Synthesis method of beta, gamma unsaturated ketone compound

Abstract

The invention relates to a synthesis method of a beta, gamma unsaturated ketone compound, which comprises the following steps: adding a primary alcohol compound, an allene compound, a cyclohexyl phosphine compound, an additive and a transition metal ruthenium catalyst into a reaction container, adding an organic solvent in a nitrogen atmosphere, reacting at 130 DEG C for 16 hours, and separating and purifying to obtain the beta, gamma unsaturated ketone compound. And a gamma unsaturated ketone compound. The beta, gamma unsaturated ketone compounds can be obtained with high selectivity by using transition metal catalysis, the phosphine ligand and the phosphonic acid additive, the reaction conditions are mild, the operability is strong, and the method has potential industrial prospects.

Description

Technical Field

[0001] The invention relates to the field of compound synthesis, and in particular to a method for synthesizing β, γ unsaturated ketone compounds. Background Art

[0002] Ketones are a class of extremely valuable organic compounds with high reactivity and relative stability. They are ideal chemical intermediates and have been widely used in the synthesis of complex natural products and drug-related molecules.

[0003] For the synthesis of ketone compounds, the traditional and common method is to use primary alcohol, under the action of an oxidant, first oxidize to aldehyde, obtain secondary alcohol by addition of a Grignard reagent to the carbonyl group, and then oxidize to ketone. Another common method also requires three steps, oxidizing the alcohol to generate carboxylic acid, then amidation, and then adding an organometallic reagent [(a) BMTrost, The Atom Economy–a Search for Synthetic Efficiency. Science. 1991, 254, 1471. (b) NZBurns, PSBaran, RWHoffmann, Redox Economy in Organic Synthesis. Angew. Chem. Int. Ed. 2009, 48, 2854-2867.]. These classical routes rely on mature transformations, but due to the need for chemically equivalent metal reagents and lengthy steps, stoichiometric waste is generated and the efficiency and atom economy are relatively low. The hydrogenation reaction of unsaturated hydrocarbons with aldehydes is one of the most direct and atom-efficient methods for synthesizing ketones. Although significant progress has been made in the intermolecular hydroacylation reaction catalyzed by transition metals, additional chelating groups must usually be present in the aldehyde to prevent the acyl-metal hydride intermediate from undergoing undesirable facile decarboxylation [(a) MC Willis, Transition Metal Catalyzed Alkene and Alkyne Hydroacylation.Chem.Rev.2010,110,725-748.(b)ATBiju,N.Kuhl,F.Glorius.Acc.Chem.Re s.2011,44,1182-1195.(c)RTDavison,ELKuker,VMDong.Acc.Chem.Res.2021,54,236-1250.(d ) Shi, Q.; Li, P.; Zhu, X.; Wang, L. GreenChem. 2016, 18, 4916. (d) SK Murphy, J.-W. Park, FA Cruz , VMDong.Science.2015,347,56-60.(e)JCLeung,MJKrische.Chem.Sci.2012,3,2202-2209.]. If primary alcohols are directly upgraded to ketones by functionalizing their α-CH bonds, the efficiency can be improved while simplifying the operation steps.However, there are limited methods for the one-step economical synthesis of ketones from primary alcohols, such as Rh-, Ru-, or Ni-catalyzed dehydrogenative functionalization or tandem radical coupling reactions of alcohols [(a) C.-H. Jun, C.-W. Huh, S.-J. Na. Angew. Chem. Int. Ed. 1998, 37, 145-147. (b) H.-S. Li, Y. Xiong, G. Zhang, Adv. Synth. Catal. 2018, 360, 4246-4251]. .(c) BJ Spinello, J. Wu, Y. Cho, MJ Krische. J. Am. Chem. Soc. 2021, 143, 13507-13512. (d) F. Shibahara, JFB ower, MJ Krische. J. Am. Chem. Soc. 2008, 130, 14120-14122. (e) CMNicklaus, AJ Minnaard, BLFeringa, JGde Vries.Chem Su Chem, 2013, 6, 1631-1635. (f) T. Verheyen, L. van Turnhout, JK Vandavasi, ESI Isbrandt, WM De Borggraeve, SG Newman. J. Am. Chem. Soc. 2019, 141, 6869-6874. (g) PF. Yang, W. Shu. Org. Lett. 2020, 22, 6203-6208. (h) Y.-F. Liang, X. Wang, C. Tang, T. Shen, J. Liu, N. Jiao. Chem. Commun. 2016, 52, 1416-1419]. Therefore, there is still a great demand for developing a low-cost, high-efficiency, and high-atom-economy method for synthesizing ketone compounds.

[0004] Allenes, unlike alkenes and alkynes, have three reactive sites, so it is very interesting and challenging to selectively control the site or regioselectivity in the reaction. Most reactions occur at the α or γ position of the allene, and the cross-coupling of allenes and alcohols has been well developed due to the generation of nucleophilic or electrophilic resonance-stabilized allylic metal intermediates during the reaction. For example, ether or alcohol products are produced by α- or γ-selective hydroalkoxylation or hydroxyalkylation [(a) NT Patil, NK Pahadi, Y. Yamamoto. Can. J. Chem. 2005, 83, 569-573. (b) Z. Zhang, RA Widenhoefer. Org. Lett. 2008, 10, 2079-2081. (c) Z. Liu, B. Breit. Angew. Chem. Iht. Ed. 2016, 55, 8440-8443. (d) JF Bower, E. Skucas, RL Patman, MJ Krische .J.Am.Chem.Soc.2007, 129, 15134-15135. (e) JRZbieg, ELMcInturff, JCLeung, MJKrische. J.Am.Chem.Soc.2011, 133, 1141-1144. (f) B.Sa m, T. Luong, MJ Krische. Angew. Chem. Int. Ed. 2015, 54, 5465-5469. (g) M. Holmes, LA Schwartz, MJ Krische. Chem. Rev. 2018, 118, 6026-6052]. Although there are at least four regioisomers in the hydroacylation of olefins with aldehydes, regardless of the stereoisomers of the olefinic double bond, Muri, Willis, Murakami, Yoshikai, Dong et al. synthesized many valuable enones through the one-step reaction of olefins with aldehydes, but all of them were α- or γ-selective hydroacylation reactions. An obvious problem of this type of reaction is that it is impossible to obtain a single, highly selective ββ-position hydroacylation product.Therefore, it is very challenging to develop a method for synthesizing ββ,γ unsaturated ketones using alcohols and allenes in one step to achieve efficient regioselectivity and chemoselectivity [(a) JD Osborne, HERandell-Sly, GS Currie, ARC Owley, MC Willis. J. Am. Chem. Soc. 2008, 130, 17232-17233. (b) Q.-A. Chen, FA Cruz, VM Dong. J. Am. Chem. Soc.2015, 137, 3157-3160. (c) T.Toyoshima, T.Miura, M.Murakami.Angew.Chem.Int.Ed.2011,50,10436-1 0439. (d) W. Ding, YKTHo, Y. Okuda, CK Wijaya, ZHTan, N. Yoshikai, Y. Okuda. Org. Lett. 2019, 21, 6173-6178]. At present, there is only one case report of β-selective hydroacylation reaction, which is the reaction of 1-phenylpropene with chelated salicylic acid catalyzed by Rh, but the α-selective hydroacylation product is still the major product [(a) K. Kokubo, K. Matsumasa, Y. Nishinaka, M. Miura, M. Nomura. Bull. Chem. Soc. Jpn. 1999, 72, 303-311]. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a method for synthesizing β, γ unsaturated ketone compounds catalyzed by transition metal ruthenium which is easy to operate and has mild reaction conditions.

[0006] In order to solve the above problems, the present invention discloses a method for synthesizing a β,γ-unsaturated ketone compound, characterized in that: the method comprises adding a primary alcohol compound, an allene compound, a cyclohexylphosphine compound, an additive and a transition metal ruthenium catalyst into a reaction container, adding an organic solvent under a nitrogen atmosphere, reacting at 130° C. for 16 hours, and obtaining a β,γ-unsaturated ketone compound by separation and purification; the molecular formula of the β,γ-unsaturated ketone compound is:

[0007]

[0008] Where: R 1 and R 3 are arbitrarily selected from any one of an alkyl group, an aromatic hetero group, an aryl group, and an alkoxy group with a carbon number greater than or equal to C1; R 2 Any one selected from hydrogen, an alkyl group greater than or equal to C1, and an aryl group.

[0009] The above reaction process can be expressed by the following formula:

[0010]

[0011] The general formula of the primary alcohol compound is:

[0012]

[0013] Where: R 1 and R 2 Any one of an alkyl group, an aromatic hetero group, and an aryl group having a carbon number greater than or equal to C1 can be selected arbitrarily.

[0014] The amount of the allene compound used is 250% of the molar amount of the primary alcohol compound. The general formula of the allene compound is:

[0015]

[0016] Where: R 2 are any one of an alkyl group, an aromatic hetero group, or an aryl group having a carbon number greater than or equal to C1, R 3 are selected from any one of hydrogen, alkyl or aryl with a C1 value, R 4 Selected from hydrogen or an alkyl group equal to C1.

[0017] The cyclohexylphosphine compound refers to any one of 1,2-bis(dicyclohexylphosphino)-ethane and tricyclohexylphosphine, and its usage is 20 mol% of the molar usage of the primary alcohol compound.

[0018] The additive is any one of diphenyl phosphonate, silver trifluoromethanesulfonate, and sodium tetrafluoroborate, and the amount of the additive is 20 mol% of the molar amount of the primary alcohol compound.

[0019] The transition metal ruthenium catalyst is triruthenium dodecacarbonyl, and its usage is 5 mol% of the molar usage of the primary alcohol compound.

[0020] The organic solvent is any one of tetrahydrofuran, 1,4-dioxane, and toluene, and its usage amount is 50 to 100 times the molar usage amount of the primary alcohol compound.

[0021] The separation and purification refers to column chromatography, and the eluent in the column chromatography refers to ethyl acetate-petroleum ether in a volume ratio of 1:10-30.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] 1. The present invention uses transition metal catalysis to obtain the hydrogenation product of the β-position of the allene and the primary alcohol in a one-pot method, which is not only low in cost and easy to operate, but also has a relatively mild reaction temperature and avoids the generation of unnecessary waste.

[0024] 2. The substrate of the present invention has a wide range of applications, and the obtained β,γ unsaturated ketone compounds have high selectivity and can be further easily converted into other ketone compounds. DETAILED DESCRIPTION

[0025] A method for synthesizing a β,γ unsaturated ketone compound, the method comprising adding a primary alcohol compound, an allene compound, a cyclohexylphosphine compound, an additive and a transition metal ruthenium catalyst into a reaction container, adding an organic solvent under a nitrogen atmosphere, reacting at 130°C for 16 hours, and obtaining the β,γ unsaturated ketone compound through separation and purification. The molecular formula of the β,γ unsaturated ketone compound is:

[0026]

[0027] Where: R 1 and R 3 are arbitrarily selected from any one of an alkyl group, an aromatic hetero group, an aryl group, and an alkoxy group with a carbon number greater than or equal to C1; R 2 Any one selected from hydrogen, an alkyl group greater than or equal to C1, and an aryl group.

[0028] The general formula of primary alcohol compounds is:

[0029]

[0030] Where: R 1 and R 2 Any one of an alkyl group, an aromatic hetero group, and an aryl group having a carbon number greater than or equal to C1 can be selected arbitrarily.

[0031] The amount of the allene compound used is 250% of the molar amount of the primary alcohol compound. The general formula of the allene compound is:

[0032]

[0033] Where: R 2 are any one of an alkyl group, an aromatic hetero group, or an aryl group having a carbon number greater than or equal to C1, R 3 are selected from any one of hydrogen, alkyl or aryl with a C1 value, R 4 Selected from hydrogen or an alkyl group equal to C1.

[0034] The cyclohexylphosphine compound refers to any one of 1,2-bis(dicyclohexylphosphino)-ethane and tricyclohexylphosphine, and its usage is 20 mol% of the molar usage of the primary alcohol compound.

[0035] The additive is any one of diphenyl phosphonate, silver trifluoromethanesulfonate and sodium tetrafluoroborate, and the amount thereof is 20 mol% of the molar amount of the primary alcohol compound.

[0036] The transition metal ruthenium catalyst is triruthenium dodecacarbonyl, and its dosage is 5 mol% of the molar dosage of the primary alcohol compound.

[0037] The organic solvent is any one of tetrahydrofuran, 1,4-dioxane and toluene, and its usage amount is 50 to 100 times of the molar usage amount of the primary alcohol compound.

[0038] Separation and purification refers to column chromatography, and the eluent in the column chromatography refers to ethyl acetate-petroleum ether in a volume ratio (ml / ml) of 1:10-30.

[0039] Embodiments 1 to 10 A method for synthesizing β,γ unsaturated ketone compounds:

[0040] 0.2mmol of primary alcohol compound, 0.04mmol of diphenyl phosphonate and a stirring magnet were added to the reaction bottle, and then the reaction bottle was brought into a glove box filled with nitrogen, and 0.5mmol of allene compound, 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent were added. Then the glove box was removed after sealing and reacted at 130°C for 16h. After cooling to room temperature, it was diluted with an appropriate amount of ethyl acetate and n-dodecane was added as an internal standard. The yield of β,γ unsaturated ketone compound 3 was determined by high pressure liquid chromatography (HP-GC) and then determined by the internal standard. Specific examples are shown in Table 1 below:

[0041]

[0042] Table 1

[0043] <![CDATA[Example a > Ligand (15 mol%) Additives (20 mol%) Yield of 3 (%) 1 DCyPE - 30 2 <![CDATA[PPh3]]> - ＜5 3 <![CDATA[PCy3]]> - 5 4 DPPE - 5 5 DCyPE <![CDATA[K3PO4]]> 0 6 DCyPE oeLh 42 7 DCyPE <![CDATA[NaBF4]]> 62 8 DCyPE <![CDATA[(PhO)2PO2H]]> 70 <![CDATA[9 c ]]> DCyPE <![CDATA[(PhO)2PO2H]]> 87 <![CDATA[10 d ]]> DCyPE <![CDATA[(PhO)2PO2H]]> 90

[0044] a Unless otherwise specified, the amount of 1 used in all reactions was 0.1 mmol and the reaction time was 20 hours; b The product yield was determined by adding internal standard n-dodecane; c 24 hours; d With 2(0.5mmol),DCyPE(20mol%),24h.

[0045]

[0046] Example 11 A method for synthesizing β,γ unsaturated ketone compounds:

[0047] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 79%.

[0048] The product is 1-(4-methylphenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0049]

[0050] NMR analysis results:

[0051] 1 H NMR (400MHz, CDCl3) δ7.81(d,J=7.8Hz,2H),7.45(d,J=7.4Hz,2H),7.34(dt,J=13.2,7.2Hz,3H),7.18 (d,J=7.8Hz,2H),5.40(s,1H),5.08(s,1H),4.55(q,J=6.8Hz,1H),2.37(s,3H),1.48(d,J=6.8Hz,3H).

[0052] 13 C NMR (101MHz, CDCl3) δ200.1,148.8,143.7,141.1,134.0,129.3,128.8,128.7,127.9,126.2,114.9,46.5,21.7,17.9.

[0053] Calculated value C 18 H 19 O[M+H] + 251.1430,test value 251.1430.

[0054] Example 12 A method for synthesizing β,γ unsaturated ketone compounds:

[0055] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 80%.

[0056] The product is 1-(4-methoxyphenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0057]

[0058] NMR analysis results:

[0059] 1 H NMR(400MHz, CDCl3) δ7.89(d,J=8.4Hz,2H),7.45(d,J=7.6Hz,2H),7.34(dt,J=13.6,7.2Hz,3H),6.86 (d,J=8.4Hz,2H),5.40(s,1H),5.09(s,1H),4.52(q,J=6.8Hz,1H),3.83(s,3H),1.48(d,J=6.8Hz,3H).

[0060] 13 C NMR (100MHz, CDCl3) δ199.0,163.4,148.9,141.1,130.9,129.5,128.7,127.9,126.2,114.8,113.8,55.5,46.3,17.9.

[0061] Calculated value C 18 H 18 O2 Na[M+H] + 289.1199, test value 289.1208.

[0062] Example 13 A method for synthesizing β,γ unsaturated ketone compounds:

[0063] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 60%.

[0064] The product is 1-(1,1'-biphenyl)-4-yl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0065]

[0066] NMR analysis results:

[0067] 1 H NMR(400MHz, CDCl3)δ7.97(d,J=8.4Hz,2H),7.64–7.57(m,4H),7.50–7.42(m,4H),7.4 1–7.31(m,4H),5.44(s,1H),5.11(s,1H),4.59(q,J=6.8Hz,1H),1.52(d,J=6.8Hz,3H).

[0068] 13 C NMR (101MHz, CDCl3) δ200.0,148.7,145.6,141.0,140.0,135.2,129.2,129.0,128.8,128.3,128.0,127.3,127.2,126.2,115.1,46.7,17.9.

[0069] Calculated value C 23 H 21 O[M+H] + 313.1587, test value 313.1584.

[0070] Example 14 A method for synthesizing β,γ unsaturated ketone compounds:

[0071] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 81%.

[0072] The product is methyl 2-methyl-3-phenyl-3-enoylbenzoate, and the structural formula is as follows:

[0073]

[0074] NMR analysis results:

[0075] 1 H NMR (400MHz, CDCl3) δ8.03(d,J=8.4Hz,2H),7.91(d,J=8.4Hz,2H),7.46–7.41(m,2H),7.39–7. 31(m,3H),5.40(s,1H),5.04(s,1H),4.54(q,J=6.8Hz,1H),3.92(s,3H),1.51(d,J=6.8Hz,3H).

[0076] 13 C NMR (100MHz, CDCl3) δ199.9,166.4,148.3,140.7,139.8,133.7,129.8,128.8,128.5,128.2,126.2,115.4,52.5,47.2,17.8.

[0077] Calculated value C 19 H 19 O3[M+H] + 295.1329, test value 295.1334.

[0078] Example 15 A method for synthesizing β,γ unsaturated ketone compounds:

[0079] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 40%.

[0080] The product is 1-(4-cyanophenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0081]

[0082] NMR analysis results:

[0083] 1 H NMR(400MHz, CDCl3) δ7.93(d,J=8.4Hz,2H),7.66(d,J=8.4Hz,2H),7.44–7.32( m,5H),5.42(s,1H),5.02(s,1H),4.48(q,J=6.8Hz,1H),1.52(d,J=6.8Hz,3H).

[0084] 13 C NMR (100MHz, CDCl3) δ198.9,148.0,140.4,139.6,132.5,129.0,128.9,128.4,126.1,118.1,116.1,115.6,47.2,17.8.

[0085] Calculated value C 18 H 16 NO[M+H] + 262.1226, test value 262.1219.

[0086] Example 16 A method for synthesizing β,γ unsaturated ketone compounds:

[0087] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 45%.

[0088] The product is 1-(4-hydroxyphenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0089]

[0090] NMR analysis results:

[0091] 1 H NMR (400MHz, CDCl3) δ7.96(d,J=8.8Hz,0H),7.84(d,J=8.8Hz,2H),7.45–7.29(m,5H),6.96(d,J=8.8Hz,0H) ,6.82(d,J=8.8Hz,2H),6.63(s,1H),5.40(s,1H),5.09(s,1H),4.54(q,J=6.8Hz,1H),1.48(d,J=6.8Hz,3H).

[0092] 13 C NMR (100MHz, CDCl3) δ199.9,160.5,148.8,141.1,131.3,128.7,127.9,126.3,115.5,115.0,46.3,17.9.

[0093] Calculated value C 16 H 18 O[M+H] + 253.1223, test value 253.1233.

[0094] Example 17 A method for synthesizing β,γ unsaturated ketone compounds:

[0095] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 88%.

[0096] The product is 1-(4-fluorophenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0097]

[0098] NMR analysis results:

[0099] 1 H NMR (400MHz, CDCl3) δ7.91 (dd, J=8.8, 5.5Hz, 2H), 7.44 (d, J=7.0Hz, 2H), 7.35 (dt, J=11.8, 6.8Hz, 3H),7.04(t,J=8.6Hz,2H),5.41(s,1H),5.06(s,1H),4.50(q,J=6.8Hz,1H),1.50(d,J=6.8Hz,3H).

[0100] 13 C NMR(100MHz,CDCl3)δ198.8,165.7(J F =252.7Hz),148.6,140.8,132.9,131.3(J F =9Hz),128.8,128.1,126.2,115.7(J F =21.6Hz),115.2,46.7,17.9.

[0101] Calculated value C 17 H 16 FO[M+H] + 255.1180, test value 255.1172.

[0102] Example 18 A method for synthesizing β,γ unsaturated ketone compounds:

[0103] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 64%.

[0104] The product is 1-(4-chlorophenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0105]

[0106] NMR analysis results:

[0107] 1 H NMR (400MHz, CDCl3) δ7.88–7.74(m,2H),7.43(d,J=6.8Hz,2H),7.40–7.29(m ,5H),5.41(s,1H),5.05(s,1H),4.48(q,J=6.8Hz,1H),1.49(d,J=6.8Hz,3H).

[0108] 13 C NMR (100MHz, CDCl3) δ199.2,148.5,140.8,139.3,134.8,130.1,128.9,128.8,128.1,126.2,115.2,46.8,17.8.

[0109] Calculated value C 17 H 16 ClO[M+H] + 271.0884,test value 271.0874.

[0110] Example 19 A method for synthesizing β,γ unsaturated ketone compounds:

[0111] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 73%.

[0112] The product is 1-(4-bromophenyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0113]

[0114] NMR analysis results:

[0115] 1 H NMR (400MHz, CDCl3) δ7.73(d,J=7.8Hz,2H),7.51(d,J=7.8Hz,2H),7.42(d,J=7.8Hz,2H), 7.38–7.30(m,3H),5.40(s,1H),5.04(s,1H),4.47(q,J=6.8Hz,1H),1.49(d,J=6.8Hz,3H).

[0116] 13 C NMR (100MHz, CDCl3) δ199.3,148.4,140.7,135.2,131.9,130.2,128.8,128.1,128.0,126.2,115.3,46.8,17.8.

[0117] Calculated value C 17 H 16 BrO[M+H] + 315.0379,test value 315.0379.

[0118] Example 20 A method for synthesizing β,γ unsaturated ketone compounds:

[0119] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 45%.

[0120] The product is 1-(2-naphthyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0121]

[0122] NMR analysis results:

[0123] 1 H NMR(400MHz, CDCl3)δ8.39(s,1H),7.98(dd,J=8.6,1.6Hz,1H),7.82–7.79(m,3H),7.59–7.45(m ,4H),7.41–7.31(m,3H),5.42(s,1H),5.14(s,1H),4.71(q,J=6.8Hz,1H),1.57(d,J=6.8Hz,3H).

[0124] 13 C NMR (100MHz, CDCl3) δ200.3,148.9,141.2,135.6,133.8,132.6,130.3,129.7 ,128.8,128.5,128.4,128.0,127.8,126.7,126.3,124.6,115.2,46.8,18.0.

[0125] Calculated value C 21 H 19 O[M+H] + 287.1430,test value 287.1430.

[0126] Example 21 A method for synthesizing β,γ unsaturated ketone compounds:

[0127] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 72%.

[0128] The product is 1-(2-thienyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0129]

[0130] NMR analysis results:

[0131] 1 H NMR (400MHz, CDCl3) δ7.61(d,J=3.6Hz,1H),7.57(d,J=4.8Hz,1H),7.43–7.37(m,2H),7.37–7.28( m,3H),7.05–7.03(m,1H),5.44(s,1H),5.21(s,1H),4.44(q,J=6.8Hz,1H),1.50(d,J=6.8Hz,3H).

[0132] 13 C NMR (100MHz, CDCl3) δ193.4,148.6,143.8,141.0,133.4,132.0,128.7,128.1,127.9,126.3,115.0,48.2,17.8.

[0133] Calculated value C 15 H 15 OS[M+H] + 243.0838,test value 243.0839.

[0134] Example 22 A method for synthesizing a β,γ unsaturated ketone compound:

[0135] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 65%.

[0136] The product is 1-(3-thienyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0137]

[0138] NMR analysis results:

[0139] 1 H NMR (400MHz, CDCl3) δ7.94(d,J=5.2Hz,1H),7.49(d,J=5.2Hz,1H),7.44(d,J=7.6Hz,2H),7.38–7.2 9(m,3H),7.24–7.23(m,1H),5.44(s,1H),5.15(s,1H),4.38(q,J=6.8Hz,1H),1.49(d,J=6.8Hz,3H).

[0140] 13 C NMR (100MHz, CDCl3) δ194.6,148.6,141.7,141.1,132.2,128.7,128.0,127.5,126.2,126.1,115.0,48.5,17.7.

[0141] Calculated value C 15 H 15 OS[M+H] + 243.0838,test value 243.0847.

[0142] Example 23 A method for synthesizing a β,γ unsaturated ketone compound:

[0143] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 81%.

[0144] The product is 1-(2-furyl)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0145]

[0146] NMR analysis results:

[0147] 1 H NMR (400MHz, CDCl3) δ7.88(s,1H),7.41–7.30(m,6H),6.70(s,1H),5.44(s,1H),5.17(s,1H),4.16(q,J=6.8Hz,1H),1.47(d,J=6.8Hz,3H).

[0148] 13 C NMR (100MHz, CDCl3) δ195.2,148.5,147.3,143.9,141.1,128.7,128.0,127.0,126.3,115.1,109.3,49.5,17.5.

[0149] Calculated value C 15 H 15 O2[M+H] + 227.1067, test value 227.1064.

[0150] Example 24 A method for synthesizing a β,γ unsaturated ketone compound:

[0151] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 70%.

[0152] The product is 1-(6-(3-adamantyl)-4-methoxyphenyl)-2-naphthyl)-2-methyl-3-phenylbutenone, and the structural formula is as follows:

[0153]

[0154] NMR analysis results:

[0155] 1 H NMR(400MHz, CDCl3)δ8.38(d,J=1.6Hz,1H),8.01–7.95(m,2H),7.89–7.80(m,2H),7.7 5(dd,J=8.4,1.6Hz,1H),7.59(d,J=2.0Hz,1H),7.55–7.46(m,3H),7.37–7.33(m,3H), 6.99(d,J=8.4Hz,1H),5.43(s,1H),5.15(s,1H),4.72(q,J=6.8Hz,1H),3.90(s,3H),2 .19(d,J=2.8Hz,6H),2.14–2.08(m,3H),1.81(t,J=3.2Hz,6H),1.57(d,J=6.8Hz,3H).

[0156] 13 C NMR (100MHz, CDCl3) δ200.2,159.1,149.0,141.7,141.3,139.2,136.0,133.4,132.7,131.4,130.1,128.8,12 8.5,128.0,126.6,126.4,126.1,125.9,125.0,124.8,115.2,112.3,55.3,46.8,40.8,37.4,37.3,29.3,18.0.

[0157] Calculated value C 38 H 38 O2Na[M+Na] + 549.2764,test value 549.2768.

[0158] Example 25 A method for synthesizing a β,γ unsaturated ketone compound:

[0159] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 91%.

[0160] The product is 1-benzyl-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0161]

[0162] NMR analysis results:

[0163] 1 H NMR (400MHz, CDCl3) δ7.38–7.29(m,5H),7.27–7.20(m,3H),7.11–7.04(m,2H),5.49(s,1H),5.15(s ,1H),3.82(q,J=6.8Hz,1H),3.75(d,J=15.6Hz,1H),3.66(d,J=15.6Hz,1H),1.30(d,J=6.8Hz,3H).

[0164] 13 C NMR (100MHz, CDCl3) δ208.2,148.1,140.9,134.5,129.6,128.7,128.0,127.0,126.4,115.2,51.0,47.8,16.5.

[0165] Calculated value C 18 H 19 O[M+H] + 251.1430,test value 251.1435.

[0166] Example 26 A method for synthesizing β,γ unsaturated ketone compounds:

[0167] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 56%.

[0168] The product is 1-(3-ethylindole)-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0169]

[0170] NMR analysis results:

[0171] 1 H NMR(400MHz, CDCl3)δ8.10(s,1H),7.39(d,J=8.0Hz,1H),7.34–7.32(m,6H),7.21–7.16(m,1H),7.09(t,J=7 .4Hz,1H),6.95(s,1H),5.49(s,1H),5.19(s,1H),3.92(q,J=6.8Hz,1H),3.87(s,2H),1.32(d,J=6.8Hz,3H).

[0172] 13 C NMR (100MHz, CDCl3) δ209.2,148.4,141.1,136.2,128.6,127.9,127.5,126.5,123.6,122.2,119.8,118.8,114.9,111.3,108.6,50.3,38.0,16.8.

[0173] Calculated value C 20 H 19 NO[M+Na] + 312.1359, test value 312.1363.

[0174] Example 27 A method for synthesizing a β,γ unsaturated ketone compound:

[0175] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 90%.

[0176] The product is 1-phenylpropyl-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0177]

[0178] NMR analysis results:

[0179] 1 H NMR (400MHz, CDCl3) δ7.36–7.27(m,4H),7.25–7.20(m,2H),7.20–7.12(m,2H),7.10(d,J=7.2Hz,2H),5.42(s,1H),5. 10(s,1H),3.68(q,J=6.8Hz,1H),2.56–2.45(m,3H),2.40-2.32(m,1H),1.87–1.80(m,2H),1.30(d,J=6.8Hz,3H).For 23':2.05(s,3H),1.71(s,3H).

[0180] 13 C NMR (101MHz, CDCl3) δ210.8,148.2,141.8,141.1,128.6,128.5,128.4,127.9,126.4,126.0,114.8,52.0,39.9,35.1,25.5,16.4.For 23':208.7,139.3,128.5,127.1,126.1,41.1,35.4,25.6,22.5,17.1.

[0181] Calculated value C 20 H 23 O[M+H] + 279.1743, test value 279.1752.

[0182] Example 28 A method for synthesizing a β,γ unsaturated ketone compound:

[0183] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 80%.

[0184] The product is 2-phenyl-3-methyl-7-benzyloxy-4-keto-1-heptene, and the structural formula is as follows:

[0185]

[0186] NMR analysis results:

[0187] 1 H NMR (400MHz, CDCl3) δ7.38–7.23(m,10H),5.42(s,1H),5.11(s,1H),4.42(s,2H),3.71(q,J=6.8Hz,1H),3 .39(t,J=6.0Hz,2H),2.68–2.55(m,1H),2.53–2.41(m,1H),1.85–1.80(m,2H),1.30(d,J=6.8Hz,3H).For 24': 4.51 (s, 2H), 3.55 (t, J = 6.0Hz, 2H), 3.75 (t, J = 7.2Hz, 2H), 2.04 (s, 3H), 1.99 (t, J = 6.4Hz, 2H), 1.73 (s, 3H).

[0188] 13 C NMR (100MHz, CDCl3) δ210.8,148.3,141.1,138.6,128.6,128.5,127.9,127.7,127.7,126.4,114.8,72.9,69.4,52.0,37.3,24.1,16.4.For 24':208.6,143.0,139.3,133.6,127.1,73.0,69.5,38.6,22.5,17.1.

[0189] Calculated value C 21 H 25 O2[M+H] + 309.1849,test value 309.1847.

[0190] Example 29 A method for synthesizing a β,γ unsaturated ketone compound:

[0191] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 73%.

[0192] The product is 1-cyclopropyl-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0193]

[0194] NMR analysis results:

[0195] 1 H NMR (400MHz, CDCl3) δ7.42–7.28(m,5H),5.49(s,1H),5.18(s,1H),3.85(q,J=6.8Hz,1H), 2.02(tt,J=7.8,4.6Hz,1H),1.34(d,J=6.8Hz,3H),1.00–0.92(m,2H),0.83–0.74(m,2H).

[0196] 13 C NMR (100MHz, CDCl3) δ211.2,148.5,141.2,128.6,127.9,126.5,115.0,53.0,19.2,16.2,11.6,11.5.

[0197] Calculated value C 14 H 16 ONa[M+Na] + 223.1093, test value 223.1096.

[0198] Example 30 A method for synthesizing a β,γ unsaturated ketone compound:

[0199] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 56%.

[0200] The product is 1-cyclopentyl-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0201]

[0202] NMR analysis results:

[0203] 1 H NMR (400MHz, CDCl3) δ7.40–7.29(m,5H),5.43(s,1H),5.09(s,1H),3.81(q,J=6. 8Hz,1H),3.00(tt,J=8.0,8.0Hz,1H),1.78–1.51(m,8H),1.31(d,J=6.8Hz,3H).

[0204] 13 C NMR (100MHz, CDCl3) δ214.1,148.3,141.3,128.6,127.9,126.4,114.8,51.5,49.7,31.1,29.8,26.3,16.8.

[0205] Calculated value C 16 H 20 ONa[M+Na] + 251.1406, test value 251.1414.

[0206] Example 31 A method for synthesizing a β,γ unsaturated ketone compound:

[0207] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 60%.

[0208] The product is 1-cyclohexyl-2-methyl-3-phenyl-3-ene-1-butanone, and the structural formula is as follows:

[0209]

[0210] NMR analysis results:

[0211] 1 H NMR (400MHz, CDCl3) δ7.42–7.28(m,5H),5.41(s,1H),5.08(s,1H),3.84(q,J=6.8Hz,1H), 2.51(tt,J=11.2,3.2Hz,1H),1.77–1.51(m,6H),1.29(d,J=6.8Hz,3H),1.25–1.11(m,4H).

[0212] 13 C NMR (100MHz, CDCl3) δ214.0,148.3,141.4,128.6,127.9,126.5,114.8,50.2,49.4,29.9,28.8,26.1,25.9,25.6,16.8.

[0213] Calculated value C 17 H 23 O[M+H] + 243.1743, test value 243.1748.

[0214] Example 32 A method for synthesizing a β,γ unsaturated ketone compound:

[0215] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 70%.

[0216] The product is (6S)-3,6,10-trimethyl-2-phenylundecane-1,9-diene-4-one, and the structural formula is as follows:

[0217]

[0218] NMR analysis results:

[0219] 1 H NMR (400MHz, CDCl3) δ7.39–7.29(m,5H),5.45(s,1H),5.13(d,J=4.0Hz,1H),5.09–4.99(m,1H),3.70(p,J=6.8Hz,1H),2.48–2.20(m,2H),2 .02–1.85(m,3H),1.68(d,J=12.2Hz,3H),1.56(d,J=2.5Hz,3H),1.32(q,J=8.0,6.8Hz,3H),1.26–1.06(m,2H),0.80(dd,J=6.4,4.4Hz,3H).

[0220] 13 C NMR (100MHz, CDCl3) δ210.8,148.2,141.2,131.5,128.6,127.9,126.5,124.5,114.8,5 2.5,52.0,48.2,48.1,37.1,36.8,28.7,28.6,25.8,25.6,25.6,19.8,19.7,17.7,16.4.

[0221] Calculated value C 20 H 29 O[M+H] + 285.2213, test value 285.2208.

[0222] Example 33 A method for synthesizing a β,γ unsaturated ketone compound:

[0223] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 76%.

[0224] The product is 1-(4,5-diphenyloxazol-2-alkyl)-4-methyl-5-phenylhexane-5-ene-3-one, and the structural formula is as follows:

[0225]

[0226] NMR analysis results:

[0227] 1 H NMR(400MHz, CDCl3)δ7.65–7.38(m,5H),7.42–7.28(m,10H),5.49(s,1H),5 .18(s,1H),3.84(q,J=6.8Hz,1H),3.17–2.93(m,4H),1.38(d,J=6.8Hz,3H).

[0228] 13 C NMR (100MHz, CDCl3) δ208.9,162.5,148.0,145.4,140.8,135.2,132.7,129.2,128. 7,128.7,128.6,128.5,128.1,128.0,126.6,126.4,115.2,52.1,37.3,22.6,16.4.

[0229] Calculated value C 28 H 26 NO2[M+H] + 408.1958, test value 408.1968.

[0230] Example 34 A method for synthesizing a β,γ unsaturated ketone compound:

[0231] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 83%.

[0232] The product is 3-(4-methoxyphenyl)-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0233]

[0234] NMR analysis results:

[0235] 1 H NMR (400MHz, CDCl3) δ7.90 (d, J=7.2Hz, 2H), 7.50 (t, J=7.4Hz, 1H), 7.40–7.36 (m, 4H), 6.89 (d, J= 8.8Hz,2H),5.34(s,1H),4.98(s,1H),4.53(q,J=6.8Hz,1H),3.83(s,3H),1.49(d,J=6.8Hz,3H).

[0236] 13 C NMR (100MHz, CDCl3) δ200.5,159.5,148.0,136.6,133.3,132.9,128.6,128.6,127.3,114.1,113.5,55.4,46.7,17.8.

[0237] Calculated value C 18 H 18 O2 Na(M+Na) + 289.1199,test value 289.1194.

[0238] Example 35 A method for synthesizing a β,γ unsaturated ketone compound:

[0239] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 92%.

[0240] The product is 3-(4-chlorophenyl)-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0241]

[0242] NMR analysis results:

[0243] 1 H NMR(400MHz, CDCl3)δ7.78(d,J=8.0Hz,2H),7.36–7.29(m,4H),7.19(d,J=8.0Hz,2H) ,5.38(s,1H),5.12(s,1H),4.50(q,J=6.8Hz,1H),2.38(s,3H),1.47(d,J=6.8Hz,3H).

[0244] 13 C NMR (100MHz, CDCl3) δ199.8,147.7,143.9,139.6,133.9,133.7,129.4,128.8,128.7,127.6,115.5,46.4,21.7,17.8.

[0245] Calculated value C 18 H 17 ClO Na(M+Na) + 307.0860,test value 307.0866.

[0246] Example 36 A method for synthesizing β,γ unsaturated ketone compounds:

[0247] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 56%.

[0248] The product is 3-(3-methylphenyl)-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0249]

[0250] NMR analysis results:

[0251] 1 H NMR (400MHz, CDCl3) δ7.90(d,J=7.2Hz,2H),7.49(t,J=7.2Hz,1H),7.38(t,J=7.8Hz,2H),7.28–7.23(m,3H ),7.15–7.11(m,1H),5.38(s,1H),5.03(s,1H),4.55(q,J=6.8Hz,1H),2.37(s,3H),1.48(d,J=6.8Hz,3H).

[0252] 13 C NMR (100MHz, CDCl3) δ200.5,148.7,140.9,138.3,136.5,132.9,128.8,128.6,128.6,128.6,127.0,123.2,114.8,46.6,21.7,17.9.

[0253] Calculated value C 18 H 19 O(M+H) + 251.1430, test value 251.1423.

[0254] Example 37 A method for synthesizing a β,γ unsaturated ketone compound:

[0255] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 91%.

[0256] The product is 3-(benzo[1,3]dioxydiol)-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0257]

[0258] NMR analysis results:

[0259] 1 H NMR (400MHz, CDCl3) δ7.94–7.86(m,2H),7.50(t,J=7.6Hz,1H),7.38(t,J=7.6Hz,2H),6.96–6.88(m,2H),6 .79(d,J=8.4Hz,1H),5.96(s,2H),5.31(s,1H),5.00(s,1H),4.48(q,J=6.8Hz,1H),1.48(d,J=6.8Hz,3H).

[0260] 13 C NMR (100MHz, CDCl3) δ200.3,148.2,148.1,147.5,136.5,135.2,132.9,128.6,119.7,114.1,108.3,106.9,101.3,46.8,17.8.

[0261] Calculated value C 18 H 16 O3 Na(M+Na) + 303.0992, test value 303.0982.

[0262] Example 38 A method for synthesizing a β,γ unsaturated ketone compound:

[0263] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and the residue is eluted with a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) for column chromatography to obtain a colorless oily product with a yield of 84%.

[0264] The product is 2-methyl-3-(naphthylacetyl-2-yl)-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0265]

[0266] NMR analysis results:

[0267] 1 H NMR(400MHz, CDCl3) δ7.92–7.90(m,3H),7.85–7.79(m,3H),7.59(dd,J=8.6,1.6Hz,1H),7.49–7.45( m,3H),7.35(t,J=7.6Hz,2H),5.55(s,1H),5.16(s,1H),4.69(q,J=6.8Hz,1H),1.56(d,J=6.8Hz,3H).

[0268] 13 C NMR (100MHz, CDCl3) δ200.4,148.5,138.1,136.5,133.5,133.1,132.9,128.6 ,128.6,128.4,128.4,127.7,126.5,126.3,124.8,124.6,115.5,46.6,18.0.

[0269] Calculated value C 21 H 19 O(M+H) + 287.1430, test value 287.1440.

[0270] Example 39 A method for synthesizing a β,γ unsaturated ketone compound:

[0271] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 65%.

[0272] The product is 3-(6-methoxypyridin-3-yl)-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0273]

[0274] NMR analysis results:

[0275] 1 H NMR (400MHz, CDCl3) δ8.16(d,J=2.8Hz,1H),7.82(d,J=7.6Hz,2H),7.56(dd,J=8.8,2.8Hz,1H),7.43(t,J=7.6Hz,1H),7.32( t,J=7.6Hz,2H),6.65(d,J=8.6Hz,1H),5.28(s,1H),5.01(s,1H),4.43(q,J=6.8Hz,1H),3.86(s,3H),1.40(d,J=6.8Hz,3H).

[0276] 13 C NMR (100MHz, CDCl3) δ200.1,163.9,145.4,144.4,136.7,136.4,133.1,129.7,128.7,128.6,114.9,110.8,53.6,46.5,17.6.

[0277] Calculated value C 17 H 18 NO2(M+H) + 268.1332, test value 268.1335.

[0278] Example 40 A method for synthesizing a β,γ unsaturated ketone compound:

[0279] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 89%.

[0280] The product is 2-methyl-3-methylene-1-phenyloctane-1-one, and the structural formula is as follows:

[0281]

[0282] NMR analysis results:

[0283] 1 H NMR (400MHz, CDCl3) δ7.96(d,J=7.2Hz,2H),7.53(t,J=7.2Hz,1H),7.43(t,J=7.6Hz,2H),4.89(s,2H),4.09(q,J= 6.8Hz,1H),2.15–1.97(m,2H),1.48–1.40(m,2H),1.34(d,J=6.8Hz,3H),1.27–1.25(m,4H),0.86(t,J=6.8Hz,3H).

[0284] 13 C NMR (100MHz, CDCl3) δ201.3,149.5,137.1,132.8,128.6,128.5,112.0,48.5,34.7,31.7,27.5,22.7,16.9,14.1.

[0285] Calculated value C 16 H 22 O Na(M+Na) + 253.1563,test value 253.1553.

[0286] Example 41 A method for synthesizing a β,γ unsaturated ketone compound:

[0287] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 78%.

[0288] The product is 5-(benzyl)-2-methyl-3-methylene-1-phenylpentane-1-one, and the structural formula is as follows:

[0289]

[0290] NMR analysis results:

[0291] 1 H NMR (400MHz, CDCl3) δ8.01–7.92(m,2H),7.52(t,J=7.2Hz,1H),7.39(t,J=7.6Hz,2H),7.34–7.28(m,5H),4.98(s,1H), 4.96(s,1H),4.49(s,2H),4.18(q,J=6.8Hz,1H),3.62(td,J=6.8,1.7Hz,2H),2.52–2.35(m,2H),1.36(d,J=6.8Hz,3H).

[0292] 13 C NMR (100MHz, CDCl3) δ201.2,146.6,138.4,136.9,132.9,128.6,128.6,128.5,127.8,127.7,113.7,73.1,69.2,48.0,34.9,16.7.

[0293] Calculated value C 20 H 23 O2(M+H) + 295.1673,test value 295.1675.

[0294] Example 42 A method for synthesizing a β,γ unsaturated ketone compound:

[0295] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 91%.

[0296] The product is 3-cyclohexyl-2-methyl-1-phenylbutane-3-ene-1-one, and the structural formula is as follows:

[0297]

[0298] NMR analysis results:

[0299] 1 H NMR (400MHz, CDCl3) δ7.99–7.91(m,2H),7.55–7.47(m,1H),7.43(d,J=7.8Hz,2H),4.92(s,1H),4.88(s,1H) ,4.12(q,J=6.8Hz,1H),1.94(t,J=11.2Hz,1H),1.84–1.65(m,5H),1.34(d,J=6.8Hz,3H),1.30–1.10(m,5H).

[0300] 13 C NMR (100MHz, CDCl3) δ201.5,154.8,137.3,132.7,128.5,128.5,110.9,47.8,43.5,33.6,33.5,26.9,26.4,17.5.

[0301] Calculated value C 17 H 23 O(M+H) + 243.1743, test value 243.1739.

[0302] Example 43 A method for synthesizing a β,γ unsaturated ketone compound:

[0303] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 51%.

[0304] The product is 2-ethyl-1,3-diphenylbutane-3-ene-1-one, and the structural formula is as follows:

[0305]

[0306] NMR analysis results:

[0307] 1 H NMR(400MHz, CDCl3)δ7.92–7.84(m,2H),7.49(t,J=7.2Hz,1H),7.44–7.29(m,7H),5.40(s,1H),5.12(s,1H),4 .36(dd,J=8.4,5.2Hz,1H),2.17(dq,J=14.2,7.4Hz,1H),1.84(dq,J=14.2,7.4Hz,1H),0.99(t,J=7.4Hz,3H).

[0308] 13 C NMR (100MHz, CDCl3) δ199.9,147.1,141.4,137.3,132.9,128.7,128.6,128.6,127.9,126.4,115.6,54.2,26.0,13.0.

[0309] Calculated value C 18 H 18 O Na(M+Na) + 273.1250,test value 273.1253.

[0310] Example 44 A method for synthesizing a β,γ unsaturated ketone compound:

[0311] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 50%.

[0312] The product is 2-phenyl-1,3-diphenylbutane-3-ene-1-one, and the structural formula is as follows:

[0313]

[0314] NMR analysis results:

[0315] 1 H NMR (400MHz, CDCl3) δ7.79(d,J=8.4Hz,2H),7.45(t,J=7.4Hz,1H),7.37–7.29(m,7H),7.25–7.21(m,4H),7.17–7.13(m, 1H), 5.46 (s, 1H), 5.22 (s, 1H), 4.75 (dd, J = 8.8, 5.0Hz, 1H), 3.55 (dd, J = 14.0, 8.8Hz, 1H), 3.06 (dd, J = 14.0, 5.0Hz, 1H).

[0316] 13 C NMR (100MHz, CDCl3) δ199.0,146.8,141.0,140.4,137.0,132.9,129.2,128.7,128.6,128.5,128.5,128.0,126.4,126.3,116.3,54.6,38.6.

[0317] Calculated value C 23 H 20 ONa(M+Na) + 335.1406,test value 335.1400.

[0318] Example 45 A method for synthesizing a β,γ unsaturated ketone compound:

[0319] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 88%.

[0320] The product is (E)-2-ethyldiene-1-phenyloctane-1-one, and the structural formula is as follows:

[0321]

[0322] NMR analysis results:

[0323] 1 H NMR (400MHz, CDCl3) δ7.68–7.59(m,2H),7.49(t,J=7.4Hz,1H),7.40(t,J=7.4Hz,2H),6.30(q,J=7 .0Hz,1H),2.48(t,J=7.4Hz,2H),1.88(d,J=7.0Hz,3H),1.42–1.25(m,8H),0.88(t,J=6.4Hz,3H).

[0324] 13 C NMR (100MHz, CDCl3) δ199.0,142.8,140.3,139.3,131.5,129.4,128.1,31.8,29.5,28.8,26.5,22.8,14.6,14.2.

[0325] Calculated value C 16 H 22 ONa(M+Na) + 253.1563,test value 253.1566.

[0326] Example 46 A method for synthesizing a β,γ-unsaturated ketone compound:

[0327] 0.2 mmol of primary alcohol compound 0.04 mmol of diphenyl phosphonate and a stirring magnet were added to the reaction flask, which was then brought into a nitrogen-filled glove box and 0.5 mmol of the allene compound was added. 0.01mmol of triruthenium dodecacarbonyl, 0.03mmol of 1,2-bis(dicyclohexylphosphino)-ethane and 2mL of anhydrous and oxygen-free toluene solvent. Then seal and remove from the glove box, react at 130°C for 16h. After cooling to room temperature, evaporate the solvent under reduced pressure, and use a mixed solvent of ethyl acetate-petroleum ether (1mL:20mL) as an eluent for column chromatography to obtain a colorless oily product with a yield of 45%.

[0328] The product is (E)-2-phenylethyl-1-phenyloctane-2-ene-1-one, and the structural formula is as follows:

[0329]

[0330] NMR analysis results:

[0331] 1 H NMR (400MHz, CDCl3) δ7.58–7.55(m,2H),7.51–7.47(m,1H),7.41–7.38(m,2H),7.30–7.25( m,2H),7.24–7.17(m,3H),6.34(q,J=7.2Hz,1H),2.84–2.73(m,4H),1.73(d,J=7.2Hz,3H).

[0332] 13 C NMR (100MHz, CDCl3) δ198.7,142.1,141.9,141.3,139.1,131.5,129.4,128.8,128.43,128.1,126.1,34.7,28.4,14.6.

[0333] Calculated value C 18 H 18 ONa(M+Na) + 273.1250, test value 273.1255.

[0334] The eluent in the above examples 1 to 46 can also be replaced by ethyl acetate-ether or ethyl acetate-n-hexane. Column chromatography can be replaced by recrystallization, thin layer chromatography or reduced pressure distillation.

[0335] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for synthesizing β,γ unsaturated ketone compounds, characterized in that: The synthesis method is to add a primary alcohol compound, an allene compound, a cyclohexylphosphine compound, an additive and a transition metal ruthenium catalyst into a reaction container, and add an organic solvent under a nitrogen atmosphere, react at 130° C. for 16 hours, and obtain a β,γ unsaturated ketone compound through separation and purification; the molecular formula of the β,γ unsaturated ketone compound is: Where: R 1 and R 3 are arbitrarily selected from any one of an alkyl group, an aromatic hetero group, an aryl group, and an alkoxy group with a carbon number greater than or equal to C1; R 2 Any one selected from hydrogen, an alkyl group greater than or equal to C1, and an aryl group.

2. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The general formula of the primary alcohol compound is: Where: R 1 and R 2 Any one of an alkyl group, an aromatic hetero group, and an aryl group having a carbon number greater than or equal to C1 can be selected arbitrarily.

3. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The amount of the allene compound used is 250% of the molar amount of the primary alcohol compound. The general formula of the allene compound is: Where: R 2 are any one of an alkyl group, an aromatic hetero group, or an aryl group having a carbon number greater than or equal to C1, R 3 are selected from any one of hydrogen, alkyl or aryl with a C1 value, R 4 Selected from hydrogen or an alkyl group equal to C1.

4. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The cyclohexylphosphine compound refers to any one of 1,2-bis(dicyclohexylphosphino)-ethane and tricyclohexylphosphine, and its usage is 20 mol% of the molar usage of the primary alcohol compound.

5. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The additive is any one of diphenyl phosphonate, silver trifluoromethanesulfonate, and sodium tetrafluoroborate, and the amount of the additive is 20 mol% of the molar amount of the primary alcohol compound.

6. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The transition metal ruthenium catalyst is triruthenium dodecacarbonyl, and its usage is 5 mol% of the molar usage of the primary alcohol compound.

7. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The organic solvent is any one of tetrahydrofuran, 1,4-dioxane, and toluene, and its usage amount is 50 to 100 times the molar usage amount of the primary alcohol compound.

8. The method for synthesizing a β,γ-unsaturated ketone compound according to claim 1, characterized in that: The separation and purification refers to column chromatography, and the eluent in the column chromatography refers to ethyl acetate-petroleum ether in a volume ratio of 1:10-30.

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