1 H NMR (400 MHz, CDCl3):δ 7.49 – 7.40 (m, 1H), 7.35 – 7.18 (m, 5H), 7.08 – 6.95 (m, 2H), 6.06 (s,1H), 2.75 – 2.54 (m, 2H), 2.20 (s, 1H), 1.15 (t, J = 7.5 Hz, 3H). 13 C NMR (151MHz, CDCl3): δ 162.2 (d, J = 245.6 Hz), 141.5, 140.7, 139.23 (d, J = 2.7 Hz),128.9 (d, J = 5.7 Hz), 128.8, 128.1, 126.7, 126.3, 115.4 (d, J = 21.1 Hz), 72.1,25.3, 15.4. 19 F NMR (565 MHz, CDCl3): δ -115.02 – -115.10 (m)。

[0133] 2-ethyl- N -methylaniline (8c): 1 H NMR (400 MHz, CDCl3): δ 7.18 (t, J = 7.7Hz, 1H), 7.09 (d, J = 7.4 Hz, 1H), 6.74 (t, J = 7.4 Hz, 1H), 6.65 (d, J = 8.0 Hz,1H), 3.73 (brs, 1H), 2.91 (s, 3H), 2.50 (q, J = 7.5 Hz, 2H), 1.27 (t, J = 7.5 Hz,3H). 13C NMR (151 MHz, CDCl3): δ 146.7, 127.74, 127.68, 127.2, 117.2, 109.6, 31.0, 23.8, 12.9.

[0134] The present invention discloses a new reaction activation mode, which can create unparalleled synthetic capabilities for different organic transformations, and establishes a new NaH-mediated activation strategy, which can effectively participate in the insertion reaction of unactivated ketones, which is difficult to achieve with existing methods. The present invention has a wide range of substrate applicability, and importantly, for the reaction of structurally complex molecules, the operation is simple and the reaction conditions are mild. This is in direct contrast to the shortcomings of the classical method using strong bases such as NaNH2, alkyl lithium or Grignard reagents, which have a narrow functional group range and complex side reactions. The two adjacent iodine in the ortho-diiodinated aromatic hydrocarbon plays a key role in the reaction. The nucleophilic attack of hydride on electrophilic iodine requires adjacent iodine as a guiding group to accelerate the process and form an aromatic ketone compound in situ with the unactivated ketone, while the monosubstituted iodobenzene lacking the participation of adjacent groups makes this process difficult. The present invention has important application potential in new organic reactions.

Claims

1. A method for preparing an aryl ketone compound by reacting an unactivated ketone with diiodobenzene, characterized in that: In the presence of sodium hydride, reacting an unactivated ketone with diiodobenzene in a solvent to obtain an aryl ketone compound; the solvent is tetrahydrofuran or DMA; The chemical structure of unactivated ketone is as follows: ； The chemical structure of diiodobenzene is as follows: ； Wherein, sub-Ar represents a phenyl group; The chemical structure of the product aryl ketone compound is as follows: ； Said The specific compound is as follows: ； ； ； ； Said The specific compound is as follows: ； The reaction temperature is room temperature to 60°C, and the reaction time is 1 to 24 hours.

2. The method for preparing an aryl ketone compound by reacting an unactivated ketone with diiodobenzene according to claim 1, characterized in that: The molar ratio of unactivated ketone, diiodobenzene and sodium hydride is 1:(1-6):(2-8).

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