1,5-dicarbonyl compound, and synthesis method and application thereof

Abstract

The application provides a 1,5-dicarbonyl compound and a synthesis method and application thereof, wherein the synthesis method of the 1,5-dicarbonyl compound comprises the following steps: under the protection of inert gas, mixing 1,3-dicarbonyl compound and olefin compound in an organic solvent, and under the action of a zirconium-containing catalyst, reacting under the conditions of stirring and light source irradiation to generate the 1,5-dicarbonyl compound. The synthesis method of the 1,5-dicarbonyl compound has the characteristics of mildness, high efficiency and green environmental protection, and can realize catalytic asymmetric process, and the synthesis method is characterized in that under the protection of inert gas, chiral or achiral 1,5-dicarbonyl compound is synthesized by using 1,3-dicarbonyl compound and olefin compound as raw materials, a zirconium-containing catalyst, and the conditions of stirring and light source irradiation. The method can directly react under the condition of inert gas protection and light irradiation, does not need to add an additive, does not generate toxic by-products, and has an atomic economy of 100%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of synthesis of dicarbonyl compounds, in particular to a 1,5-dicarbonyl compound and a synthesis method and application thereof. BACKGROUND

[0002] Zirconium is a kind of metal widely existing in nature, with abundant reserves and relatively low price. Various complexes containing this metal can be used as Lewis acid in organic compound conversion and polymer compound synthesis. However, the research on visible light promoted zirconium catalytic reaction is relatively scarce, and further expansion is needed.

[0003] In 1962, Professor Paul de Mayo discovered that 1,3-dicarbonyl compounds and olefins undergo [2+2] cycloaddition under light conditions, and then undergo reverse Aldol reaction to obtain 1,5-dicarbonyl compounds, which is called de Mayo reaction. This reaction has been successfully applied to the total synthesis of various natural products and drug active molecules, and has high practical value. The synthesis of 1,5-dicarbonyl compounds can be realized through de Mayo reaction. This compound is widely used in medical treatment, material, scientific research and other fields, and some compounds have antitumor, blood lipid and cholesterol lowering, antibacterial and other biological activities. At the same time, this compound is an important intermediate in synthetic chemistry and chemical industry, which can be used to synthesize heterocyclic compounds and other organic compounds in organic conversion. Therefore, the method for efficiently synthesizing this compound may have high practical value.

[0004] At present, there is almost no report on visible light promoted organic conversion reaction involving zirconium complex. Some reports on the visible light responsiveness of zirconium complex are focused on MOF materials rather than as catalytically active center to participate in the reaction. 1,5-dicarbonyl compounds are mainly obtained by Michael addition process, that is, by 1,4-nucleophilic addition of nucleophilic reagent containing carbonyl group with α,β-unsaturated carbonyl compound.

[0005] However, when using Michael addition process to synthesize 1,5-dicarbonyl compounds, the raw materials have high toxicity, the reaction conditions are relatively harsh, the synthesis efficiency of non-chiral 1,5-dicarbonyl compounds is low, and chiral 1,5-dicarbonyl compounds are difficult to obtain. For de Mayo reaction, the reaction usually uses high-energy ultraviolet light source, which is not environmentally friendly, and limits its application range. The process promoted by visible light has been successfully realized only in recent years, and the efficiency still has room for further improvement. SUMMARY

[0006] Therefore, one object of the present application is to provide a synthesis method of 1,5-dicarbonyl compounds, which is characterized in that, under the protection of inert gas, 1,3-dicarbonyl compounds and olefin compounds are used as raw materials, a zirconium-containing catalyst is used, and chiral or achiral 1,5-dicarbonyl compounds are synthesized under the conditions of stirring and light source irradiation. The method has the characteristics of mildness, high efficiency, greenness and environmental protection, and can realize catalytic asymmetric process. The method can occur under the condition of direct light irradiation under the protection of inert gas, without heating and without adding additives, and no toxic by-products are generated, with an atomic economy of 100%, and the raw materials can be recycled and reused.

[0007] Another object of the present application is to provide a 1,5-dicarbonyl compound.

[0008] Still another object of the present application is to provide an application of a 1,5-dicarbonyl compound.

[0009] To achieve the above objects, the first aspect of the present application provides a synthesis method of 1,5-dicarbonyl compounds, which is characterized in that, the method comprises:

[0010] Under the protection of inert gas, 1,3-dicarbonyl compounds and olefin compounds are mixed in an organic solvent, and the 1,5-dicarbonyl compounds are generated by reacting under the action of a zirconium-containing catalyst under the conditions of stirring and light source irradiation.

[0011] In some embodiments, the inert atmosphere includes but is not limited to one or more of nitrogen, helium, argon, etc.

[0012] It should be noted that the synthesis method of 1,5-dicarbonyl compounds of the embodiments of the present application can be used for the synthesis of chiral 1,5-dicarbonyl compounds, and can also be used for the synthesis of achiral 1,5-dicarbonyl compounds, and the main difference between the two is that the types of zirconium-containing catalysts are different.

[0013] Specifically, when used for the synthesis of chiral 1,5-dicarbonyl compounds:

[0014] In some embodiments, the zirconium-containing catalyst includes a first catalyst and a second catalyst, the first catalyst includes but is not limited to one or more of ZrCl4, Zr(OTf3)4, ZrBr4, Zr(O n Pr)4, ZrF4, ZrOCl2, Zr(OH)4, Zr(OAc)4, Zr[(PhO)2POO]4, Zr[( p OMePhO)2POO]4, Zr[( p ClPhO)2POO]4, Zr[( p BrPhO)2POO]4; and the second catalyst is a chiral phosphoric acid. In some embodiments, the chiral phosphoric acid has a structure of formula (I):

[0015]

[0016] wherein R 1 , R 2 is independently selected from phenyl, one of the following.

[0017] At this time, in some embodiments, the 1,3-dicarbonyl compound has a structure of formula (III), in which formula (III), R 5 is phenyl or substituted phenyl, and R 6 is phenyl, substituted phenyl, C1-4alkyl.

[0018]

[0019] In some embodiments, the olefin compound has a structure of formula (IV), in which formula (IV), R 7 is phenyl or substituted phenyl.

[0020]

[0021] In some embodiments, the 1,5-dicarbonyl compound is a chiral 1,5-dicarbonyl compound having a structure of formula (V),

[0022]

[0023] In formula (V), R 8 is phenyl or substituted phenyl, and R 9 is phenyl, substituted phenyl, C1-4alkyl, and R 10 is phenyl or substituted phenyl.

[0024] The principle of the synthesis reaction of the chiral 1,5-dicarbonyl compound can be expressed as formula (1):

[0025]

[0026] It should be noted that R 8 is the same as R 5 , R 9 is the same as R 6 , R 10 is the same as R 7 . Among them, when R 5 and R 8 are substituted phenyl, the substituents include but are not limited to alkoxy, alkyl, haloalkyl, halogen, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. When R 9 and R 6 are phenyl.When it is a phenyl group containing a substituent, the substituent is not limited to alkoxy, alkyl, haloalkyl, halogen, etc., including but not limited to C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, etc. 10 and R 7 When the phenyl group contains a substituent, the substituent includes but is not limited to alkoxy, alkyl, haloalkyl, halogen, etc., including but not limited to C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, etc.

[0027] In some embodiments, the method for synthesizing a chiral 1,5-dicarbonyl compound comprises the following steps:

[0028] Before the 1,3-dicarbonyl compound and the olefin compound react, the 1,3-dicarbonyl compound is reacted with a first catalyst and a second catalyst to generate an intermediate represented by formula (II), and the intermediate represented by formula (II) and the olefin compound are mixed in an organic solvent and reacted under stirring and light irradiation to generate a chiral 1,5-dicarbonyl compound;

[0029]

[0030] In formula (II), R 3 is a phenyl group or a phenyl group containing a substituent, R 4 It should be noted that in the synthesis of chiral 1,5-dicarbonyl compounds, R 3 、R 5 、R 8 The three are the same, R 4 、R 6 With R 9 When the three are the same, when they are each a phenyl group containing a substituent, the specific selection of the substituent is as above (R 8 With R 5 Same, R 9 With R 6 Same situation) as described above, no further details will be given here.

[0031] In other embodiments, the method for synthesizing chiral 1,5-dicarbonyl compounds further comprises the step of: before the reaction of the 1,3-dicarbonyl compound and the olefin compound, first reacting a portion of the 1,3-dicarbonyl compound with the first catalyst and the second catalyst to generate the intermediate of the above formula (II), and then mixing the intermediate of formula (II), another portion of the 1,3-dicarbonyl compound and the olefin compound in an inert atmosphere in an organic solvent and reacting under stirring and light source irradiation to generate the chiral 1,5-dicarbonyl compound. Preferably, the molar amount of the 1,3-dicarbonyl compound used to generate the intermediate of the above formula (II) by reacting with the first catalyst and the second catalyst is m mol, and the molar amount of the 1,3-dicarbonyl compound used to mix the intermediate of formula (II) and the olefin compound in an inert atmosphere in an organic solvent is n mol, m:n = 1:(1-20), including but not limited to 1:20, 1:10, 1:5, 1:2 or 1:1, etc.

[0032] It can be understood that in the synthesis process of the chiral 1,5-dicarbonyl compound of the present application, the intermediate of formula (II) can be obtained by pre-mixing the first catalyst and the second catalyst (chiral phosphoric acid) and the 1,3-dicarbonyl compound of formula (III) and then separating. This intermediate can be irradiated with a light source under stirring conditions to obtain the target compound of formula (V), or it can replace the first catalyst and the second catalyst (chiral phosphoric acid) as a catalyst for the reaction of the 1,3-dicarbonyl compound of formula (III) and the olefin compound of formula (IV) to undergo the same reaction. Among them, the first catalyst is ZrCl4, the second catalyst is Formula (III) is Formula (IV) is Formula (V) is The intermediate formula (II) is For example, a possible reaction principle involved is shown in formulas (1-1)-(1-5):

[0033]

[0034]

[0035]

[0036]

[0037]

[0038] Among them, [formula (II)] * Formula (II) in the excited state, formula (IX), formula (X) are respectively:

[0039]

[0040] In some embodiments, the organic solvent is one or more of chloroform, dichloromethane, and 1,2-dichloroethane. Preferably, the organic solvent is chloroform.

[0041] In some embodiments, the light source is visible light. Preferably, the light source is a 10W 400nm LED.

[0042] In some embodiments, the amount of the first catalyst added is 2.5-7.5 mol%, including but not limited to 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 5.5 mol%, 6 mol%, 6.5 mol%, 7 mol% or 7.5 mol%, etc.

[0043] In some embodiments, the amount of the second catalyst added is 10-20 mol%, including but not limited to 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%, 16 mol%, 17 mol%, 18 mol%, 19 mol% or 20 mol%, etc.

[0044] As a possible example, in the synthesis of chiral 1,5-dicarbonyl compounds, the first catalyst is ZrCl4 and the second catalyst is The amount of the first catalyst added was 5 mol%, and the amount of the second catalyst added was 15 mol%.

[0045] In the present application, when the method for synthesizing a 1,5-dicarbonyl compound is used for the synthesis of an achiral 1,5-dicarbonyl compound:

[0046] In some embodiments, zirconium-containing catalysts include but are not limited to ZrCl4, Zr[(PhO)2POO]4, Zr[( p OMePhO)2POO]4、Zr[( p ClPhO)2POO]4、Zr[( p BrPhO)2POO]4, Zr(O n Pr)4, Zr(HPO4)2, ZrOCl2, Zr(OH)4, Zr(OAc)4, ZrH2, Cp2ZrCl2, CpZrCl3, ( nOne or more of indene ZrCl2 (CAS: 100080-82-8), indene ZrCl3 (CAS: 82161-76-0), and indene ZrCl2 (CAS: 12148-49-1). The structural formulas of indene ZrCl2 (CAS: 100080-82-8), indene ZrCl3 (CAS: 82161-76-0), and indene ZrCl2 (CAS: 12148-49-1) are as follows:

[0047] Indene ZrCl2: Indene ZrCl3: Indene 2ZrCl 2:

[0048] In other embodiments, the zirconium-containing catalyst includes a first catalyst and a second catalyst, wherein the first catalyst is ZrCl4 and the second catalyst is achiral phosphoric acid. As a non-limiting example, the molar ratio of the first catalyst to the second catalyst during the synthesis of the achiral 1,5-dicarbonyl compound is 2-1:3-0.01, including but not limited to 1:1, 1:2, 1:3, 2:1, or 1:0.01.

[0049] In some embodiments, non-chiral phosphoric acid as the second catalyst includes but is not limited to (PhO)2POOH, ( p OMePhO)2POOH, ( p ClPhO)2POOH, ( p BrPhO)2POOH or more.

[0050] In some embodiments, the 1,3-dicarbonyl compound has the structure of formula (VI),

[0051]

[0052] In formula (VI), R 11 is a phenyl group or a phenyl group containing a substituent, R 12 It is one of phenyl, phenyl containing a substituent, C1-3 alkyl, and amino containing a substituent.

[0053] In some embodiments, the olefin compound has the structure of formula (VII),

[0054]

[0055] In formula (VII), R 13 is one of hydrogen, phenyl, C1-8 aryl containing a substituent, C1-18 alkyl, and acetoxy, R 14 and R 15each independently is one of hydrogen, phenyl, substituted C1-8 aryl, C1-18 alkyl, acetoxy.

[0056] In some embodiments, the 1,5-dicarbonyl compound is an achiral 1,5-dicarbonyl compound having the structure of Formula (VIII),

[0057]

[0058] In Formula (VIII), R 16 is phenyl or substituted phenyl, R 17 is one of phenyl, substituted phenyl, C1-3 alkyl, substituted amino, R 18 is one of phenyl, substituted C1-8 aryl, C1-18 alkyl, acetoxy, R 19 and R 20 each independently is one of phenyl, substituted C1-8 aryl, C1-18 alkyl, acetoxy.

[0059] In this application, the principle of the synthesis reaction of the achiral 1,5-dicarbonyl compound can be expressed as Formula (2):

[0060]

[0061] wherein, R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , R 15 is the same as R 20 . Wherein, when R 11 and R 16 are substituted phenyl, the substituents include but are not limited to alkoxy, alkyl, halogen, haloalkyl, cyano, etc., including but not limited to C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, etc. When R 12 and R 17 are substituted phenyl, the substituents include but are not limited to cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4 alkoxy, C1-4 alkyl, C1-4 haloalkyl, etc.; when R 12 and R 17 are substituted amino, the substituents include but are not limited to phenyl, benzyl, phenyl containing a first substituent, etc., and the first substituent includes but is not limited to C1-4 haloalkyl, C1-4 alkyl, etc. When R 13 and R 18When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. 14 When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. 19 When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. 15 When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc. 20 When R1and R2are a substituted phenyl group, the substituents include, but are not limited to, cyano, haloalkyl, halogen, alkyl, alkoxy, etc., including but not limited to C1-4alkoxy, C1-4alkyl, C1-4haloalkyl, etc.

[0062] In some embodiments, the organic solvent is one or more of dichloromethane, chloroform, ethyl acetate, ethanol, acetonitrile, isopropanol, 1,2-dichloroethane. Preferably, the organic solvent is dichloromethane (DCM) in the synthesis of achiral 1,5-dicarbonyl compounds, preferably 0.1 M dichloromethane (DCM).

[0063] In some embodiments, the light source is a 10W 400-440nm visible light. Preferably, the light source is a 10W 440nm LED; when R1in formula (VI) is C1-3alkyl or NHBn, a 10W 400nm LED is used. 12 When R1in formula (VI) is C1-3alkyl or NHBn, a 10W 400nm LED is used.

[0064] In some embodiments, the amount of zirconium-containing catalyst added in the synthesis of achiral 1,5-dicarbonyl compounds is 2-10 mol%, including but not limited to 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol%, etc.

[0065] As one possible example, the zirconium-containing catalyst in the synthesis of achiral 1,5-dicarbonyl compounds is indenyl ZrCl2(CAS: 100080-82-8), and the amount of addition is 2 mol%. When R1in formula (VI) is a substituted amino group, the amount of addition of the zirconium-containing catalyst is 10 mol%. 12 When R1in formula (VI) is a substituted amino group, the amount of addition of the zirconium-containing catalyst is 10 mol%.

[0066] In some embodiments, whether in the synthesis of chiral 1,5-dicarbonyl compounds or in the synthesis of achiral 1,5-dicarbonyl compounds, the molar amount of 1,3-dicarbonyl compounds is a mol, the molar amount of olefin compounds is b mol, and a and b satisfy the following relationship: a-1 / b-1=1 / 2, a and b are both greater than 0. As non-limiting examples, the value of a / b includes but is not limited to 1, 1 / 2, 1 / 3, or 2, etc. Preferably, the value of a / b is 1 / 2.

[0067] To achieve the above object, the second aspect of the present application provides a 1,5-dicarbonyl compound or a pharmaceutically acceptable salt thereof as shown in general formula (V), which is synthesized by the synthesis method of the present application,

[0068]

[0069] In formula (V), R 8 is phenyl or phenyl containing a substituent, R 9 is one of phenyl, phenyl containing a substituent, C1-4alkyl, R 10 is phenyl or phenyl containing a substituent.

[0070] To achieve the above object, the third aspect of the present application relates to the application of the 1,5-dicarbonyl compound or the pharmaceutically acceptable salt thereof as shown in general formula (V) of the present application or the 1,5-dicarbonyl compound synthesized by the synthesis method of the present application in the field of biological medicine or the field of heterocyclic compound synthesis.

[0071] The synthesis method of the 1,5-dicarbonyl compound of the present application can bring the following beneficial effects:

[0072] Under the protection of inert gas, the chiral or achiral 1,5-dicarbonyl compound is synthesized by using zirconium-containing catalyst under the conditions of stirring and light source irradiation, with the characteristics of mild and efficient, green and environmental protection, and the catalytic asymmetric process can be realized. The method can directly react under the protection of inert gas and light irradiation, without heating and adding additives, without generating toxic by-products, with 100% atomic economy, and the raw materials can be recycled and reused.

[0073] The terms of the present application are explained as follows. For specific terms, if the meaning in the present application is inconsistent with the meaning commonly understood by those skilled in the art, the meaning in the present application shall prevail; if not defined in the present application, it has the meaning commonly understood by those skilled in the art. Unless otherwise stated, the terms used in the present application have the following meanings:

[0074] In the present application, the term "substituted" means that one or more hydrogen atoms in the given structure are replaced by a specific substituent. Unless otherwise indicated, one substituent group can be substituted at each substitutable position of the given structure. When more than one position in the given structure can be substituted by one or more substituents selected from a specific group, the substituents can be the same or different at each position. "Phenyl containing a substituent" or "substituted phenyl" means mono- or poly-substituted phenyl.

[0075] In the present application, the term "C1-xx alkyl" means a straight chain or branched alkyl group having 1 to xx (xx means the upper limit of the number of carbon atoms, for example, when xx is 10, it means the upper limit of the number of carbon atoms is 10) carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, butyl, t-butyl, pentyl, hexyl, and the like, which can be interpreted as including each of the structural forms of alkyl groups from C1, C2, C3, C4, C5, C6, C7, C8,... CX (for example, C10), and are not limited to the above examples.

[0076] In the present application, the term "aryl" means an aromatic carbocyclic group having a single ring (such as phenyl), multiple rings (such as naphthyl), or a fused ring in which at least one ring is aromatic (such as 1,2,3,4-tetrahydronaphthyl). For example, an aryl group having 5 to 20 (for example, 5 to 15 or 5 to 10) carbon atoms. Specific examples include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, acenaphthyl, and the like.

[0077] In the present application, the term "acetoxy" is a functional group having the structure -O-C(=O)-CH3.

[0078] In the present application, the term "alkoxy" is generally represented by RO-, and means a functional group composed of an alkyl group and an oxygen atom, for example, methoxy (CH3O-), ethoxy (C2H5O-), propoxy (C3H7O-), and the like.

[0079] In the present application, the term "halogen" means fluorine, chlorine, bromine, or iodine.

[0080] In the present application, the term "halogen" means fluorine, chlorine, bromine, or iodine.

[0081] In the present application, the term "benzyl" means a group (C6H5CH2-) obtained by removing one hydrogen atom from the methyl carbon of a toluene molecule.

[0082] In the present application, the term "cyano" means a group (-CN) in which a carbon atom and a nitrogen atom are connected by a triple bond.

[0083] As used herein in the specification and claims, the term "pharmaceutically acceptable" is intended to mean pharmaceutically or medically acceptable, i.e., that which is useful in preparing a pharmaceutical composition that is generally safe, non-toxic and / or desirable, and that which is generally accepted in the art for use in connection with the preparation of pharmaceuticals. For example, a pharmaceutically acceptable salt is not only one that is pharmaceutically and medicinally acceptable, but also one that is not directly useful in the clinic, but can be used in the preparation of the compounds of the present application and removed by appropriate methods before the final use in the clinic. For example, a pharmaceutically acceptable salt includes not only a medicinal salt that can be used in the clinic, but also a salt that cannot be directly used in the clinic, but can be used in the preparation of the compounds of the present application and removed in the subsequent process. As used herein, the term "pharmaceutically acceptable salt" includes conventional salts with pharmaceutically acceptable inorganic or organic acids or inorganic or organic bases, and salts with quaternary ammonium and acids. Examples of suitable acid salts include, but are not limited to, hydrochloride, hydrobromide, sulfate, phosphate, nitrate, perchlorate, fumarate, acetate, propionate, pyruvate, succinate, glycolate, formate, lactate, maleate, tartrate, citrate, embonate, malonate, glutarate, hydroxymaleate, phenylacetate, glutamate, benzoate, salicylate, fumarate, toluenesulfonate, methanesulfonate, naphthalene-2-sulfonate, benzenesulfonate, hydroxynaphthoate, hydroiodide, malate, stearate, tannate, and the like. Others such as oxalate, although not pharmaceutically acceptable by itself, can be used to prepare salts used as intermediates to obtain the compounds of the present application and their pharmaceutically acceptable salts. More specific examples of suitable base salts include sodium salt, lithium salt, potassium salt, magnesium salt, aluminum salt, calcium salt, zinc salt, ammonium salt, triethylamine salt, t-butylamine salt, N,N'-dibenzylethylenediamine salt, procaine salt, chloroprocaine salt, choline salt, diethanolamine salt, ethylenediamine salt, and N-methylglucosamine salt, and the like.

[0084] Additional aspects and advantages of the application will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION

[0085] The embodiments of the present application are described in detail below, which are exemplary and intended to explain the present application, and cannot be understood as a limitation of the present application.

[0086] In the application, the disclosure of numerical ranges includes all values and further subdivided range disclosures within the entire range, including the endpoints and subranges given to these ranges.

[0087] In the application, the raw materials, equipment, etc. involved, if not specially stated, are raw materials, equipment that can be self-made by commercial means or known methods; the methods involved, if not specially stated, are conventional methods.

[0088] In the present application, the meanings represented by the abbreviations of various functional groups are shown in Table 1:

[0089] Table 1 Functional group abbreviations and their meanings

[0090]

[0091]

[0092] Define the chiral phosphoric acid formula (I) structure

[0093]

[0094] In, R 1 、R 2 all The situation is formula (I)-1, R 1 、R 2 all The situation is formula (I)-2, R 1 、R 2 In the case of homophenyl (Ph), the formula is (I)-3, R 1 、R 2 all The situation is formula (I)-4, R 1 、R 2 all The situation is formula (Ⅰ)-5.

[0095] The nuclear magnetic resonance fluorine spectra in the following examples of this application are 13 C spectrum.

[0096] Example 1 (Template reaction)

[0097]

[0098] In a dry 10 mL schlenk tube, (III)-1 (0.1 mmol, 1.0 equivalent), ZrCl4 (0.005 mmol, 5 mol%) and (I)-1 (0.015 mmol, 15 mol%) were added; then (IV)-1 (0.2 mmol, 2.0 equivalent) was dissolved in dry CHCl3 (0.2 mL) and added to the schlenk tube with a syringe. The resulting mixture was subjected to a freeze-ventilation-thaw degassing process three times until all the gas in the system was replaced with nitrogen. At this time, a solid was generated in the reaction tube, which was the intermediate (R) represented by formula (II)-1. 3 =Ph, R 4= Me) from (III)-1, ZrCl4and (I)-1. The reaction tube was placed about 1 cm from a 10 W 400 nm LED light source and the reaction was irradiated while stirring for 2 h (i.e. the reaction time was 2 h). At this time the solids in the reaction tube had disappeared and the solution was directly purified by silica gel column chromatography to give the target product (V)-1 as the major product in 90% yield with 91% ee.

[0099] H NMR (400 MHz, Chloroform-d) δ 7.88 (dd, J = 7.7, 1.7 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 4.91 (dd, J = 8.2, 6.0 Hz, 1H), 2.60 (dt, J = 12.1, 6.0 Hz, 1H), 2.57 - 2.50 (m, 2H), 2.16 (s, 3H), 2.14 - 2.06 (m, 1H); C NMR (101 MHz, Chloroform-d) δ 207.34, 195.96, 135.63, 133.45, 128.84, 128.22, 42.50, 40.58, 29.95, 23.87; F NMR (376 MHz, Chloroform-d) δ -140.92 - -141.25 (m), -154.26 (t, J = 20.9 Hz), -160.78 - -160.99 (m).

[0100] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 10:90, flow rate = 1.0 mL / min, wavelength = 240 nm, retention time: 12.30 min (major), 10.13 min (minor), specific optical rotation [a] D 25 = +4.2 (c = 3.31, CHCl3).

[0101] Infrared spectrum (thin film, cm -1 ) 2919, 2850, 1715, 1692, 1654, 1597, 1521, 1499, 1448, 1369, 1298, 1264, 1224, 1161, 1123, 1059, 980, 940, 893, 852, 774, 700, 661.

[0102] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 14 O2F5 + 357.0908, found 357.0909.

[0103] Example 2 (intermediate equivalent reaction)

[0104] In a dry 50 mL round-bottom flask, (III)-1 (5 mmol, 1.0 equivalent), ZrCl4(0.025 mmol, 5 mol%) and (I)-1 (0.075 mmol, 15 mol%) were added, and then dry CHCl3(1.0 mL) was added to the flask with a syringe. The mixture was stirred at room temperature for 2 min, at which time solid was generated in the flask. The solid was the intermediate (R 3 = Ph, R 4 = Me) generated from (III)-1, ZrCl4and (I))-1; after the solid was separated by suction filtration, (II)-1 (0.1 mmol, 1.0 equivalent) was added to a dry 10 mL schlenk tube, and then (IV)-1 (0.2 mmol, 2.0 equivalents) was dissolved in dry CHCl3(0.2 mL) and added to the schlenk tube with a syringe. The mixture was degassed by a freeze-purge-thaw degassing process three times, so that the gas in the system was completely replaced by nitrogen. The reaction tube was placed about 1 cm away from a 10W 400 nm LED light source, and the reaction system was irradiated for 2 h while stirring. Then H2O (2 mmol, 20.0 equivalents) was added. The solution was directly purified by silica gel column chromatography to obtain the main product, which was the target product (V)-1, with a yield of 85% and an ee value of 80%.

[0105]

[0106] Example 3 (intermediate catalytic reaction)

[0107]

[0108]

[0109] In a dry 50 mL round-bottom flask, (III)-1 (5 mmol, 1.0 equivalent), ZrCl4(0.025 mmol, 5 mol%) and (I)-1 (0.075 mmol, 15 mol%) were added, and then dry CHCl3(1.0 mL) was added to the flask with a syringe. The mixture was stirred at room temperature for 2 min, at which time solid was generated in the flask. The solid was the intermediate (R 3 = Ph, R 4= Me), generated from (III)-1, ZrCl4and (I)-1. After the solid was separated by suction filtration, (II)-1 (0.1 mmol, 1.0 equiv) was added to a dry 10 mL schlenk tube, then (IV)-1 (0.2 mmol, 2.0 equiv) was dissolved in dry CHCl3(0.2 mL) and added to the schlenk tube with a syringe. The resulting mixture was degassed by a freeze-pump-thaw degassing procedure for three times to make sure the gas in the system was replaced by nitrogen. The reaction tube was placed at about 1 cm from a 10 W 400 nm LED light source, and the reaction system was irradiated for 2 h while stirring. At this time, the solid in the reaction tube disappeared, and the solution was directly purified by silica gel column chromatography to give the target product (V)-1 as the main product with a yield of 88% and an ee value of 91%.

[0110] Example 4 (intermediate catalytic reaction)

[0111]

[0112] In a dry 50 mL round-bottom flask, (III)-18 (5 mmol, 1.0 equiv), ZrCl4(0.025 mmol, 5 mol%) and (I)-1 (0.075 mmol, 15 mol%) were added, and dry CHCl3(1.0 mL) was added to the flask with a syringe. The mixture was stirred at room temperature for 2 min, and at this time, a solid was generated in the flask, which was the intermediate (II)-2 (R 3 = R 4 = Ph), generated from (III)-18, ZrCl4and (I)-1. After the solid was separated by suction filtration, (II)-2 (0.1 mmol, 1.0 equiv) was added to a dry 10 mL schlenk tube, then (IV)-1 (0.2 mmol, 2.0 equiv) was dissolved in dry CHCl3(0.2 mL) and added to the schlenk tube with a syringe. The resulting mixture was degassed by a freeze-pump-thaw degassing procedure for three times to make sure the gas in the system was replaced by nitrogen. The reaction tube was placed at about 1 cm from a 10 W 400 nm LED light source, and the reaction system was irradiated for 2 h while stirring, and then H2O (2 mmol, 20.0 equiv) was added. The solution was directly purified by silica gel column chromatography to give the target product (V)-24 as the main product with a yield of 81% and an ee value of 76%.

[0113] Example 5 (intermediate catalytic reaction)

[0114] In a dry 50 mL round bottom flask, (III)-18 (5 mmol, 1.0 equiv), ZrCl4(0.025 mmol, 5 mol%) and (I)-1 (0.075 mmol, 15 mol%) were added, then dry CHCl3(1.0 mL) was added into the flask by syringe, and the mixture was stirred at room temperature for 2 min, at this time, solid was generated in the flask, which was the intermediate of formula (II)-2 (R 3 = R 4 = Ph) generated from (III)-18, ZrCl4and (I)-1; after the solid was separated by suction filtration, (III)-18 (0.1 mmol, 1.0 equiv) was added into a dry 10 mL schlenk tube, then (II)-2 (0.005 mmol, 5 mol%) was added, (IV)-1 (0.2 mmol, 2.0 equiv) was dissolved in dry CHCl3(0.2 mL) and added into the schlenk tube by syringe, the mixture was degassed by freeze-pump-thaw process for three times, so that the gas in the system was replaced by nitrogen, the reaction tube was placed at a distance of about 1 cm from a 10W 400 nm LED light source, and the reaction system was irradiated for 2 h while stirring. At this time, the solid in the reaction tube disappeared, and the solution was directly purified by silica gel column chromatography to obtain the target product (V)-24 as the main product, with a yield of 86% and an ee value of 81%.

[0115]

[0116] Example 6

[0117] This example is basically the same as Example 1, except that:

[0118]

[0119] 1,3-dicarbonyl compound is of formula (III)-2, and 1,5-dicarbonyl compound is of formula (V)-2; the reaction time is 3 h; the target product obtained is (V)-2, with a yield of 90% and an ee value of 81%.

[0120] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.87 (dd, J = 8.4, 1.3 Hz, 2H), 7.56-7.50 (m, 1H), 7.42 (dd, J = 8.4, 7.0 Hz, 2H), 4.91 (dd, J = 8.4, 6.2 Hz, 1H), 2.68-2.54 (m, 1H), 2.49 (t, J = 6.7 Hz, 2H), 2.40 (q, J = 7.4 Hz, 2H), 2.20-2.03 (m, 1H), 1.05 (t, J = 7.3 Hz, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 210.16, 196.01, 135.65, 133.42, 128.84, 128.24, 42.60, 39.22, 35.98, 23.94, 7.76.

[0121] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 243 nm, retention time: 11.76 min (major), 7.50 min (minor), specific optical rotation [α] D 25 = +12.1 (c = 1.96, CHCl3).

[0122] Infrared spectrum (thin film, cm -1 ) 2977, 2938, 2855, 1712, 1692, 1655, 1597, 1521, 1499, 1448, 1375, 1297, 1261, 1223, 1118, 994, 959, 910, 856, 768, 699, 662.

[0123] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 19 H 16 O2F5 + 371.1065, found 371.1064.

[0124] Example 7

[0125] This example is basically the same as Example 1, except that:

[0126] The 1,3-dicarbonyl compound has the structure of formula (III)-3, and the 1,5-dicarbonyl compound has the structure of formula (V)-3; the reaction time is 3 h; the obtained target product is (V)-3, the yield of which is 79%, and the ee value of which is 80%.

[0127]

[0128] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.91-7.84 (m, 2H), 7.56-7.50 (m, 1H), 7.42 (t, J = 7.7 Hz, 2H), 4.91 (dd, J = 8.4, 6.2 Hz, 1H), 2.58 (dt, J = 13.6, 6.6 Hz, 1H), 2.53-2.45 (m, 2H), 2.35 (t, J = 7.3 Hz, 2H), 2.16-2.03 (m, 1H), 1.69-1.50 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 209.71, 196.02, 135.66, 133.42, 128.83, 128.24, 44.77, 42.60, 39.64, 23.89, 17.25, 13.66.

[0129] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 243 nm, retention time: 8.77 min (major), 7.47 min (minor), specific optical rotation [α] D 25 = +9.9 (c = 2.28, CHCl3).

[0130] Infrared spectrum (thin film, cm -1 ) 2963, 2933, 2877, 1709, 1693, 1597, 1521, 1499, 1448, 1374, 1296, 1261, 1221, 1123, 992, 963, 770, 699, 661, 609.

[0131] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 20 H 18 O2F5 + 185.1221, found 385.1219.

[0132] Example 8

[0133] This example is essentially the same as Example 1, except that:

[0134]

[0135] 1,3-dicarbonyl compound structure is formula (III)-4, 1,5-dicarbonyl compound structure is formula (V)-4; the reaction time is 2.5h; the obtained target product is (V)-4, the yield is 80%, and the ee value is 90%.

[0136] H NMR (400 MHz, Chloroform-d) δ 7.95 - 7.81 (m, 2H), 7.57 - 7.50 (m, 1H), 7.43 (dd, J = 8.4, 7.0 Hz, 2H), 4.93 (dd, J = 8.4, 5.9 Hz, 1H), 2.69 - 2.44 (m, 4H), 2.19 - 1.99 (m, 1H), 1.07 (d, J = 6.9 Hz, 6H); C NMR (101 MHz, Chloroform-d) δ 213.51, 196.08, 135.66, 133.42, 128.84, 128.27, 42.59, 40.86, 37.23, 23.91, 18.21 (d, J = 2.6 Hz).

[0137] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 243 nm, retention time: 6.67 min (major), 5.64 min (minor). Specific optical rotation [a] D 25 = -9.6 (c = 2.18, CHCl3).

[0138] Infrared spectrum (thin film, cm -1 ) 2971, 2932, 2876, 1693, 1655, 1597, 1521, 1499, 1448, 1384, 1368, 1261, 1224, 1124, 990, 959, 778, 699, 662.

[0139] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 20 H 18 O2F5 + 385.1221, found 385.1220.

[0140] Example 9

[0141] This example is basically the same as example 1, except that:

[0142]

[0143] 1,3-dicarbonyl compound structure is formula (III)-5, 1,5-dicarbonyl compound structure is formula (V)-5; the reaction time is 10h; the obtained target product is (V)-5, the yield is 88%, and the ee value is 14%.

[0144] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.96-7.85 (m, 2H), 7.57-7.49 (m, 1H), 7.47-7.39 (m, 2H), 4.95 (dd, J = 8.6, 5.5 Hz, 1H), 2.66-2.50 (m, 3H), 2.18-1.99 (m, 1H), 1.10 (s, 9H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 214.88, 196.13, 135.69, 133.39, 128.82, 128.29, 44.09, 42.57, 33.54, 26.40, 24.15.

[0145] High performance liquid chromatography analysis: Daicel Chiralpak IC-H, isopropanol / n-hexane = 2:98, flow rate = 0.5 mL / min, wavelength = 242 nm, retention time: 20.91 min (major), 19.51 min (minor), specific optical rotation [α] D 25 = +0.9 (c = 2.27, CHCl3).

[0146] Infrared spectrum (thin film, cm -1 ) 2969, 236, 2912, 1872, 1698, 1655, 1597, 1521, 1500, 1448, 1367, 1288, 1223, 1123, 1047, 994, 963, 925, 861, 764, 698, 661, 614.

[0147] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 21 H 20 O2F5 + 399.1378, found 399.1376.

[0148] Example 10

[0149] This example is basically the same as example 1, except that:

[0150] 1,3-dicarbonyl compound structure is formula (III)-6, 1,5-dicarbonyl compound structure is formula (V)-6; reaction time is 0.5h; the obtained target product is (V)-6, the yield is 99%, and the ee value is 69%.

[0151]

[0152] NMR (400 MHz, Chloroform-d) δ 7.86 (d, J = 8.9 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.84 (dd, J = 8.1, 6.0 Hz, 1H), 3.83 (s, 3H), 2.67 - 2.43 (m, 3H), 2.13 (s, 3H), 2.11 - 2.02 (m, 1H); NMR (101 MHz, Chloroform-d) δ 207.48, 194.25, 163.75, 130.61, 128.40, 114.03, 55.48, 42.14, 40.68, 29.95, 23.99.

[0153] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 272 nm, retention time: 23.53 min (major), 11.91 min (minor), specific optical rotation [a] D 25 = -5.8 (c = 2.94, CHCl3).

[0154] IR (thin film, cm -1 ) 2955, 2921, 2849, 1715, 1682, 1599, 1576, 1521, 1498, 1420, 1367, 1311, 1258, 1170, 1121, 1029, 980, 893, 841, 755, 613, 592, 513.

[0155] HRMS (APCI source) m / z: [M+H] + Calcd for C 19 H 16 O3F5 + 387.1014, found 387.1011.

[0156] Example 11

[0157] This example is basically the same as Example 1, except that:

[0158]

[0159] 1,3-dicarbonyl compound structure is formula (III)-7, 1,5-dicarbonyl compound structure is formula (V)-7; the reaction time is 0.5 h; the obtained target product is (V)-7, the yield is 94%, and the ee value is 87%.

[0160] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.75 (d, J = 8.3 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 4.85 (dd, J = 8.1, 6.0 Hz, 1H), 2.63-2.47 (m, 3H), 2.37 (s, 3H), 2.13 (s, 3H), 2.10-2.03 (m, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 207.34, 195.49, 144.39, 133.09, 129.52, 128.34, 42.39, 40.65, 29.91, 23.92, 21.59.

[0161] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 252 nm, retention time: 14.92 min (major), 7.44 min (minor), specific optical rotation [α] D 25 = -1.2 (c = 2.59, CHCl3).

[0162] Infrared spectrum (thin film, cm -1 ) 2925, 2855, 1715, 1688, 1607, 1521, 1498, 1410, 1369, 1263, 1229, 1183, 1161, 1122, 979, 893, 826, 789, 754, 612, 479.

[0163] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 19 H 16 O2F5 + 371.1065, found 371.1063.

[0164] Example 12

[0165] This example is basically the same as example 1, except that:

[0166]

[0167] 1,3-dicarbonyl compound structure is formula (III)-8, 1,5-dicarbonyl compound structure is formula (V)-8; the reaction time is 2h; the obtained target product is (V)-8, the yield is 96%, and the ee value is 15%.

[0168] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.86-7.78 (m, 2H), 7.47-7.41 (m, 2H), 4.87 (dd, J = 8.1, 6.1 Hz, 1H), 2.68-2.46 (m, 3H), 2.13 (s, 3H), 2.10-2.04 (m, 1H), 1.30 (s, 9H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 207.40, 195.29, 157.36, 132.85, 128.28, 125.84, 42.32, 40.67, 35.15, 30.98, 29.94, 23.97.

[0169] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 252 nm, retention time: 6.32 min (major), 9.86 min (minor), specific optical rotation [α] D 25 = +1.6 (c = 2.89, CHCl3).

[0170] Infrared spectrum (thin film, cm -1 ) 2964, 2908, 1871, 1716, 1688, 1604, 1521, 1498, 1408, 1365, 1267, 122, 1191, 1161, 1109, 1059, 980, 893, 846, 747, 708, 630, 594, 558.

[0171] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 22 H 22 O2F5 + 413.1534, found 413.1531.

[0172] Example 13

[0173] This example is basically the same as example 1, except that:

[0174]

[0175] 1,3-dicarbonyl compound structure is formula (III)-9, 1,5-dicarbonyl compound structure is formula (V)-9; the reaction time is 2h; the obtained target product is (V)-9, the yield is 75%, and the ee value is 4%.

[0176] NMR (400 MHz, CHLOROFORM-d) δ 7.98 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 8.2 Hz, 2H), 4.91 (dd, J = 8.5, 5.6 Hz, 1H), 2.56 (ttdd, J = 14.9, 8.0, 6.9, 3.7 Hz, 3H), 2.14 (s, 3H), 2.08 (q, J = 7.3, 6.0 Hz, 1H); NMR (101 MHz, CHLOROFORM-d) δ 207.20, 195.20, 138.39, 134.71 (q, J = 32.7 Hz), 128.58, 125.94 (q, J = 3.7 Hz), 42.80, 40.26, 29.96, 29.69, 23.72.

[0177] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 254 nm, retention time: 5.92 min (major), 7.79 min (minor), specific optical rotation [α] D 25 = +3.0 (c = 1.31, CHCl3).

[0178] IR (thin film, cm -1 ) 2955, 2921, 2852, 1715, 1701, 1522, 1500, 1410, 1323, 1167, 1126, 1067, 981, 893, 859, 752, 599, 511.

[0179] HRMS (APCI source) m / z: [M+H] + Calcd for C 19 H 13 O2F8 + 425.0782, found 425.0780.

[0180] Example 14

[0181] This example is basically the same as Example 1, except that:

[0182]

[0183] 1,3-dicarbonyl compound structure is formula (III)-10, 1,5-dicarbonyl compound structure is formula (V)-10; the reaction time is 1.5h; the obtained target product is (V)-10, the yield is 95%, and the ee value is 93%.

[0184] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.01-7.83 (m, 2H), 7.10 (t, J=8.6 Hz, 2H), 4.86 (dd, J=8.4, 5.7 Hz, 1H), 2.71-2.43 (m, 3H), 2.13 (s, 3H), 2.11-2.02 (m, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 207.35, 194.37, 165.83 (d, J=255.9 Hz), 131.92 (d, J=2.7 Hz), 130.97 (d, J=9.3 Hz), 116.05 (d, J=22.0 Hz), 42.45, 40.44, 29.96, 23.87.

[0185] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 246 nm, retention time: 9.29 min (major), 6.60 min (minor), specific optical rotation [α] D 25 = -1.6 (c = 3.67, CHCl3).

[0186] Infrared spectrum (thin film, cm -1 ) 3077, 2925, 2854, 1715, 1693, 1597, 1521, 1498, 1410, 1369, 1230, 1158, 1123, 1059, 981, 893, 845, 752, 610, 507, 431.

[0187] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 13 O2F6 + 375.0814, found 375.0811.

[0188] Example 15

[0189] This example is basically the same as example 1, except that:

[0190]

[0191] 1,3-dicarbonyl compound structure is formula (III)-11, 1,5-dicarbonyl compound structure is formula (V)-11; the reaction time is 1 h; the obtained target product is (V)-11, the yield is 92%, and the ee value is 95%.

[0192] H NMR (400 MHz, Chloroform-d) δ 8.05-7.86 (m, 2H), 7.19-7.02 (m, 2H), 4.89 (dd, J = 8.6, 5.9 Hz, 1H), 2.64-2.54 (m, 1H), 2.54-2.43 (m, 2H), 2.40 (qd, J = 7.4, 1.2 Hz, 2H), 2.15-2.03 (m, 1H), 1.05 (t, J = 7.3 Hz, 3H); C NMR (101 MHz, Chloroform-d) δ 210.21, 194.44, 165.83 (d, J = 255.8 Hz), 131.92 (d, J = 3.2 Hz), 131.00 (d, J = 9.3 Hz), 116.05 (d, J = 21.9 Hz), 42.55, 39.08, 36.00, 23.93, 7.76.

[0193] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 245 nm, retention time: 8.74 min (major), 6.49 min (minor), specific optical rotation [α] D 25 = -1.4 (c = 2.50, CHCl3).

[0194] IR (thin film, cm -1 ) 2979, 2939, 2921, 2851, 1713, 1693, 1597, 1521, 1499, 1411, 1298, 1230, 1158, 1120, 995, 960, 911, 847, 741, 603, 506.

[0195] HRMS (APCI source) m / z: [M+H] + Calcd for C 19 H 15 O2F6 + 389.0971, found 389.0971.

[0196] Example 16

[0197] This example is basically the same as Example 1, except that:

[0198] This example is basically the same as Example 1, except that:

[0199] 1,3-dicarbonyl compound structure is formula (III)-12, 1,5-dicarbonyl compound structure is formula (V)-12; the reaction time is 1.5h; the obtained target product is (V)-12, the yield is 93%, and the ee value is 90%.

[0200] H NMR (400 MHz, Chloroform-d) δ 7.98-7.87 (m, 2H), 7.18-7.04 (m, 2H), 4.89 (dd, J = 8.6, 6.0 Hz, 1H), 2.62-2.52 (m, 1H), 2.50-2.40 (m, 2H), 2.35 (t, J = 7.4 Hz, 2H), 2.14-2.03 (m, 1H), 1.58 (q, J = 7.4 Hz, 2H), 0.90 (t, J = 7.4 Hz, 3H); C NMR (101 MHz, Chloroform-d) δ 209.78, 194.44, 165.83 (d, J = 255.8 Hz), 131.92 (d, J = 3.1 Hz), 131.00 (d, J = 9.4 Hz), 116.05 (d, J = 22.0 Hz), 44.78, 42.55, 39.50, 23.88, 17.24, 13.65.

[0201] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 245 nm, retention time: 7.85 min (major), 6.37 min (minor), specific optical rotation [α] D 25 = -2.8 (c = 3.13, CHCl3).

[0202] Infrared spectrum (thin film, cm -1 ) 2964, 2935, 2878, 1693, 1597, 1521, 1499, 1410, 1373, 1298, 1234, 1158, 1123, 995, 964, 843, 750, 603, 507.

[0203] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 20 H 17 O2F6 + 403.1127, found 403.1123.

[0204] Example 17

[0205] This example is essentially the same as Example 1, except that:

[0206]

[0207] 1,3-dicarbonyl compound structure is formula (III)-13, 1,5-dicarbonyl compound structure is formula (V)-13; reaction time is 1.5 h; the obtained target product is (V)-13, the yield is 88%, and the ee value is 92%.

[0208] H NMR (400 MHz, Chloroform-d) δ 8.03 - 7.91 (m, 2H), 7.17 - 7.03 (m, 2H), 4.91 (dd, J = 8.7, 5.5 Hz, 1H), 2.67 - 2.41 (m, 4H), 2.17 - 2.03 (m, 1H), 1.07 (dd, J = 7.0, 2.0 Hz, 6H); C NMR (101 MHz, Chloroform-d) δ 213.52, 194.47, 165.84 (d, J = 255.9 Hz), 131.94 (d, J = 3.0 Hz), 131.03 (d, J = 9.3 Hz), 116.03 (d, J = 22.0 Hz), 42.55, 40.86, 37.10, 23.91, 18.20 (d, J = 3.6 Hz).

[0209] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 245 nm, retention time: 6.23 min (major), 5.70 min (minor), specific optical rotation [a] D 25 = -7.3 (c = 1.35, CHCl3).

[0210] Infrared spectrum (thin film, cm -1 ) 2972, 2931, 276, 2854, 1694, 1597, 1521, 1499, 409, 1298, 1231, 1158, 1124, 994, 963, 847, 765, 603, 506.

[0211] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 20 H 17 O2F6 + 403.1127, found 403.1124.

[0212] Example 18

[0213] This example is essentially the same as Example 1 except that:

[0214]

[0215] 1,3-dicarbonyl compound structure is formula (III)-14, 1,5-dicarbonyl compound structure is formula (V)-14; reaction time is 0.5 h; the obtained target product is (V)-14, the yield is 87%, and the ee value is 91%.

[0216] NMR (400 MHz, CDC13) δ 7.91 - 7.76 (m, 2H), 7.44 - 7.35 (m, 2H), 4.85 (dd, J = 8.4, 5.6 Hz, 1H), 2.67 - 2.43 (m, 3H), 2.13 (s, 3H), 2.12 - 2.01 (m, 1H); NMR (101 MHz, CDC13) δ 207.31, 194.83, 139.97, 133.88, 129.65, 129.21, 42.51, 40.40, 29.96, 23.80.

[0217] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 253 nm, retention time: 12.08 min (major), 6.86 min (minor), specific optical rotation [a] D 25 = +4.2 (c = 2.37, CHCl3).

[0218] IR (thin film, cm -1 ) 2926, 2872, 2855, 1715, 1693, 1590, 1521, 1499, 1400, 1369, 1262, 122, 1161, 1122, 1092, 1059, 981, 893, 849, 750, 593, 553, 531, 480.

[0219] HRMS (APCI source) m / z: [M+H] + Calcd for C 18 H 13 O2F5Cl + 391.0519, found 391.0514.

[0220] Example 19

[0221] This example is essentially the same as Example 1 except that:

[0222] This example is essentially the same as Example 1 except that:

[0223] 1,3-dicarbonyl compound structure is formula (III)-15, 1,5-dicarbonyl compound structure is formula (V)-15; the reaction time is 0.5 h; the obtained target product is (V)-15, the yield is 90%, and the ee value is 80%.

[0224] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.81-7.69 (m, 2H), 7.61-7.47 (m, 2H), 4.84 (dd, J = 8.4, 5.7 Hz, 1H), 2.67-2.41 (m, 3H), 2.13 (s, 3H), 2.11-1.97 (m, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 207.25, 195.03, 134.33, 132.20, 129.71, 128.68, 42.50, 40.39, 29.94, 23.80.

[0225] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 257 nm, retention time: 15.84 min (major), 7.63 min (minor), specific optical rotation [α] D 25 = +3.9 (c = 3.27, CHCl3).

[0226] Infrared spectrum (thin film, cm -1 ) 2925, 2854, 1715, 1693, 1585, 1521, 1499, 1396, 1370, 1262, 1221, 1162, 1124, 1071, 980, 893, 848, 764, 593, 548, 11, 473.

[0227] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 13 O2F5Br + 435.0014, found 435.0012.

[0228] Example 20

[0229] This example is basically the same as example 1, except that:

[0230]

[0231] 1,3-dicarbonyl compound structure is formula (III)-16, 1,5-dicarbonyl compound structure is formula (V)-16; the reaction time is 1.5h; the obtained target product is (V)-16, the yield is 92%, and the ee value is 85%.

[0232] H NMR (400 MHz, Chloroform-d) δ 7.76 (td, J = 7.5, 1.9 Hz, 1H), 7.46 (dddd, J = 8.3, 7.2, 5.1, 1.9 Hz, 1H), 7.21 (td, J = 7.6, 1.1 Hz, 1H), 7.01 (ddd, J = 11.1, 8.3, 1.1 Hz, 1H), 4.69 (dd, J = 8.5, 5.1 Hz, 1H), 2.53 (dddd, J = 20.5, 15.8, 8.0, 5.1 Hz, 3H), 2.13 (s, 3H), 2.07 - 1.98 (m, 1H); C NMR (101 MHz, Chloroform-d) δ 207.07, 194.91, 160.47 (d, J = 252.8 Hz), 134.72 (d, J = 9.0 Hz), 131.04 (d, J = 2.9 Hz), 124.91 (d, J = 3.3 Hz), 124.77, 116.33 (d, J = 23.5 Hz), 46.98 (d, J = 6.0 Hz), 40.76, 29.89, 23.81.

[0233] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 235 nm, retention time: 9.36 min (major), 7.63 min (minor), specific optical rotation [a] D 25 = +2.8 (c = 2.54, CHCl3).

[0234] Infrared spectrum (thin film, cm -1 ) 2921, 2850, 1715, 1695, 1610, 1521, 1499, 1452, 136, 1276, 1215, 1162, 1125, 1048, 981, 894, 765, 641, 533, 456.

[0235] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 13 O2F6 + 375.0814, found 375.0810.

[0236] Example 21

[0237] This example is essentially the same as Example 1, except that:

[0238]

[0239] 1,3-dicarbonyl compound structure is formula (III)-17, 1,5-dicarbonyl compound structure is formula (V)-17; reaction time is 2 h; the obtained target product is (V)-17, the yield is 90%, and the ee value is 77%.

[0240] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.62 (dt, J = 7.9, 1.3 Hz, 1H), 7.56 (ddd, J = 9.3, 2.7, 1.6 Hz, 1H), 7.40 (td, J = 8.0, 5.5 Hz, 1H), 7.22 (tdd, J = 8.1, 2.7, 1.0 Hz, 1H), 4.85 (dd, J = 8.4, 5.6 Hz, 1H), 2.66-2.46 (m, 3H), 2.13 (s, 3H), 2.11-2.01 (m, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 207.19, 194.76, 162.86 (d, J = 248.7 Hz), 137.67 (d, J = 6.2 Hz), 130.53 (d, J = 7.6 Hz), 123.84 (d, J = 2.9 Hz), 120.51 (d, J = 21.3 Hz), 115.14 (d, J = 22.6 Hz), 42.70, 40.37, 29.88, 23.81.

[0241] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 239 nm, retention time: 11.27 min (major), 7.15 min (minor), specific optical rotation [α] D 25 = -4.6 (c = 2.01, CHCl3).

[0242] Infrared spectrum (thin film, cm -1 ) 3075, 2928, 2857, 1715, 1697, 1588, 1521, 1499, 1441, 1370, 1265, 1154, 1122, 982, 881, 815, 787, 739, 676, 446.

[0243] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H13 O2F6 + 375.0814, found 375.0811.

[0244] Example 22

[0245] This example is substantially the same as Example 1, except that:

[0246]

[0247] 1,3-dicarbonyl compound structure is formula (III)-10, olefin compound structure is formula (IV)-2, 1,5-dicarbonyl compound structure is formula (V)-18; reaction time is 2 h; the obtained target product is (V)-18, the yield is 83%, and the ee value is 79%.

[0248] NMR (400 MHz, Chloroform-d) δ 8.04 - 7.93 (m, 2H), 7.37 - 7.20 (m, 5H), 7.09 - 6.99 (m, 2H), 4.64 - 4.56 (m, 1H), 2.45 - 2.39 (m, 2H), 2.37 (ddd, J = 7.8, 6.0, 1.7 Hz, 1H), 2.17 - 2.10 (m, 1H), 2.09 (s, 3H); NMR (101 MHz, Chloroform-d) δ 208.46, 197.94, 165.56 (d, J = 255.0 Hz), 138.87, 132.96 (d, J = 3.2 Hz), 131.41 (d, J = 9.2 Hz), 129.13, 128.24, 127.37, 115.64 (d, J = 21.9 Hz), 52.20, 40.83, 30.01, 27.58.

[0249] HPLC analysis: Daicel Chiralpak IC-H, isopropanol / n-hexane = 30:70, flow rate = 1.0 mL / min, wavelength = 246 nm, retention time: 10.67 min (major), 13.78 min (minor), specific optical rotation [α] D 25 = -3.2 (c = 1.81, CHCl3).

[0250] IR (thin film, cm -1 ) 3064, 3028, 2928, 2855, 1712, 1679, 1596, 1506, 1453, 1409, 1366, 1268, 1231, 1156, 976, 845, 762, 702, 595, 522.

[0251] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 18 O2F + 285.1285, found285.1282.

[0252] Example 23

[0253] This example is substantially the same as Example 1, except that:

[0254]

[0255] 1,3-dicarbonyl compound structure is formula (III)-10, olefin compound structure is formula (IV)-3, 1,5-dicarbonyl compound structure is formula (V)-19; reaction time is 1 h; the obtained target product is (V)-19, the yield is 77%, and the ee value is 84%.

[0256] H NMR (400 MHz, Chloroform-d) δ 8.01 - 7.93 (m, 2H), 7.16 - 7.08 (m, 4H), 7.03 (t, J = 8.6 Hz, 2H), 4.56 (dd, J = 7.7, 6.4 Hz, 1H), 2.47 - 2.37 (m, 2H), 2.37 - 2.31 (m, 1H), 2.28 (s, 3H), 2.14 - 2.03 (m, 4H); C NMR (101 MHz, Chloroform-d) δ 208.50, 198.06, 165.52 (d, J = 254.8 Hz), 137.05, 135.78, 133.03 (d, J = 2.9 Hz), 131.38 (d, J = 9.3 Hz), 129.82, 128.10, 115.59 (d, J = 21.9 Hz), 51.85, 40.87, 29.97, 27.54, 21.01.

[0257] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 3:97, flow rate = 1.0 mL / min, wavelength = 244 nm, retention time: 25.38 min (major), 21.28 min (minor), specific optical rotation [α] D 25 = -48.8 (c = 1.79, CHCl3).

[0258] Infrared spectrum (thin film, cm -1) 2955, 2924, 2855, 1712, 1679, 1595, 1506, 1408, 1363, 1266, 1230, 1155, 975, 846, 815, 787, 750, 659, 594, 547, 514.

[0259] High resolution mass (APCI source) m / z: [M+H] + Calcd for C 19 H 19 O2F + 299.1442, found 299.1438.

[0260] Example 24

[0261] This example is substantially the same as Example 1, except that:

[0262] 1,3-dicarbonyl compound structure is formula (III)-10, olefin compound structure is formula (IV)-4, 1,5-dicarbonyl compound structure is formula (V)-20; reaction time is 1.5 h; the obtained target product is (V)-20, the yield is 81%, and the ee value is 83%.

[0263]

[0264] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.00-7.93 (m, 2H), 7.25-7.19 (m, 2H), 7.10-7.02 (m, 2H), 7.02-6.95 (m, 2H), 4.62 (dd, J = 8.1, 6.2 Hz, 1H), 2.45-2.37 (m, 2H), 2.37-2.31 (m, 1H), 2.09 (s, 3H), 2.07-1.98 (m, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 208.30 (d, J = 2.6 Hz), 197.91, 165.66 (d, J = 255.3 Hz), 162.04 (d, J = 246.5 Hz), 134.55 (d, J = 3.3 Hz), 132.81 (d, J = 2.7 Hz), 131.37 (d, J = 9.3 Hz), 129.80 (d, J = 8.1 Hz), 116.01 (d, J = 21.6 Hz), 115.73 (d, J = 21.8 Hz), 51.18, 40.68, 30.00, 27.67.

[0265] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 246 nm, retention time: 26.92 min (major), 20.48 min (minor), specific optical rotation [a] D 25 = -18.4 (c = 1.39, CHCl3).

[0266] IR spectrum (thin film, cm -1 ) 2957, 2925, 2853, 1712, 1680, 1595, 1506, 1409, 1363, 1224, 1155, 1100, 1013, 833, 793, 704, 607, 547, 516, 431.

[0267] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 17 O2F2 + 303.1191, found 303.1189.

[0268] Example 25

[0269] This example is basically the same as Example 1, except that:

[0270]

[0271] 1,3-dicarbonyl compound is of formula (III)-10, olefin compound is of formula (IV)-5, 1,5-dicarbonyl compound is of formula (V)-21; reaction time is 1 h; the obtained target product is (V)-21, the yield is 90%, and ee value is 92%.

[0272] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.00-7.93 (m, 2H), 7.30-7.26 (m, 2H), 7.22-7.17 (m, 2H), 7.10-7.03 (m, 2H), 4.62 (t, J = 7.1 Hz, 1H), 2.47-2.39 (m, 2H), 2.39-2.31 (m, 1H), 2.09 (s, 3H), 2.08-2.01 (m, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 208.21, 197.65, 165.68 (d, J = 255.4 Hz), 137.31, 133.32, 132.74 (d, J = 2.1 Hz), 131.35 (d, J = 9.3 Hz), 129.58, 129.27, 115.75 (d, J = 21.9 Hz), 51.30, 40.60, 30.00, 27.52.

[0273] High performance liquid chromatography analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 3:97, flow rate = 1.0 mL / min, wavelength = 245 nm, retention time: 28.58 min (major), 24.16 min (minor), specific optical rotation [α] D 25 = -9.7 (c = 2.35, CHCl3).

[0274] Infrared spectrum (thin film, cm -1 ) 2956, 2925, 2853, 1712, 1679, 1595, 1506, 1491, 1409, 1363, 1231, 1156, 1092, 1014, 819, 784, 750, 692, 607, 531, 504.

[0275] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 18 H 16 O2FCl + 319.0896, found 319.0894.

[0276] Example 26

[0277] This example is essentially the same as Example 1, except that:

[0278]

[0279] 1,3-dicarbonyl compound structure is formula (III)-10, olefin compound structure is formula (IV)-6, 1,5-dicarbonyl compound structure formula is (V)-22; the reaction time is 1h; the obtained target product is (V)-22, the yield is 80%, and the ee value is 88%.

[0280] H NMR (400 MHz, Chloroform-d) δ 8.11 - 7.93 (m, 2H), 7.58 (d, J = 8.1 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.14 - 7.05 (m, 2H), 4.75 (t, J = 7.1 Hz, 1H), 2.49 - 2.37 (m, 3H), 2.17 - 2.05 (m, 4H); C NMR (101 MHz, Chloroform-d) δ 208.09, 197.37, 165.80 (d, J = 255.8 Hz), 142.90, 132.67 (d, J = 2.5 Hz), 131.39 (d, J = 9.4 Hz), 129.71 (q, J = 32.5 Hz), 128.65, 126.02 (q, J = 3.8 Hz), 115.86 (d, J = 22.0 Hz), 51.67, 40.55, 30.01, 27.62.

[0281] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 3:97, flow rate = 1.0 mL / min, wavelength = 248 nm, retention time: 18.01 min (major), 15.31 min (minor), specific optical rotation [α] D 25 = -3.9 (c = 1.68, CHCl3).

[0282] Infrared spectrum (thin film, cm -1 ) 2957, 2926, 2854, 1714, 1681, 1596, 1507, 1410, 1323, 1157, 1111, 1068, 1018, 836, 751, 685, 607, 525.

[0283] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 19 H 17 O2F4 + 353.1159, found 353.1155.

[0284] Example 27

[0285] This example is basically the same as Example 1, except that:

[0286]

[0287] 1,3-dicarbonyl compound structure is formula (III)-10, olefin compound structure is formula (IV)-7, 1,5-dicarbonyl compound structure is formula (V)-23; the reaction time is 1.5h; the obtained target product is (V)-23, the yield is 80%, and the ee value is 81%.

[0288] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.06-7.90 (m, 2H), 7.19 (td, J=9.1, 8.7, 6.3 Hz, 1H), 7.12-7.00 (m, 2H), 6.88-6.75 (m, 2H), 4.97-4.84 (m, 1H), 2.51-2.30 (m, 3H), 2.10 (s, 3H), 2.07-1.94 (m, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 207.71, 197.18, 165.83 (d, J=255.5 Hz), 163.75-161.16 (m), 161.07-158.33 (m), 132.40, 131.17 (d, J=9.4 Hz), 129.91 (dd, J=9.6, 5.2 Hz), 121.76 (d, J=11.8 Hz), 115.84 (d, J=22.0 Hz), 112.22 (dd, J=21.3, 3.7 Hz), 104.10 (t, J=26.2 Hz), 43.01, 40.57, 29.91, 26.62.

[0289] High performance liquid chromatography analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 248 nm, retention time: 21.77 min (major), 25.62 min (minor), specific optical rotation [α] D 25 = -2.3 (c = 1.68, CHCl3).

[0290] Infrared spectrum (thin film, cm -1 ) 3077, 2927, 1855, 1714, 1683, 1595, 1502, 1410, 1367, 1275, 1231, 1156, 1139, 1095, 965, 846, 816, 750, 611, 561, 505, 468, 427.

[0291] High resolution mass spectrum (APCI source) m / z: [M+H] +Calcd for C 18 H 16 O2F3 + 321.1097, found321.1093.

[0292] Example 28

[0293] This example is essentially the same as Example 1, except that:

[0294]

[0295] 1,3-dicarbonyl compound structure is formula (III)-18, 1,5-dicarbonyl compound structure is formula (V)-24; reaction time is 1 h; the target product obtained is (V)-24, the yield is 90%, and the ee value is 81%.

[0296] NMR (400 MHz, CDC13) δ 7.92 (t, J = 8.7 Hz, 4H), 7.61 - 7.50 (m, 2H), 7.44 (q, J = 8.2 Hz, 4H), 5.04 (t, J = 7.3 Hz, 1H), 3.09 (t, J = 6.8 Hz, 2H), 2.78 (dq, J = 14.0, 7.0 Hz, 1H), 2.30 (dq, J = 14.0, 6.9 Hz, 1H); NMR (101 MHz, CDC13) δ 198.86, 196.05, 136.53, 135.61, 133.42, 133.29, 128.82, 128.64, 128.24, 127.91, 42.63, 35.65, 24.40.

[0297] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 10:90, flow rate = 1.0 mL / min, wavelength = 242 nm, retention time: 10.13 min (major), 12.30 min (minor), specific optical rotation [a] D 25 = -19.1 (c = 2.96, CHCl3).

[0298] IR (thin film, cm -1 ) 3359, 3062, 2936, 2641, 2422, 1967, 1688, 1655, 1597, 1581, 1522, 1501, 1149, 1273, 1221, 1182, 1124, 1001, 970, 948, 864, 847, 723, 700, 661.

[0299] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 23 H 16 O2F5 + 419.1065, found419.1061.

[0300] Example 29

[0301] This example is essentially the same as Example 1, except that:

[0302]

[0303] 1,3-dicarbonyl compound structure is formula (III)-18, olefin compound structure is formula (IV)-2, 1,5-dicarbonyl compound structure is formula (V)-25; reaction time is 1 h; the obtained target product is (V)-25, the yield is 95%, and the ee value is 70%.

[0304] H NMR (400 MHz, Chloroform-d) δ 8.01 - 7.97 (m, 2H), 7.94 - 7.88 (m, 2H), 7.53 (d, J = 7.4 Hz, 1H), 7.50 - 7.36 (m, 5H), 7.35 - 7.25 (m, 4H), 7.24 - 7.19 (m, 1H), 4.79 (t, J = 7.3 Hz, 1H), 2.98 (qt, J = 17.2, 6.9 Hz, 2H), 2.60 (dq, J = 14.3, 7.2 Hz, 1H), 2.39 - 2.21 (m, 1H); C NMR (101 MHz, Chloroform-d) δ 199.85, 199.57, 139.11, 136.77, 136.59, 132.99, 132.88, 129.00, 128.73, 128.51, 128.47, 128.28, 127.98, 127.18, 52.40, 35.93, 28.26.

[0305] HPLC analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 241 nm, retention time: 19.93 min (major), 24.04 min (minor), specific optical rotation [α] D 25 = -80.5 (c = 2.84, CHCl3).

[0306] Infrared spectrum (thin film, cm -1) 3060, 3026, 2933, 1681, 1597, 1580, 1492, 447, 1409, 1367, 1275, 1222, 1178, 1001, 980, 751, 734, 698, 568, 518.

[0307] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 23 H 21 O2 + 329.1536, found 329.1532.

[0308] Example 30

[0309] This example is essentially the same as Example 1, except that:

[0310]

[0311] 1,3-dicarbonyl compound structure is formula (III)-18, olefin compound structure is formula (IV)-3, 1,5-dicarbonyl compound structure is formula (V)-26; reaction time is 1 h; the obtained target product is (V)-26, the yield is 93%, and the ee value is 66%.

[0312] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.99 (d, J = 7.5 Hz, 2H), 7.95-7.87 (m, 2H), 7.54 (t, J = 7.4 Hz, 1H), 7.42 (dp, J = 21.0, 7.5 Hz, 5H), 7.20 (d, J = 7.8 Hz, 2H), 7.10 (d, J = 7.8 Hz, 2H), 4.75 (t, J = 7.3 Hz, 1H), 3.11-2.85 (m, 2H), 2.58 (dd, J = 14.0, 7.1 Hz, 1H), 2.28 (m, 4H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 199.92, 199.69, 136.82, 136.79, 136.62, 136.02, 132.97, 132.82, 129.71, 128.73, 128.50, 128.45, 128.15, 127.99, 52.02, 35.96, 28.22, 20.98.

[0313] High performance liquid chromatography analysis: Daicel Chiralpak AD-H, isopropanol / n-hexane = 20:80, flow rate = 1.0 mL / min, wavelength = 241 nm, retention time: 10.17 min (major), 11.41 min (minor), specific optical rotation [α] D25 = -75.2 (c = 2.81, CHCl3).

[0314] Infrared spectrum (thin film, cm -1 ) 3344, 3058, 3025, 2924, 2858, 1683, 1597, 1580, 1512, 1448, 1411, 1366, 1275, 1223, 1179, 1112, 1022, 1001, 979, 806, 750, 729, 670, 557.

[0315] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 24 H 23 O2 + 343.1693, found 343.1691.

[0316] Example 31

[0317] This example is basically the same as Example 1, except that:

[0318] The 1,3-dicarbonyl compound has the structure of formula (III)-18, the olefin compound has the structure of formula (IV)-4, and the 1,5-dicarbonyl compound has the structure of formula (V)-27; the reaction time is 1 h; the target product obtained is (V)-27, which has a yield of 84% and an ee value of 75%.

[0319]

[0320] H NMR (400 MHz, Chloroform-d) δ 8.03 - 7.94 (m, 2H), 7.95 - 7.84 (m, 2H), 7.59 - 7.50 (m, 1H), 7.50 - 7.46 (m, 1H), 7.45 - 7.36 (m, 4H), 7.28 (ddd, J = 9.7, 5.9, 3.2 Hz, 2H), 6.98 (t, J = 8.6 Hz, 2H), 4.80 (t, J = 7.4 Hz, 1H), 3.16 - 2.81 (m, 2H), 2.59 (dd, J = 14.1, 7.1 Hz, 1H), 2.27 (dt, J = 14.0, 6.9 Hz, 1H); C NMR (101 MHz, Chloroform-d) δ 199.70, 199.52, 161.90 (d, J = 246.1 Hz), 136.69, 136.40, 134.79 (d, J = 3.2 Hz), 133.05 (d, J = 3.4 Hz), 129.83 (d, J = 8.0 Hz), 128.67, 128.54, 127.93, 115.97, 115.76, 51.36, 35.75, 28.27.

[0321] HPLC analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 10:90, flow rate = 1.0 mL / min, wavelength = 241 nm, retention time: 25.77 min (major), 18.48 min (minor), specific optical rotation [a] D 25 = -102.4 (c = 1.87, CHCl3).

[0322] IR spectrum (thin film, cm -1 ) 3347, 3064, 2932, 2857, 1967, 1898, 1683, 1597, 1580, 1507, 1448, 1417, 1367, 1277, 1224, 1179, 1158, 1098, 1074, 1001, 979, 960, 832, 752, 731, 690, 556, 516.

[0323] HRMS (APCI source) calcd for C 23 H 19 O2F: 346.1369, found 346.1372.

[0324] Example 32

[0325] This example is essentially the same as Example 1, except that:

[0326]

[0327] 1,3-dicarbonyl compound structure is formula (III)-18, olefin compound structure is formula (IV)-8, 1,5-dicarbonyl compound structure formula is (V)-28; the reaction time is 1h; the obtained target product is (V)-28, the yield is 88%, and the ee value is 76%.

[0328] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.97 (d, J = 7.7 Hz, 2H), 7.90 (d, J = 7.8 Hz, 2H), 7.58-7.46 (m, 2H), 7.40 (dt, J = 12.7, 7.8 Hz, 6H), 7.20 (d, J = 8.2 Hz, 2H), 4.79 (t, J = 7.4 Hz, 1H), 2.97 (dt, J = 10.2, 6.9 Hz, 2H), 2.59 (dd, J = 14.1, 7.1 Hz, 1H), 2.34-2.19 (m, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.54, 199.13, 138.07, 136.60, 136.25, 133.08, 133.05, 132.05, 129.97, 128.63, 128.53, 128.50, 127.89, 121.18, 51.52, 35.66, 28.03.

[0329] High performance liquid chromatography analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 240 nm, retention time: 28.08 min (major), 23.84 min (minor), specific optical rotation [α] D 25 = -65.6 (c = 2.72, CHCl3).

[0330] Infrared spectrum (thin film, cm -1 ) 3346, 3060, 2959, 2932, 1967, 1773, 1683, 1596, 1580, 1487, 1448, 1405, 1367, 1275, 1222, 1199, 1178, 1074, 1011, 1001, 978, 810, 754, 703, 689, 530.

[0331] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 23 H 20 O2Br + 407.0641, found 407.0637.

[0332] Example 33

[0333] This example is substantially the same as Example 1, except that:

[0334]

[0335] 1,3-dicarbonyl compound structure is formula (III)-18, olefin compound structure is formula (IV)-6, 1,5-dicarbonyl compound structure is formula (V)-29; reaction time is 1 h; the obtained target product is (V)-29, the yield is 85%, and the ee value is 50%.

[0336] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.06-7.96 (m, 2H), 7.94-7.88 (m, 2H), 7.61-7.51 (m, 4H), 7.43 (ddd, J = 17.7, 8.9, 6.6 Hz, 6H), 4.91 (t, J = 7.3 Hz, 1H), 2.99 (q, J = 6.9 Hz, 2H), 2.63 (dq, J = 14.2, 7.1 Hz, 1H), 2.29 (dq, J = 13.8, 6.8 Hz, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 199.53, 199.01, 143.19, 136.65, 136.28, 133.30, 133.18, 129.67, 129.34, 128.71, 128.59, 127.95, 125.94 (q, J = 3.8 Hz), 123.98 (d, J = 272.0 Hz), 51.92, 35.69, 28.21.

[0337] High performance liquid chromatography analysis: Daicel Chiralpak OJ-H, isopropanol / n-hexane = 5:95, flow rate = 1.0 mL / min, wavelength = 242 nm, retention time: 15.49 min (major), 12.90 min (minor), specific optical rotation [α] D 25 = -49.3 (c = 1.49, CHCl3).

[0338] Infrared spectrum (thin film, cm -1 ) 3349, 3062, 2934, 1922, 1811, 1683, 1617, 1597, 1581, 1449, 1419, 1367, 1325, 1277, 11223, 1166, 1124, 1069, 1017, 1001, 977, 831, 752, 728, 699, 666, 610, 569, 528.

[0339] High resolution mass spectrum (APCI source) m / z: [M+H] + Calcd for C 24 H 20 O2F3 + 397.1410found 397.1407.

[0340] Example 34

[0341]

[0342] In a dry 10 mL schlenk tube, (VI)-1 (0.1 mmol, 1.0 equiv) and indenyl ZrCl2 (CAS: 100080-82-8) (0.002 mmol, 2 mol%) were added, then (VII)-1 (0.2 mmol, 2.0 equiv) was dissolved in dry DCM (1.0 mL) and added into the schlenk tube with a syringe, the resulting mixture was degassed by freeze-purge-thaw degassing process for three times, so that the gas in the system was completely replaced by nitrogen, the reaction tube was placed at a distance of about 1 cm from the 10W 440 nm LED light source, and the reaction system was irradiated for 2.5 h (i.e. the reaction time was 2.5 h) while stirring. The solution was directly purified by silica gel column chromatography to obtain the main product (VIII)-1 as the target product with a yield of 99%.

[0343] H NMR (400 MHz, Chloroform-d) δ 8.01 - 7.97 (m, 2H), 7.94 - 7.88 (m, 2H), 7.53 (d, J = 7.4 Hz, 1H), 7.50 - 7.36 (m, 5H), 7.35 - 7.25 (m, 4H), 7.24 - 7.19 (m, 1H), 4.79 (t, J = 7.3 Hz, 1H), 2.98 (qt, J = 17.2, 6.9 Hz, 2H), 2.60 (dq, J = 14.3, 7.2 Hz, 1H), 2.39 - 2.21 (m, 1H); C NMR (101 MHz, Chloroform-d) δ 199.85, 199.57, 139.11, 136.77, 136.59, 132.99, 132.88, 129.00, 128.73, 128.51, 128.47, 128.28, 127.98, 127.18, 52.40, 35.93, 28.26.

[0344] Infrared spectrum (thin film, cm -1) 3060, 3026, 2933, 1681, 1597, 1580, 1492, 447, 1409, 1367, 1275, 1222, 1178, 1001, 980, 751, 734, 698, 568, 518.

[0345] High resolution mass spectrum (APCI source) calcd for C 23 H 21 O2: 329.1539, found 325.1539.

[0346] Example 35

[0347] This example is essentially the same as Example 34, except that:

[0348] The olefin compound structure is formula (VII)-2,1,5-dicarbonyl compound structure formula is (VIII)-2; the target product obtained is (VIII)-2, and the yield is 89%.

[0349]

[0350] NMR (400 MHz, Chloroform-d) δ 7.93 (dd, J = 8.3, 1.4 Hz, 2H), 7.85 (dd, J = 8.4, 1.3 Hz, 2H), 7.57 - 7.51 (m, 1H), 7.43 (dd, J = 8.6, 7.1 Hz, 3H), 7.35 (dd, J = 8.4, 7.0 Hz, 2H), 7.20 (d, J = 6.9 Hz, 1H), 7.15 - 7.06 (m, 3H), 4.93 (dd, J = 8.8, 5.3 Hz, 1H), 3.12 (dt, J = 17.3, 6.7 Hz, 1H), 3.01 (dt, J = 17.3, 7.0 Hz, 1H), 2.55 (m, 4H), 2.18 (dtd, J = 14.1, 7.1, 5.3 Hz, 1H); NMR (101 MHz, Chloroform-d) δ 200.33, 200.07, 137.96, 136.95, 136.82, 135.38, 133.02, 132.80, 131.12, 128.55, 128.50, 128.43, 128.03, 127.28, 127.10, 126.63, 48.69, 36.26, 27.63, 19.76.

[0351] Infrared spectrum (thin film, cm -1) 3345, 3062, 3025, 2962, 2930, 1722, 1683, 1597, 1580, 1490, 1448, 1409, 1365, 1261, 1222, 1180, 1100, 1027, 799, 750, 731, 690, 600, 553, 454.

[0352] High resolution mass spectrum (APCI source) calcd for C 24 H 23 O2: 343.1693, found 343.1694.

[0353] Example 36

[0354] This example is essentially the same as Example 34, except that:

[0355]

[0356] The olefin compound structure is formula (VII)-3, 1,5-dicarbonyl compound structure formula is (VIII)-3; the target product obtained is (VIII)-3, and the yield is 98%.

[0357] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.02-7.95 (m, 2H), 7.94-7.86 (m, 2H), 7.58-7.35 (m, 6H), 7.17 (d, J = 7.8 Hz, 1H), 7.10 (d, J = 5.9 Hz, 2H), 7.02 (d, J = 7.5 Hz, 1H), 4.73 (t, J = 7.3 Hz, 1H), 3.02 (dt, J = 17.1, 7.2 Hz, 1H), 2.92 (dt, J = 17.1, 6.7 Hz, 1H), 2.58 (dd, J = 14.1, 7.1 Hz, 1H), 2.29 (m, 4H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 200.00, 199.69, 139.08, 138.75, 136.91, 136.75, 133.03, 132.90, 128.90, 128.85, 128.81, 128.57, 128.52, 128.06, 128.05, 125.52, 52.45, 36.06, 28.39, 21.42.

[0358] Infrared spectrum (thin film, cm -1 ) 3059, 3026, 2930, 2861, 1681, 1597, 1580, 1489, 1448, 1366, 1261, 1213, 1180, 1094, 1074, 1057, 1002, 982, 796, 748, 126, 692.

[0359] High resolution mass spectrum (APCI source) calcd for C 24 H 23 O2:343.1693, found 343.1695.

[0360] Example 37

[0361] This example is essentially the same as Example 34, except that:

[0362]

[0363] The olefin compound structure is formula (VII)-4,1,5-dicarbonyl compound structure formula is (VIII)-4; the target product obtained is (VIII)-4, and the yield is 87%.

[0364] H NMR (400 MHz, Chloroform-d) δ 8.02 - 7.96 (m, 2H), 7.94 - 7.86 (m, 2H), 7.56 - 7.50 (m, 1H), 7.42 (dt, J = 18.7, 7.7 Hz, 5H), 7.22 (d, J = 8.4 Hz, 2H), 6.96 - 6.74 (m, 2H), 4.73 (t, J = 7.4 Hz, 1H), 3.74 (s, 3H), 3.16 - 2.85 (m, 2H), 2.56 (dd, J = 14.0, 7.1 Hz, 1H), 2.27 (dt, J = 14.0, 7.0 Hz, 1H); C NMR (101 MHz, Chloroform-d) δ 199.94, 199.79, 158.67, 136.78, 136.61, 132.98, 132.81, 131.00, 129.33, 128.70, 128.50, 128.45, 127.98, 114.40, 55.13, 51.48, 35.90, 28.22.

[0365] IR spectrum (thin film, cm -1 ) 3343, 3060, 3002, 2955, 2933, 2836, 1682, 1608, 1597, 1581, 1511, 1449, 1367, 1303, 1178, 1111, 1075, 1034, 11001, 981, 828, 750, 733, 690, 563, 532.

[0366] High resolution mass spectrum (APCI source) calcd for C 24 H 23 O3:359.1642, found 359.1643.

[0367] Example 38

[0368] This example is essentially the same as Example 34, except that:

[0369]

[0370] The olefin compound structure is formula (VII)-5, and the 1,5-dicarbonyl compound structure is formula (VIII)-5; the target product obtained is (VIII)-5, with a yield of 95%.

[0371] NMR hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.03-7.94 (m, 2H), 7.95-7.84 (m, 2H), 7.59-7.50 (m, 1H), 7.50-7.46 (m, 1H), 7.45-7.36 (m, 4H), 7.28 (ddd, J = 9.7, 5.9, 3.2 Hz, 2H), 6.98 (t, J = 8.6 Hz, 2H), 4.80 (t, J = 7.4 Hz, 1H), 3.16-2.81 (m, 2H), 2.59 (dd, J = 14.1, 7.1 Hz, 1H), 2.27 (dt, J = 14.0, 6.9 Hz, 1H); NMR carbon spectrum (101 megahertz, deuterated chloroform) δ 198.27, 197.98, 166.93 (d, J = 17.3 Hz), 164.40 (d, J = 17.6 Hz), 138.97, 133.23 (d, J = 3.0 Hz), 132.96 (d, J = 2.9 Hz), 131.46 (d, J = 9.3 Hz), 130.68 (d, J = 9.3 Hz), 129.19, 128.26, 127.41, 115.78 (d, J = 2.3 Hz), 115.56 (d, J = 2.2 Hz), 52.44, 35.82, 28.26; NMR fluorine spectrum (377 megahertz, deuterated chloroform) δ -115.15.

[0372] Infrared spectrum (thin film, cm -1 ) 3347, 3064, 2932, 2857, 1967, 1898, 1683, 1597, 1580, 1507, 1448, 1417, 1367, 1277, 1224, 1179, 1158, 1098, 1074, 1001, 979, 960, 832, 752, 731, 690, 556, 516.

[0373] High resolution mass spectrum (APCI source) calcd for C 23 H 20 O2F: 347.1442, found 347.1443.

[0374] Example 39

[0375] This example is essentially the same as Example 34 except that:

[0376]

[0377] The olefinic compound structure is Formula (VII)-6 and the 1,5-diketone compound structure is Formula (VIII)-6; the target product obtained is (VIII)-6 in 99% yield.

[0378] H NMR (400 MHz, Chloroform-d) δ 8.02 - 7.95 (m, 2H), 7.94 - 7.87 (m, 2H), 7.51 (dd, J = 15.3, 7.4 Hz, 2H), 7.41 (dt, J = 10.5, 7.6 Hz, 4H), 7.35 (d, J = 2.3 Hz, 1H), 7.21 (d, J = 3.8 Hz, 3H), 4.80 (t, J = 7.3 Hz, 1H), 2.98 (qt, J = 17.4, 6.8 Hz, 2H), 2.59 (dq, J = 14.3, 7.1 Hz, 1H), 2.27 (dq, J = 13.9, 6.9 Hz, 1H); C NMR (101 MHz, Chloroform-d) δ 199.56, 198.98, 141.08, 136.63, 136.27, 134.73, 133.15, 133.08, 130.19, 128.68, 128.58, 128.53, 128.28, 127.92, 127.46, 126.53, 51.75, 35.72, 28.19.

[0379] Infrared spectrum (thin film, cm -1 ) 3345, 3060, 2959, 2932, 2872, 1967, 1812, 1723, 1683, 1596, 1580, 1473, 1448, 1431, 1367, 1276, 1222, 1180, 1124, 1080, 1001, 980, 884, 842, 783, 755, 718, 689, 595, 569, 548, 491.

[0380] High resolution mass spectrum (APCI source) calcd for C 23 H 20 O2Cl: 363.1146, found 363.1148.

[0381] Example 40

[0382] This example is essentially the same as Example 34 except that:

[0383] The olefin compound has the structure of formula (VII)-7 and the 1,5-diketone compound has the structure of formula (VIII)-7; the target product obtained is (VIII)-7 with a yield of 99%.

[0384]

[0385] H NMR (400 MHz, chloroform-d) δ 7.97 (d, J = 7.7 Hz, 2H), 7.90 (d, J = 7.8 Hz, 2H), 7.58 - 7.46 (m, 2H), 7.40 (dt, J = 12.7, 7.8 Hz, 6H), 7.20 (d, J = 8.2 Hz, 2H), 4.79 (t, J = 7.4 Hz, 1H), 2.97 (dt, J = 10.2, 6.9 Hz, 2H), 2.59 (dd, J = 14.1, 7.1 Hz, 1H), 2.34 - 2.19 (m, 1H); C NMR (101 MHz, chloroform-d) δ 199.54, 199.13, 138.07, 136.60, 136.25, 133.08, 133.05, 132.05, 129.97, 128.63, 128.53, 128.50, 127.89, 121.18, 51.52, 35.66, 28.03.

[0386] Infrared spectrum (thin film, cm -1 ) 3346, 3060, 2959, 2932, 1967, 1773, 1683, 1596, 1580, 1487, 1448, 1405, 1367, 1275, 1222, 1199, 1178, 1074, 1011, 1001, 978, 810, 754, 703, 689, 530.

[0387] High resolution mass spectrum (APCI source) calcd for C 23 H 20 O2Br: 407.0641, found 407.0643.

[0388] Example 41

[0389] This example is essentially the same as Example 34, except that:

[0390]

[0391] The olefin compound has the structure of formula (VII)-8 and the 1,5-diketone compound has the structure of formula (VIII)-8; the target product obtained is (VIII)-8 with a yield of 97%.

[0392] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.92 (t, J = 8.7 Hz, 4H), 7.61-7.50 (m, 2H), 7.44 (q, J = 8.2 Hz, 4H), 5.04 (t, J = 7.3 Hz, IH), 3.09 (t, J = 6.8 Hz, 2H), 2.78 (dq, J = 14.0, 7.0 Hz, IH), 2.30 (dq, J = 14.0, 6.9 Hz, IH); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.86, 196.05, 136.53, 135.61, 133.42, 133.29, 128.82, 128.64, 128.24, 127.91, 42.63, 35.65, 24.40; nuclear magnetic resonance fluorine spectrum (377 megahertz, deuterated chloroform) δ -140.83 - -140.98 (m), -154.31 (t, J = 20.9 Hz), -160.87 (td, J = 22.1, 7.9 Hz).

[0393] -140.98 (m), -154.31 (t, J = 20.9 Hz), -160.87 (td, J = 22.1, 7.9 Hz).

[0394] Infrared spectrum (thin film, cm -1 ) 3359, 3062, 2936, 2641, 2422, 1967, 1688, 1655, 1597, 1581, 1522, 1501, 1149, 1273, 1221, 1182, 1124, 1001, 970, 948, 864, 847, 723, 700, 661.

[0395] High resolution mass spectrum (APCI source) calcd for C 23 H 16 O2F5: 419.1065, found 419.1064.

[0396] Example 42

[0397] This example is essentially the same as Example 34, except that:

[0398]

[0399] The olefin compound structure is formula (VII)-9, and the 1,5-diketone compound structure is formula (VIII)-9; the target product obtained is (VIII)-9, with a yield of 99%.

[0400] H NMR (400 MHz, chloroform-d) δ 8.06 - 7.96 (m, 2H), 7.94 - 7.88 (m, 2H), 7.61 - 7.51 (m, 4H), 7.43 (ddd, J = 17.7, 8.9, 6.6 Hz, 6H), 4.91 (t, J = 7.3 Hz, 1H), 2.99 (q, J = 6.9 Hz, 2H), 2.63 (dq, J = 14.2, 7.1 Hz, 1H), 2.29 (dq, J = 13.8, 6.8 Hz, 1H); C NMR (101 MHz, chloroform-d) δ 199.53, 199.01, 143.19, 136.65, 136.28, 133.30, 133.18, 129.67, 129.34, 128.71, 128.59, 127.95, 125.94 (q, J = 3.8 Hz), 123.98 (d, J = 272.0 Hz), 51.92, 35.69, 28.21.

[0401] Infrared spectrum (thin film, cm -1 ) 3349, 3062, 2934, 1922, 1811, 1683, 1617, 1597, 1581, 1449, 1419, 1367, 1325, 1277, 11223, 1166, 1124, 1069, 1017, 1001, 977, 831, 752, 728, 699, 666, 610, 569, 528.

[0402] High resolution mass spectrum (APCI source) calcd for C 24 H 20 O2F3: 397.1410, found 397.1411.

[0403] Example 43

[0404] This example is essentially the same as Example 34, except that:

[0405]

[0406] The olefin compound structure is formula (VII)-10, and the 1,5-dicarbonyl compound structure is formula (VIII)-10; the target product obtained is (VIII)-10, with a yield of 99%.

[0407] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.98 (d, J = 7.6 Hz, 2H), 7.90 (d, J = 7.5 Hz, 2H), 7.58-7.45 (m, 2H), 7.41 (dt, J = 14.8, 7.5 Hz, 4H), 7.33 (d, J = 8.2 Hz, 2H), 7.03 (d, J = 8.3 Hz, 2H), 4.82 (t, J = 7.4 Hz, 1H), 3.08-2.87 (m, 2H), 2.58 (dd, J = 14.1, 7.1 Hz, 1H), 2.34-2.19 (m, 4H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.85, 199.57, 169.32, 149.82, 136.77, 136.59, 136.52, 133.14, 129.34, 128.80, 128.64, 128.62, 128.05, 122.11, 51.57, 35.89, 28.40, 21.15.

[0408] Infrared spectrum (thin film, cm -1 ) 3341, 3085, 3060, 3036, 2928, 2872, 2360, 2341, 1756, 1677, 1596, 1580, 1504, 1447, 1367, 1275, 1195, 1166, 1001, 977, 959, 911, 836, 751, 688, 553.

[0409] High resolution mass spectrum (APCI source) calcd for C 25 H 22 O4: 386.1518, found 386.1514.

[0410] Example 44

[0411] This example is substantially the same as Example 34, except that:

[0412]

[0413] The olefin compound structure is formula (VII)-11, and the 1,5-diketone compound structure is formula (VIII)-11; the reaction time is 5 h, and the target product obtained is (VIII)-11, with a yield of 99%.

[0414] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.07-8.00 (m, 2H), 7.95-7.88 (m, 2H), 7.85-7.72 (m, 4H), 7.58-7.32 (m, 9H), 4.98 (t, J = 7.3 Hz, 1H), 3.02 (qt, J = 17.3, 6.9 Hz, 2H), 2.71 (dt, J = 14.1, 7.1 Hz, 1H), 2.43 (dt, J = 14.0, 6.9 Hz, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.95, 199.63, 136.89, 136.73, 136.71, 133.68, 133.07, 132.99, 132.60, 128.95, 128.84, 128.58, 128.06, 127.81, 127.67, 127.32, 126.28, 125.97, 52.59, 36.00, 28.35.

[0415] Infrared spectrum (thin film, cm -1 ) 3342, 3056, 2931, 2872, 2360, 2341, 1677, 1596, 1579, 1507, 1447, 1364, 1275, 1262, 1195, 1180, 978, 861, 815, 749, 722, 687, 478.

[0416] High resolution mass spectrum (APCI source) calcd for C 27 H 22 O2: 378.1620, found 378.1613.

[0417] Example 45

[0418] This example is basically the same as Example 34, except that:

[0419]

[0420] The olefin compound structure is formula (VII)-12, and the 1,5-dicarbonyl compound structure is formula (VIII)-12; the reaction time is 5 h, and the obtained target product is (VIII)-12, with a yield of 88%.

[0421] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.85-7.79 (m, 2H), 7.55-7.48 (m, 3H), 7.42-7.35 (m, 7H), 7.30 (s, 1H), 7.27-7.20 (m, 2H), 2.84 (ddd, J = 14.5, 9.8, 6.0 Hz, 2H), 2.49 (dt, J = 10.1, 5.8 Hz, 2H), 1.67 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 203.06, 199.90, 143.67, 136.64, 136.28, 132.92, 131.88, 129.59, 129.06, 128.48, 128.06, 128.04, 127.11, 126.22, 54.15, 34.74, 34.08, 24.33.

[0422] Infrared spectrum (thin film, cm -1 ) 3337, 3059, 1025, 2974, 1934, 1967, 1679, 1597, 1580, 1496, 1447, 1366, 1317, 1281, 1244, 1180, 1077, 1029, 1002, 166, 846, 761, 742, 715, 702, 690, 572.

[0423] High resolution mass spectrum (ESI source) calcd for C 24 H 22 O2Na + : 365.1512, found 365.1515.

[0424] Example 46

[0425] This example is basically the same as Example 34, except that:

[0426]

[0427] The olefin compound structure is formula (VII)-13, and the 1,5-dicarbonyl compound structure is formula (VIII)-13; the reaction time is 20 h, and the target product obtained is (VIII)-13, with a yield of 99%.

[0428] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.87-7.77 (m, 2H), 7.57-7.46 (m, 3H), 7.46-7.33 (m, 3H), 7.32-7.16 (m, 6H), 2.98-2.67 (m, 2H), 2.56-2.39 (m, 5H), 1.64 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 203.00, 199.86, 140.43, 137.45, 136.72, 136.32, 132.99, 131.98, 129.62, 128.54, 128.17, 128.09, 126.98, 126.78, 53.82, 34.75, 34.11, 24.37, 15.61.

[0429] Infrared spectrum (thin film, cm -1 ) 3338, 3058, 2979, 2921, 2360, 2341, 1902, 1673, 1596, 1578, 1559, 1492, 1446, 1365, 1276, 1240, 1179, 1100, 965, 822, 748, 689, 659, 571.

[0430] High resolution mass spectrum (APCI source) calcd for C 25 H 24 O2S: 388.1497, found 388.1491.

[0431] Example 47

[0432] This example is basically the same as Example 34, except that:

[0433]

[0434] The olefin compound structure is formula (VII)-14, and the 1,5-dicarbonyl compound structure is formula (VIII)-14; the reaction time is 20 h, and the target product obtained is (VIII)-14, with a yield of 85%.

[0435] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.94-7.77 (m, 2H), 7.61-7.47 (m, 3H), 7.47-7.36 (m, 5H), 7.34-7.19 (m, 4H), 6.63 (s, 1H), 2.84 (ddd, J = 13.4, 8.9, 6.9 Hz, 2H), 2.47 (ddd, J = 9.3, 6.6, 2.0 Hz, 2H), 1.65 (s, 3H), 1.54 (s, 9H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 203.26, 200.02, 152.73, 137.97, 137.50, 136.71, 136.42, 132.97, 131.90, 129.62, 128.53, 128.13, 128.10, 126.92, 118.92, 80.69, 53.69, 34.78, 34.14, 28.35, 24.30.

[0436] Infrared spectrum (thin film, cm -1 ) 3340, 2977, 2931, 2361, 2341, 2294, 1723, 1672, 1594, 121, 1448, 1407, 1366, 1261, 12333, 1155, 1052, 977, 906, 838, 765, 749, 737, 689, 574.

[0437] High resolution mass spectrum (APCI source) calcd for C 29 H 31 NO4: 457.2253, found 457.2242.

[0438] Example 48

[0439] This example is substantially the same as Example 34, except that:

[0440]

[0441] The olefin compound structure is formula (VII)-15, and the 1,5-dicarbonyl compound structure is formula (VIII)-15; the reaction time is 2.5 h, and the obtained target product is (VIII)-15, and the yield is 88%.

[0442] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.77-7.72 (m, 2H), 7.59 (d, J = 7.8 Hz, 2H), 7.52-7.44 (m, 1H), 7.42 (d, J = 7.8 Hz, 4H), 7.38-7.28 (m, 7H), 7.24 (t, J = 7.3 Hz, 2H), 7.17 (t, J = 7.7 Hz, 2H), 2.89-2.81 (m, 2H), 2.76 (dt, J = 10.4, 4.1 Hz, 2H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 201.29, 199.91, 141.39, 137.22, 136.78, 132.81, 131.68, 129.90, 129.20, 128.45, 128.39, 127.96, 127.78, 127.06, 64.12, 36.00, 35.20.

[0443] Infrared spectrum (thin film, cm -1 ) 3337, 3058, 3032, 2979, 1967, 1683, 1597, 1580, 1495, 147, 1364, 1281, 1224, 1180, 1377, 1094, 1001, 990, 968, 845, 753, 701, 653, 587.

[0444] High resolution mass spectrum (APCI source) calcd for C 29 H 25 O2: 405.1849, found 405.1852.

[0445] Example 49

[0446] This example is basically the same as Example 34, except that:

[0447]

[0448] The olefin compound structure is formula (VII)-16, and the 1,5-dicarbonyl compound structure is formula (VIII)-16; the reaction time is 24 h, and the obtained target product is (VIII)-16, and the yield is 79%.

[0449] H NMR (400 MHz, chloroform-d) δ 7.84 - 7.76 (m, 2H), 7.62 - 7.56 (m, 2H), 7.52 (d, J = 7.4 Hz, 1H), 7.46 - 7.37 (m, 3H), 7.37 - 7.30 (m, 4H), 7.29 - 7.23 (m, 3H), 3.14 (ddd, J = 16.0, 11.8, 4.2 Hz, 1H), 2.62 (ddd, J = 16.0, 11.8, 4.2 Hz, 1H), 2.49 (ddd, J = 13.6, 11.8, 4.2 Hz, 1H), 2.20 (ddd, J = 13.5, 11.8, 4.2 Hz, 1H), 1.69 (ddd, J = 8.6, 5.7, 2.8 Hz, 1H), 0.76 - 0.65 (m, 1H), 0.48 - 0.31 (m, 2H), 0.17 - 0.04 (m, 1H); C NMR (101 MHz, chloroform-d) δ 201.79, 199.94, 141.29, 136.76, 136.36, 132.92, 131.96, 130.02, 128.50, 128.47, 128.17, 128.05, 128.02, 127.25, 57.33, 34.17, 30.85, 18.03, 3.87, 0.15.

[0450] Infrared spectrum (thin film, cm -1 ) 3060, 3023, 2924, 2853, 2361, 2341, 1676, 1597, 1579, 1493, 1447, 1277, 1237, 1179, 1002, 972, 846, 790, 751, 704, 690, 581.

[0451] High resolution mass spectrum (APCI source) calcd for C 26 H 24 O2: 368.1776, found 368.1768.

[0452] Example 50

[0453] This example is essentially the same as Example 34, except that:

[0454]

[0455] The olefin compound structure is formula (VII)-17, and the 1,5-dicarbonyl compound structure is formula (VIII)-17; the reaction time is 20 h, and the target product obtained is (VIII)-17, with a yield of 83%.

[0456] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.78 (dd, J = 8.4, 1.4 Hz, 2H), 7.73-7.67 (m, 2H), 7.58 (dd, J = 8.4, 1.3 Hz, 2H), 7.51 (t, J = 7.4 Hz, 1H), 7.46-7.31 (m, 6H), 7.25 (dd, J = 8.4, 7.1 Hz, 2H), 3.15 (ddd, J = 14.5, 9.1, 6.1 Hz, 1H), 2.96-2.68 (m, 3H), 1.99 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.98, 196.24, 169.17, 137.34, 136.75, 135.29, 132.96, 132.15, 129.11, 128.91, 128.52, 128.37, 128.08, 128.01, 125.04, 88.50, 32.54, 31.81, 21.17.

[0457] Infrared spectrum (thin film, cm -1 ) 3351, 3087, 3059, 3027, 2959, 2845, 2360, 2341, 1740, 1680, 1492, 1447, 1368, 1255, 1216, 1182, 1101, 1002, 881, 848, 748, 699, 689, 660, 635, 606, 578, 522.

[0458] High resolution mass spectrum (APCI source) calcd for C 25 H 22 O4: 386.1518, found 386.1508.

[0459] Example 51

[0460] This example is basically the same as Example 34, except that:

[0461] The olefin compound structure is formula (E)-(VII)-18 (E configuration), and the 1,5-dicarbonyl compound structure is formula (VIII)-18; the reaction time is 2.5 h, and the target product obtained is (VIII)-18, with a yield of 80%, mainly diastereoisomers, with a d.r. value of 9.0:1.

[0462]

[0463] NMR (400 MHz, CDC13) δ 8.14 - 7.11 (m, 15H), 4.61 (d, J = 9.5 Hz, 1H), 3.27 (dd, J = 15.1, 3.7 Hz, 1H), 3.10 (dtt, J = 9.8, 6.4, 3.3 Hz, 1H), 2.74 (dd, J = 15.1, 9.2 Hz, 1H), 0.83 (d, J = 6.8 Hz, 3H); NMR (101 MHz, CDC13) δ 199.97, 199.82, 137.45, 137.08, 136.94, 132.97, 128.99, 128.82, 128.62, 128.55, 128.42, 128.33, 127.98, 127.29, 59.06, 44.34, 33.54, 17.39.

[0464] IR (thin film, cm"1) -1 ) 3337, 3060, 3057, 2965, 2933 1966, 1680, 1597, 1580, 1492, 1517, 1363, 1278, 1214, 1179, 1074, 1001, 94, 894, 837, 751, 698, 658, 526.

[0465] HRMS (APCI source) calcd for C 24 H 23 O2: 343.1693, found 343.1692.

[0466] Example 52

[0467] This example is essentially the same as Example 51, except that:

[0468] The olefin compound has the structure of formula (Z)-(VII)-18 (Z configuration); the target product obtained is (VIII)-18 with a yield of 83%, mainly diastereoisomers with a d.r. value of 3.5:1.

[0469]

[0470] Example 53

[0471] This example is essentially the same as Example 34, except that:

[0472]

[0473] The olefin compound has the structure of formula (VII)-19 and the 1,5-dicarbonyl compound has the structure of formula (VIII)-19; the reaction time is 10 h; the target product obtained is (VIII)-19 with a yield of 70%.

[0474] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.08-7.99 (m, 2H), 7.96-7.85 (m, 2H), 7.61-7.16 (m, 11H), 5.40 (s, 1H), 3.26 (d, J = 17.3 Hz, 1H), 2.98 (d, J = 17.3 Hz, 1H), 0.81-0.53 (m, 3H), 0.50-0.33 (m, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.78, 199.72, 137.50, 137.36, 137.05, 133.07, 132.88, 129.84, 128.89, 128.72, 128.58, 128.55, 128.01, 127.37, 54.84, 45.33, 18.72, 9.18, 8.30.

[0475] Infrared spectrum (thin film, cm -1 ) 3350, 3061, 3005, 2924, 2361, 2341, 1680, 1596, 1580, 1447, 1358, 1274, 1208, 1179, 1077, 1023, 978, 833, 751, 689, 652, 599, 513.

[0476] High resolution mass spectrum (APCI source) calcd for C 25 H 22 O2: 354.1620, found 354.1612.

[0477] Example 54

[0478] This example is substantially the same as Example 34, except that:

[0479]

[0480] The olefin compound structure is formula (VII)-20, and the 1,5-dicarbonyl compound structure is formula (VIII)-20; the reaction time is 10 h, and the target product obtained is (VIII)-20, with a yield of 60%.

[0481] NMR (400 MHz, chloroform-d) δ 8.10 - 7.99 (m, 2H), 7.91 (d, J = 7.5 Hz, 2H), 7.54 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.3 Hz, 1H), 7.40 (ddd, J = 22.0, 10.7, 7.2 Hz, 6H), 7.30 (t, J = 7.3 Hz, 2H), 7.26 (d, J = 7.0 Hz, 1H), 5.40 (s, 1H), 3.26 (d, J = 17.2 Hz, 1H), 2.99 (d, J = 17.3 Hz, 1H), 0.68 (t, J = 6.2 Hz, 1H), 0.64 - 0.57 (m, 2H), 0.50 - 0.35 (m, 1H); NMR (101 MHz, chloroform-d) δ 199.70, 199.64, 137.52, 137.38, 137.01, 132.96, 132.78, 129.78, 128.80, 128.50, 128.47, 127.95, 127.30, 54.84, 45.22, 18.73, 9.16, 8.28.

[0482] Infrared spectrum (thin film, cm -1 ) 3060, 3005, 2918, 236, 2341, 1680, 1596, 1580, 1596, 1580, 1491, 1447, 1358, 1266, 1208, 1178, 1001, 833, 797, 751, 733, 688, 651, 599, 512.

[0483] High resolution mass spectrum (APCI source) calcd for C 25 H 22 O2: 354.1620, found 354.1612.

[0484] Example 55

[0485] This example is essentially the same as Example 34, except that:

[0486]

[0487] The olefin compound structure is formula (VII)-21, and the 1,5-diketone compound structure is formula (VIII)-21; the reaction time is 10 h, and the target product obtained is (VIII)-21, with a yield of 81%.

[0488] H NMR (400 MHz, chloroform-d) δ 7.86 - 7.80 (m, 2H), 7.62 (dd, J = 8.2, 1.4 Hz, 2H), 7.59 - 7.55 (m, 1H), 7.50 (d, J = 7.4 Hz, 1H), 7.38 (td, J = 10.0, 8.9, 6.9 Hz, 4H), 7.29 - 7.21 (m, 4H), 6.74 (s, 1H), 3.04 (ddd, J = 16.1, 10.8, 5.0 Hz, 1H), 2.87 (ddd, J = 16.4, 10.7, 5.4 Hz, 1H), 2.75 - 2.51 (m, 2H), 1.75 (s, 3H); C NMR (101 MHz, chloroform-d) δ 200.21, 199.41, 159.97, 154.66, 136.73, 136.57, 133.00, 132.20, 128.75, 128.54, 128.34, 128.28, 128.08, 124.19, 123.00, 120.94, 111.40, 103.06, 51.51, 33.90, 32.76, 23.12.

[0489] Infrared spectrum (thin film, cm -1 ) 3085, 3060, 2981, 2933, 2360, 2341, 1679, 1596, 1578, 1449, 1365, 1251, 1239, 1212, 1169, 965, 941, 883, 750, 738, 689, 570.

[0490] High resolution mass spectrum (APCI source) calcd for C 26 H 22 O3: 382.1569, found 382.1564.

[0491] Example 56

[0492] This example is essentially the same as Example 34, except that:

[0493]

[0494] The olefin compound structure is formula (VII)-22, and the 1,5-dicarbonyl compound structure is formula (VIII)-22; the reaction time is 20 h, and the target product obtained is (VIII)-22, with a yield of 91%.

[0495] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.86-7.76 (m, 2H), 7.55-7.48 (m, 3H), 7.40 (t, J = 7.6 Hz, 3H), 7.33 (dd, J = 5.0, 2.9 Hz, 1H), 7.26 (t, J = 7.8 Hz, 2H), 7.21 (dd, J = 3.0, 1.4 Hz, 1H), 6.96 (dd, J = 5.0, 1.4 Hz, 1H), 2.85 (ddd, J = 26.6, 10.2, 5.9 Hz, 2H), 2.50 (ddd, J = 10.3, 7.3, 5.5 Hz, 2H), 1.66 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 202.97, 199.81, 144.99, 136.85, 136.74, 132.99, 131.90, 129.20, 128.55, 128.16, 128.09, 126.76, 126.64, 120.46, 52.14, 34.48, 34.10, 24.57.

[0496] Infrared spectrum (thin film, cm -1 ) 3062, 3025, 2974, 2931, 2360, 2341, 1673, 1596, 1579, 1447, 1365, 1280, 1242, 1211, 1179, 977, 929, 749, 714, 689, 666.

[0497] High resolution mass spectrum (APCI source) calcd for C 22 H 20 O2S: 348.1184, found 348.1182.

[0498] Example 57

[0499] This example is substantially the same as Example 34, except that:

[0500]

[0501] The olefin compound structure is formula (VII)-23, and the 1,5-dicarbonyl compound structure is formula (VIII)-23; the reaction time is 10 h, and the target product obtained is (VIII)-23, with a yield of 70%.

[0502] H NMR (400 MHz, chloroform-d) δ 8.03 - 7.95 (m, 2H), 7.95 - 7.86 (m, 2H), 7.60 - 7.49 (m, 2H), 7.44 (dt, J = 15.5, 7.6 Hz, 4H), 3.60 (dtd, J = 8.6, 6.5, 4.8 Hz, 1H), 3.17 - 2.98 (m, 1H), 2.85 (ddd, J = 17.1, 8.3, 6.6 Hz, 1H), 2.34 - 2.14 (m, 1H), 2.14 - 1.96 (m, 1H), 1.86 - 1.73 (m, 1H), 1.53 (dd, J = 14.6, 6.7 Hz, 1H), 1.29 (dq, J = 7.3, 3.9, 3.2 Hz, 4H), 0.85 (q, J = 5.1, 3.6 Hz, 3H); C NMR (101 MHz, chloroform-d) δ 204.04, 199.92, 137.26, 136.79, 133.02, 132.99, 128.69, 128.53, 128.24, 128.00, 45.12, 35.91, 32.27, 29.51, 26.09, 22.81, 13.87.

[0503] Infrared spectrum (thin film, cm -1 ) 3350, 3061, 2956, 2930, 2858, 173, 1683, 1597, 1580, 1448, 1345, 1270, 1224, 1180, 1124, 1074, 1001, 972, 752, 705, 689.

[0504] High resolution mass spectrum (APCI source) calcd for C 21 H 25 O2: 309.1849, found 309.1851.

[0505] Example 58

[0506] This example is essentially the same as Example 34, except that:

[0507]

[0508] The olefin compound structure is formula (VII)-24, and the 1,5-dicarbonyl compound structure is formula (VIII)-24; the reaction time is 20 h, and the target product obtained is (VIII)-24, with a yield of 51%.

[0509] NMR (400 MHz, CDC13) δ 7.97 (d, J = 7.7 Hz, 2H), 7.90 (d, J = 7.7 Hz, 2H), 7.54 (d, J = 9.3 Hz, 2H), 7.47 - 7.33 (m, 4H), 3.60 (t, J = 6.7 Hz, 1H), 3.05 (dd, J = 16.3, 8.0 Hz, 1H), 2.92 - 2.77 (m, 1H), 2.31 - 2. (m, 1H), 2.02 (dd, J = 13.8, 6.9 Hz, 1H), 1.80 (dd, J = 14.1, 7.2 Hz, 1H), 1.51 (dt, J = 13.8, 6.7 Hz, 1H), 1.23 (d, J = 13.0 Hz, 24H), 0.88 (d, J = 6.4 Hz, 3H); NMR (101 MHz, CDC13) δ 204.09, 199.97, 137.28, 136.81, 133.05, 133.03, 128.72, 128.57, 128.28, 128.04, 45.19, 35.96, 32.60, 31.94, 29.77, 29.70, 29.66, 29.63, 29.57, 29.43, 29.38, 27.38, 26.10, 22.71, 14.14.

[0510] IR (thin film, cm -1 ) 2922, 2852, 2360, 2341, 1680, 1597, 1580, 1448, 1275, 1261, 1220, 972, 763, 689.

[0511] HRMS (APCI source) calcd for C 31 H 44 O2: 448.3341, found 448.3340.

[0512] Example 59

[0513] This example is essentially the same as Example 34, except that:

[0514]

[0515] The olefin compound structure is formula (VII)-25 and the 1,5-dicarbonyl compound structure is formula (VIII)-25; the reaction time is 10 h, and the target product obtained is (VIII)-25, with a yield of 93%.

[0516] H NMR (400 MHz, chloroform-d) δ 7.88 (dd, J = 8.3, 1.4 Hz, 2H), 7.81 - 7.67 (m, 2H), 7.57 - 7.50 (m, 1H), 7.47 (d, J = 7.4 Hz, 1H), 7.45 - 7.36 (m, 4H), 2.90 (td, J = 10.4, 5.4 Hz, 2H), 2.38 (ddd, J = 14.3, 10.8, 5.4 Hz, 1H), 2.15 - 1.91 (m, 2H), 1.74 (dd, J = 14.3, 7.3 Hz, 1H), 1.32 (s, 3H), 0.87 (t, J = 7.5 Hz, 3H); C NMR (101 MHz, chloroform-d) δ 208.28, 199.85, 139.16, 136.72, 133.08, 131.22, 128.59, 128.35, 128.08, 127.56, 51.31, 33.99, 33.37, 32.41, 22.34, 8.88.

[0517] Infrared spectrum (thin film, cm -1 ) 3060, 2968, 2933, 2361, 2341, 1672, 1597, 1579, 1447, 1366, 1277, 1213, 1178, 1002, 970, 744, 717, 689, 655, 568.

[0518] High resolution mass spectrum (APCI source) calcd for C 20 H 22 O2: 294.1620, found 294.1613.

[0519] Example 60

[0520] This example is essentially the same as Example 34, except that:

[0521]

[0522] The olefin compound has the structure of formula (VII)-26 and the 1,5-diketone compound has the structure of formula (VIII)-26; the reaction time is 20 h, and the target product obtained is (VIII)-26, with a yield of 85%.

[0523] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.93 (ddd, J = 8.5, 6.2, 1.8 Hz, 4H), 7.44 (ddt, J = 36.3, 15.5, 7.3 Hz, 6H), 3.84 - 3.60 (m, 2H), 3.21 - 2.95 (m, 2H), 2.48 (t, J = 7.5 Hz, 2H), 2.28 - 2.01 (m, 4H), 1.61 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.78, 198.32, 175.29, 136.61, 135.78, 133.14, 132.11, 128.58, 128.29, 128.16, 127.87, 65.16, 44.21, 33.83, 31.28, 31.12, 22.36, 18.76.

[0524] Infrared spectrum (thin film, cm -1 ) 3350, 2983, 2920, 2360, 2341, 1675, 1596, 1579, 1447, 1411, 1276, 1261, 1179, 1147, 969, 745, 707, 690, 583, 483.

[0525] High resolution mass spectrum (APCI source) calcd for C 22 H 23 NO3: 349.1678, found 349.1476.

[0526] Example 61

[0527] This example is substantially the same as Example 34, except that:

[0528]

[0529] The olefin compound structure is formula (VII)-27, and the 1,5-dicarbonyl compound structure is formula (VIII)-27; the reaction time is 10 h, and the target product obtained is (VIII)-27, with a yield of 70%.

[0530] H NMR (400 MHz, chloroform-d) δ 8.10 - 7.84 (m, 2H), 7.82 - 7.70 (m, 2H), 7.67 - 7.48 (m, 2H), 7.44 (td, J = 7.6, 1.5 Hz, 4H), 7.40 - 7.30 (m, 5H), 5. (s, 2H), 3.91 (s, 2H), 3.25 - 2.81 (m, 4H), 2.57 - 2.29 (m, 4H), 1.62 (s, 2H); C NMR (101 MHz, chloroform-d) δ 206.71, 198.95, 155.27, 138.42, 136.78, 136.53, 133.30, 131.84, 128.65, 128.58, 128.51, 128.01, 127.88, 127.72, 67.10, 50.14, 41.12, 34.03, 32.96.

[0531] Infrared spectrum (thin film, cm -1 ) 3058, 2923, 2872, 2360, 2341, 2278, 1684, 1597, 1430, 1360, 1277, 1215, 1146, 1092, 961, 733, 692, 456.

[0532] High resolution mass spectrum (APCI source) calcd for C 29 H 29 NO4: 455.2097, found 455.2095.

[0533] Example 62

[0534] This example is essentially the same as Example 34, except that:

[0535]

[0536] The olefin compound has the structure of formula (VII)-28 and the 1,5-diketone compound has the structure of formula (VIII)-28; the reaction time is 10 h, and the target product obtained is (VIII)-28, with a yield of 60%.

[0537] H NMR (400 MHz, chloroform-d) δ 7.91 (dd, J = 8.3, 1.4 Hz, 2H), 7.80 (dd, J = 8.3, 1.4 Hz, 2H), 7.57 - 7.52 (m, 1H), 7.46 (dt, J = 21.2, 7.5 Hz, 3H), 7.35 (t, J = 7.8 Hz, 2H), 3.71 (dt, J = 8.3, 4.3 Hz, 1H), 3.09 (dd, J = 16.9, 8.5 Hz, 1H), 2.93 (dd, J = 16.9, 5.1 Hz, 1H), 2.73 (dd, J = 7.3, 3.9 Hz, 1H), 1.92 (ddd, J = 14.4, 7.3, 3.8 Hz, 2H), 1.76 (dd, J = 7.5, 3.8 Hz, 1H), 1.63 (d, J = 9.0 Hz, 3H), 1.56 - 1.37 (m, 2H); C NMR (101 MHz, chloroform-d) δ 203.60, 199.76, 137.06, 136.79, 132.94, 132.88, 128.71, 128.49, 128.23, 128.05, 46.50, 38.76, 33.57, 29.25, 25.74, 23.71, 22.79.

[0538] Infrared spectrum (thin film, cm -1 ) 3337, 3059, 2993 0, 2856, 1680, 1597, 1580, 1448, 1370, 1324, 1280, 1253, 1214, 1178, 1010, 981, 946, 854, 752, 700, 691, 662, 567.

[0539] High resolution mass spectrum (APCI source) calcd for C 21 H 23 O2: 307.1693, found 307.1695.

[0540] Example 63

[0541] This example is essentially the same as Example 34, except that:

[0542]

[0543] The olefin compound structure is formula (VII)-29, and the 1,5-dicarbonyl compound structure is formula (VIII)-29; the reaction time is 10 h, and the target product obtained is (VIII)-29, with a yield of 70%.

[0544] H NMR (400 MHz, chloroform-d) δ 8.12 - 7.98 (m, 2H), 7.98 - 7.85 (m, 2H), 7.69 - 7.51 (m, 2H), 7.51 - 7.37 (m, 4H), 5.94 (ddd, J = 17.1, 10.3, 8.7 Hz, 1H), 5.34 - 5.09 (m, 2H), 4.25 (td, J = 8.4, 6.6 Hz, 1H), 3.37 - 3.06 (m, 1H), 2.99 (ddd, J = 17.4, 7.2, 6.0 Hz, 1H), 2.37 (dd, J = 13.9, 6.8 Hz, 1H), 2.12 - 1.97 (m, 1H); C NMR (101 MHz, chloroform-d) δ 200.64, 199.75, 136.91, 136.48, 133.16, 133.09, 129.26, 128.64, 128.61, 128.19, 128.02, 118.53, 50.58, 35.51, 26.19.

[0545] Infrared spectrum (thin film, cm -1 ) 3060, 2922, 2852, 2360, 2341, 1678, 1634, 1596, 1579, 1447, 1364, 1276, 1278, 1179, 992, 924, 751, 699, 568.

[0546] High resolution mass spectrum (APCI source) calcd for C 19 H 18 O2: 278.1307, found 278.1298.

[0547] Example 64

[0548] This example is essentially the same as Example 34, except that:

[0549]

[0550] The olefin compound structure is formula (VII)-30, and the 1,5-dicarbonyl compound structure is formula (VIII)-30; the reaction time is 10 h, and the target product obtained is (VIII)-30, with a yield of 80%.

[0551] H NMR (400 MHz, chloroform-d) δ 8.08 - 7.96 (m, 2H), 7.88 - 7.79 (m, 2H), 7.58 - 7.47 (m, 2H), 7.47 - 7.29 (m, 4H), 5.14 (dt, J = 5.2, 1.1 Hz, 2H), 2.94 - 2.72 (m, 2H), 2.32 (dddd, J = 47.6, 14.2, 11.0, 5.2 Hz, 2H), 1.78 (s, 3H), 1.42 (s, 3H); C NMR (101 MHz, chloroform-d) δ 203.44, 200.01, 148.00, 136.94, 136.83, 132.97, 132.33, 128.96, 128.56, 128.26, 128.07, 112.62, 55.67, 33.92, 31.63, 22.76, 20.67.

[0552] Infrared spectrum (thin film, cm -1 ) 3474 3061, 2972, 2923, 2854, 2361, 2341, 1675, 1636, 1597, 1579, 1447, 1380, 1277, 1260, 1237, 1209, 1179, 966, 896, 747, 689, 578.

[0553] High resolution mass spectrum (APCI source) calcd for C 21 H 22 O2: 306.1620, found 306.1613.

[0554] Example 65

[0555] This example is essentially the same as Example 34, except that:

[0556] The olefin compound structure is formula (VII)-31 and the 1,5-diketone compound structure is formula (VIII)-31; the reaction time is 15 h, and the target product obtained is (VIII)-31, with a yield of 84%, mainly as diastereoisomers, with a d.r. value of 1.3:1.

[0557]

[0558] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.91-7.85 (m, 2H), 7.84-7.80 (m, 2H), 7.57-7.47 (m, 2H), 7.44-7.38 (m, 4H), 5.38 (dt, J = 5.5, 1.9 Hz, 1H), 3.01-2.83 (m, 2H), 2.51-2.25 (m, 2H), 2.23-1.83 (m, 5H), 1.62 (d, J = 2.2 Hz, 3H), 1.53-1.32 (m, 2H), 1.24 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 208.78, 199.87 (d, J = 7.6 Hz), 139.49, 136.70, 134.10, 133.10, 131.16, 128.58, 128.37, 128.08, 127.59, 120.41, 54.09, 40.59, 33.98, 31.14, 26.24, 25.26, 23.32, 18.19.

[0559] Infrared spectrum (thin film, cm -1 ) 3057, 2927, 2360, 2341, 1679, 1597, 1449, 1379, 1277, 1260, 1212, 1179, 976, 958, 746, 689, 591, 567, 430, 413.

[0560] High resolution mass spectrum (APCI source) calcd for C 25 H 28 O2: 360.2089, found 360.2085.

[0561] Example 66

[0562] This example is substantially the same as Example 34, except that:

[0563]

[0564] The olefin compound structure is formula (VII)-32, and the 1,5-dicarbonyl compound structure is formula (VIII)-32; the reaction time is 10 h, and the obtained target product is (VIII)-32, and the yield is 87%.

[0565] H NMR (400 MHz, CDC13) δ 7.77 - 7.70 (m, 2H), 7.58 - 7.46 (m, 3H), 7.39 - 7.17 (m, 11H), 6.81 (d, J = 8.8 Hz, 2H), 5.04 (p, J = 6.3 Hz, 1H), 2.90 - 2.65 (m, 4H), 1.59 (s, 6H), 1.14 (t, J = 6.9 Hz, 6H);13C NMR (101 MHz, CDC13) δ 201.03, 199.67, 173.49, 154.70, 140.39, 137.11, 136.72, 133.88, 132.99, 132.95, 131.86, 130.62, 129.82, 128.56, 128.50, 127.98, 127.93, 118.55, 79.12, 68.99, 63.11, 35.73, 35.08, 25.44, 25.32, 21.55, 21.51.

[0566] Infrared spectrum (thin film, cm -1 ) 3059, 298, 2933, 2360, 2341, 1906, 1727, 1677, 1597, 1579, 1507, 1491, 1447, 13117, 1280, 1246, 1178, 1149, 1100, 1002, 972, 930, 820, 744, 691, 585.

[0567] High resolution mass spectrum (APCI source) calcd for C 36 H 35 ClO5: 582.2173, found 582.2168.

[0568] Example 67

[0569] This example is essentially the same as Example 34, except that:

[0570]

[0571] The olefin compound structure is formula (VII)-33, and the 1,5-dicarbonyl compound structure is formula (VIII)-33; the reaction time is 10 h, and the target product obtained is (VIII)-33, with a yield of 97%, mainly as diastereoisomers, with a d.r. value of 1.2:1.

[0572] H NMR (400 MHz, chloroform-d) δ 7.79 - 7.73 (m, 2H), 7.57 (d, J = 7.8 Hz, 2H), 7.53 - 7.40 (m, 3H), 7.39 - 7.23 (m, 9H), 7.24 - 7.12 (m, 3H), 3.66 (q, J = 7.0 Hz, 1H), 3.55 (s, 3H), 2.90 - 2.70 (m, 4H), 1.41 (d, J = 7.2 Hz, 3H); C NMR (101 MHz, chloroform-d) δ 201.25, 199.89, 174.68, 141.76, 141.29, 140.72, 140.62, 137.31, 136.89, 132.86, 131.68, 129.95, 129.22, 129.02, 128.77, 128.55, 128.45, 128.02, 127.80, 127.21, 126.06, 64.32, 51.95, 45.46, 45.36, 35.22, 18.50.

[0573] Infrared spectrum (thin film, cm -1 ) 3057, 2982, 2937, 2360, 2341, 1733, 1676, 1597, 1580, 1489, 1434, 1263, 1222, 1168, 1068, 969, 750, 734, 700, 572.

[0574] High resolution mass spectrum (APCI source) calcd for C 33 H 30 O4: 490.2144, found 490.2140.

[0575] Example 68

[0576] This example is essentially the same as Example 34, except that:

[0577]

[0578] The olefin compound structure is formula (VII)-34, and the 1,5-dicarbonyl compound structure is formula (VIII)-34; the reaction time is 20 h, and the target product obtained is (VIII)-34, with a yield of 90%, mainly as diastereoisomers, with a d.r. value of 3.0:1.

[0579] H NMR (400 MHz, deuterated chloroform) δ7.89 (d, J = 7.6 Hz, 2H), 7.79 (d, J = 7.2 Hz, 2H), 7.57–7.35 (m, 6H), 7.18 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 7.9 Hz, 2H), 3.71–3.62 (m, 4H), 3.08–2.83 (m, 2H), 2.70–

[0580] 2.50 (m, 3H), 2.40 (t, J = 12.5 Hz, 1H), 2.25–2.04 (m, 1H), 1.71 (dddd, J = 68.5, 12.4, 9.6, 6.6 Hz, 4H), 1.47 (dd, J = 7.2, 2.0 Hz, 3H); C NMR (101 MHz, deuterated chloroform) δ 206.86, 199.91, 175.1 4,140.10,138.12,137.91,136.69,133.13,131.49,129.14,128.61,128.38,128.10,128.01,127.43,61.11,52.02,48.81,45.01,35.85,35.08,29.93,27.94,22.43,18.61.

[0581] Infrared spectrum (thin film, cm -1 )3056,2949,2874,2360,2341,1734,1669,1596,1579,1512,1435,1260,1207,1165,1066,1001,970,859,748,690,567,538.

[0582] High-resolution mass spectrometry (APCI source) calcd for C 31 H 32 O4:468.2301,found 468.2236.

[0583] Example 69

[0584] This embodiment is basically the same as embodiment 34, except that:

[0585]

[0586] The olefin compound has a structure of formula (VII)-35, and the 1,5-dicarbonyl compound has a structure of formula (VIII)-35; the reaction time is 10 hours, and the target product obtained is (VIII)-35 with a yield of 99%.

[0587] H NMR (400 MHz, CDC13) δ 7.85 - 7.73 (m, 2H), 7.60 - 7.54 (m, 2H), 7.54 - 7.46 (m, 1H), 7.41 - 7.33 (m, 4H), 7.20 (dd, J = 8.3, 7.4 Hz, 2H), 7.10 (d, J = 1.7 Hz, 1H), 2.83 (ddd, J = 9.6, 5.9, 4.8 Hz, 2H), 2.63 - 2.42 (m, 4H), 1.76 - 1.64 (m, 5H), 1.38 (s, 9H), 1.11 (d, J = 16.9 Hz, 6H);13C NMR (101 MHz, CDC13) δ 203.57, 200.16, 154.09, 150.56, 139.14, 137.86, 136.79, 136.38, 132.90, 132.10, 129.19, 128.51, 128.06, 128.00, 120.57, 117.61, 54.39, 43.15, 41.39, 34.96, 33.99, 32.79, 31.71, 29.28, 28.39, 23.94.

[0588] IR (thin film, cm -1 ) 3086, 3062, 2953, 2862, 2360, 2341, 1676, 1597, 1589, 1447, 1361, 1277, 1259, 1236, 1179, 976, 953, 749, 716, 689, 605.

[0589] High resolution mass spec (APCI source) calcd for C 31 H 38 O2: 466.2872, found 466.2866.

[0590] Example 70

[0591] This example is essentially the same as Example 34, except that:

[0592] The olefin compound structure is formula (VII)-36 and the 1,5-dicarbonyl compound structure is formula (VIII)-36; the reaction time is 48 h, and the target product obtained is (VIII)-36, with a yield of 55%.

[0593]

[0594] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.85 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 7.7 Hz, 2H), 7.55-7.29 (m, 6H), 4.02 (d, J = 7.8 Hz, IH), 2.79-2.46 (m, 3H), 2.17-1.09 (m, 23H), 1.00 (s, 3H), 0.84-0.71 (m, 4H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 208.27, 200.03, 140.71, 136.54, 133.01, 131.41, 128.51, 128.49, 128.29, 127.96, 66.50, 66.08, 53.56, 51.26, 48.19, 39.04, 36.89, 36.05, 35.85, 35.19, 34.56, 32.09, 31.99, 30.79, 28.96, 28.51, 25.17, 20.92, 16.73, 16.34, 11.17.

[0595] Infrared spectrum (thin film, cm -1 ) 3368, 2921, 2853, 2360, 2341, 1681, 1660, 1597, 1447, 1262, 1210, 1178, 1009, 966, 748, 691.

[0596] High resolution mass spectrum (APCI source) calcd for C 35 H 44 O3: 512.3290, found 512.3280.

[0597] Example 71

[0598] This example is essentially the same as Example 34, except that:

[0599]

[0600] The 1,3-dicarbonyl compound is of the structure of formula (VI)-2, the olefin compound is of the structure of formula (VII)-37, and the 1,5-dicarbonyl compound is of the structure of formula (VIII)-37; the reaction time is 2.5 h, and the target product obtained is (VIII)-37, with a yield of 99%.

[0601] H NMR (400 MHz, CDC13) δ 8.04 - 7.94 (m, 2H), 7.94 - 7.84 (m, 2H), 7.34 - 7.25 (m, 4H), 7.23 - 7.16 (m, 1H), 6.94 - 6.81 (m, 4H), 4.72 (t, J = 7.3 Hz, 1H), 3.82 (d, J = 16.9 Hz, 6H), 3.04 - 2.93 (m, 1H), 2.86 (dt, J = 16.7, 6.7 Hz, 1H), 2.58 (dt, J = 14.0, 7.2 Hz, 1H), 2.25 (dt, J = 13.9, 6.9 Hz, 1H);13C NMR (101 MHz, CDC13) δ 198.53, 198.13, 163.36, 163.28, 139.65, 131.03, 130.28, 129.92, 129.64, 128.90, 128.22, 127.02, 113.64, 113.62, 55.38, 55.34, 52.10, 35.71, 28.61.

[0602] IR (thin film, cm -1 ) 3061, 2962, 2935, 2839, 1671, 1600, 1574, 1510, 1454, 1419, 1363, 1313, 1259, 1163, 1114, 1029, 982, 837, 752, 702.

[0603] High resolution mass spec (APCI source) calcd for C 25 H 25 O4: 389.1747, found 389.1750.

[0604] Example 72

[0605] This example is essentially the same as Example 34, except that:

[0606]

[0607] 1,3-dicarbonyl compound is of formula (VI)-3, olefin compound structure is of formula (VII)-37, and 1,5-dicarbonyl compound structure is of formula (VIII)-38; reaction time is 2.5 h, and the target product obtained is (VIII)-38 with a yield of 97%.

[0608] H NMR (400 MHz, CDC13) δ 7.89 (d, J = 8.2 Hz, 2H), 7.81 (d, J = 8.1 Hz, 2H), 7.35 - 7.27 (m, 4H), 7.24 - 7.15 (m, 5H), 4.76 (t, J = 7.3 Hz, 1H), 3.05 - 2.82 (m, 2H), 2.59 (dt, J = 14.1, 7.2 Hz, 1H), 2.39 (s, 3H), 2.34 (s, 3H), 2.32 - 2.22 (m, 1H);13C NMR (101 MHz, CDC13) δ 199.56, 199.21, 143.72, 143.66, 139.41, 134.35, 134.13, 129.18, 129.16, 128.93, 128.87, 128.27, 128.12, 127.07, 52.29, 35.89, 28.38, 21.56, 21.52.

[0609] Infrared spectrum (thin film, cm -1 ) 3337, 3060, 3029, 2925, 1923, 1679, 1606, 1572, 1492, 1453, 1408, 1365, 1277, 1227, 1179, 1119, 1072, 102, 977, 842, 790, 750, 701, 566, 519.

[0610] High resolution mass spectrum (APCI source) calcd for C 25 H 25 O2: 357.1849, found 357.1852.

[0611] Example 73

[0612] This example is essentially the same as Example 34, except that:

[0613]

[0614] 1,3-dicarbonyl compound is formula (VI)-4, olefin compound structure is formula (VII)-37, 1,5-dicarbonyl compound structure is formula (VIII)-39; reaction time is 2.5 h, and the obtained target product is (VIII)-39, with a yield of 80%.

[0615] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.92 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H), 7.36 (d, J = 8.6 Hz, 2H), 7.32-7.22 (m, 5H), 4.71 (t, J = 7.3 Hz, 1H), 3.06-2.82 (m, 2H), 2.58 (dd, J = 14.1, 7.1 Hz, 1H), 2.27 (dd, J = 14.0, 6.9 Hz, 1H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.58, 198.27, 139.53, 139.39, 138.72, 135.04, 134.80, 130.17, 129.42, 129.18, 128.88, 128.83, 128.21, 127.43, 52.44, 35.79, 28.06.

[0616] Infrared spectrum (thin film, cm -1 ) 3350, 3062, 3028, 2959, 2933, 1684, 1588, 1570, 1489, 1399, 1366, 1276, 1221, 1175, 1093, 1013, 984, 827, 766, 748, 700, 569, 533, 517.

[0617] High resolution mass spectrum (APCI source) calcd for C 23 H 19 O2Cl2: 397.0757, found 397.0760.

[0618] Example 74

[0619] This example is basically the same as Example 34, except that:

[0620]

[0621] The 1,3-dicarbonyl compound is formula (VI)-5, the olefin compound structure is formula (VII)-37, and the 1,5-dicarbonyl compound structure is formula (VIII)-40; the reaction time is 2.5 h, and the obtained target product is (VIII)-40, with a yield of 92%.

[0622] H NMR (400 MHz, chloroform-d) δ 8.02 - 7.92 (m, 2H), 7.92 - 7.82 (m, 2H), 7.25 (d, J = 6.4 Hz, 4H), 7.20 - 7.15 (m, 1H), 7.03 (dt, J = 21.6, 8.7 Hz, 4H), 4.68 (t, J = 7.3 Hz, 1H), 3.05 - 2.77 (m, 2H), 2.53 (dq, J = 14.3, 7.2 Hz, 1H), 2.23 (dt, J = 13.9, 7.0 Hz, 1H); C NMR (101 MHz, chloroform-d) δ 198.27, 197.98, 166.93 (d, J = 17.3 Hz), 164.40 (d, J = 17.6 Hz), 138.97, 133.23 (d, J = 3.0 Hz), 132.96 (d, J = 2.9 Hz), 131.46 (d, J = 9.3 Hz), 130.68 (d, J = 9.3 Hz), 129.19, 128.26, 127.41, 115.78 (d, J = 2.3 Hz), 115.56 (d, J = 2.2 Hz), 52.44, 35.82, 28.26; F NMR (377 MHz, chloroform-d) δ -105.15, -105.19.

[0623] Infrared spectrum (thin film, cm -1 ) 3345, 3064, 3029, 2933 1683, 1597, 1506, 1454, 1409, 1367, 1272, 1230, 1156, 1099, 1012, 985, 842, 752, 702, 606, 566, 521.

[0624] High resolution mass spectrum (APCI source) calcd for C 23 H 19 O2F2: 365.1348, found 365.1348.

[0625] Example 75

[0626] This example is essentially the same as Example 34, except that:

[0627]

[0628] The 1,3-dicarbonyl compound is of formula (VI)-6, the olefin compound is of formula (VII)-37, and the 1,5-dicarbonyl compound is of formula (VIII)-41; the reaction time is 2.5 h, and the target product obtained is (VIII)-41 in a yield of 89%.

[0629] NMR (400 MHz, CDC13) δ 8.04 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.27 (dq, J = 15.4, 7.7 Hz, 5H), 4.74 (t, J = 7.3 Hz, IH), 2.98 (q, J = 7.0 Hz, 2H), 2.58 (dq, J = 14.2, 7.1 Hz, IH), 2.30 (dt, J = 14.0, 7.0 Hz, IH); NMR (101 MHz, CDC13) δ 198.79, 198.48, 139.35, 139.18, 138.28, 134.51 (d, J = 25.0 Hz), 134.18 (d, J = 25.2 Hz), 129.37, 129.11, 128.37, 128.28, 127.69 125.65 (q, J = 3.7 Hz), 125.69 (q, J = 3.7 Hz), 123.57 (d, J = 272.7 Hz), 123.51 (d, J = 272.7 Hz), 52.80, 36.07, 27.86; 19 NMR (377 MHz, CDC13) δ -63.14, -63.21.

[0630] IR (thin film, cm"1) 3064, 3029, 2936, 1689, 1600, 1582, 1512, 1454, 1410, 1326, 1275, 1221, 1169, 1130, 1067, 1016, 987, 856, 833, 746, 725, 600. -1 )3064,3029,2936,1689,1600,1582,1512,1454,1410,1326,1275,1221,1169,1130,1067,1016,987,856,833,746,725,600.

[0631] HRMS (APCI source) calcd for C 25 H 19 O2F6: 465.1284, found 465.1288.

[0632] Example 76

[0633] This example is essentially the same as Example 34, except that:

[0634]

[0635] The 1,3-dicarbonyl compound is of the formula (VI)-7, the olefin compound is of the formula (VII)-37, and the 1,5-dicarbonyl compound is of the formula (VIII)-42; the reaction time is 2.5 h, and the target product obtained is (VIII)-42, with a yield of 77%.

[0636] NMR (400 MHz, CDC13) δ 8.02 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 8.1 Hz, 2H), 7.74 (d, J = 8.1 Hz, 2H), 7.67 (d, J = 8.2 Hz, 2H), 7.31 (t, J = 7.1 Hz, 2H), 7.24 (dd, J = 9.8, 7.9 Hz, 3H), 4.71 (t, J = 7.3 Hz, 1H), 2.98 (td, J = 6.8, 3.5 Hz, 2H), 2.57 (dd, J = 14.1, 7.1 Hz, 1H), 2.29 (dd, J = 14.1, 7.1 Hz, 1H); NMR (101 MHz, CDC13) δ 198.27, 197.99, 139.51, 139.40, 137.83, 132.49, 132.37, 129.42, 129.10, 128.37, 128.19, 127.80, 117.81, 117.78, 116.44, 116.17, 52.76, 35.94, 27.60.

[0637] IR (thin film, cm -1 ) 3359, 3062, 2930, 2230, 1688, 1606, 1566, 1491, 1453, 1404, 1368, 1312, 1272, 1219, 1175, 1113, 1031, 987, 834, 739, 703, 576, 546.

[0638] HRMS (APCI source) calcd for C 25 H 19 O2N2: 379.1441, found 379.1445.

[0639] Example 77

[0640] This example is essentially the same as Example 34, except that:

[0641]

[0642] The 1,3-dicarbonyl compound is formula (VI)-8, the olefin compound structure is formula (VII)-37, and the 1,5-dicarbonyl compound structure is formula (VIII)-43; the reaction tube is placed at a distance of about 1 cm from a 10W 400nm LED light source, the reaction time is 2.5h, and the target product obtained is (VIII)-43, with a yield of 94%.

[0643] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.01-7.93 (m, 2H), 7.51-7.44 (m, 1H), 7.37 (dd, J = 8.3, 6.8 Hz, 2H), 7.33-7.24 (m, 4H), 7.24-7.17 (m, 1H), 4.70-4.59 (m, 1H), 2.47-2.31 (m, 3H), 2.18-2.09 (m, 1H), 2.08 (s, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 208.38, 199.47, 138.96, 136.57, 132.89, 128.98, 128.68, 128.48, 128.24, 127.19, 52.18, 40.91, 29.92, 27.60.

[0644] Infrared spectrum (thin film, cm -1 ) 3084, 3027, 2961, 2933, 1714, 1680, 1597, 1490, 1368, 1269, 1176, 1159, 1072, 756, 699.

[0645] High resolution mass spectrum (APCI source) calcd for C 18 H 19 O2: 267.1380, found 267.1382.

[0646] Example 78

[0647] This example is basically the same as Example 34, except that:

[0648]

[0649] The 1,3-dicarbonyl compound is formula (VI)-9, the olefin compound structure is formula (VII)-37, and the 1,5-dicarbonyl compound structure is formula (VIII)-44; the reaction tube is placed about 1 cm away from a 10W 400nm LED light source, the reaction time is 2.5h, and the obtained target product is (VIII)-44, with a yield of 95%.

[0650] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.95 (dd, J = 8.4, 1.4 Hz, 2H), 7.50-7.44 (m, 1H), 7.37 (dd, J = 8.3, 6.9 Hz, 2H), 7.28 (d, J = 5.6 Hz, 4H), 7.20 (td, J = 5.6, 3.1 Hz, 1H), 4.67 (dd, J = 8.0, 6.0 Hz, 1H), 2.56-2.28 (m, 5H), 2.22-2.03 (m, 1H), 1.02 (t, J = 7.3 Hz, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 211.15, 199.61, 139.08, 136.71, 132.91, 129.01, 128.73, 128.52, 128.33, 127.21, 52.30, 39.59, 35.93, 27.75, 7.82.

[0651] Infrared spectrum (thin film, cm -1 ) 3361, 3184, 3061, 2972, 2921, 2851, 2361, 2341, 1710, 1678, 1597, 1492, 1447, 1371, 1342, 1262, 1176, 1160, 1115, 1073, 982, 955, 832, 756, 666, 570, 517.

[0652] High resolution mass spectrum (APCI source) calcd for C 19 H 20 O2: 280.1463, found 280.1458.

[0653] Example 79

[0654] This example is basically the same as Example 34, except that:

[0655]

[0656] The 1,3-dicarbonyl compound is formula (VI)-10, the olefin compound structure is formula (VII)-37, and the 1,5-dicarbonyl compound structure is formula (VIII)-45; the reaction tube is placed about 1 cm away from a 10W 400nm LED light source, the reaction time is 2.5h, and the obtained target product is (VIII)-45, with a yield of 87%.

[0657] H NMR (400 MHz, chloroform-d) δ 8.02 - 7.88 (m, 2H), 7.49 - 7.42 (m, 1H), 7.37 (dd, J = 8.4, 6.9 Hz, 2H), 7.28 (d, J = 5.5 Hz, 4H), 7.23 - 7.09 (m, 1H), 4.72 - 4.61 (m, 1H), 2.49 - 2.34 (m, 3H), 2.31 (t, J = 7.3 Hz, 2H), 2.11 (d, J = 7.2 Hz, 1H), 1.56 (q, J = 7.4 Hz, 2H), 0.87 (t, J = 7.4 Hz, 3H); C NMR (101 MHz, chloroform-d) δ 210.74, 199.63, 139.08, 136.73, 132.91, 129.00, 128.73, 128.52, 128.33, 127.21, 52.28, 44.77, 40.00, 27.71, 17.28, 13.72.

[0658] Infrared spectrum (thin film, cm -1 ) 3360, 3184, 2960, 2921, 2851, 2361, 2341, 1708, 1678, 1597, 1447, 1261, 1159, 1126, 959, 753, 697, 570, 517.

[0659] High resolution mass spectrum (APCI source) calcd for C 20 H 22 O2: 294.1620, found 294.1611.

[0660] Example 80

[0661] This example is essentially the same as Example 34, except that:

[0662]

[0663] 1,3-dicarbonyl compound is formula (VI)-11, olefin compound structure is formula (VII)-37, 1,5-dicarbonyl compound structure is formula (VIII)-46; the reaction tube is placed at a distance of about 1 cm from a 10W 400nm LED light source, the reaction time is 2.5h, and the obtained target product is (VIII)-45, with a yield of 91%.

[0664] H NMR (400 MHz, chloroform-d) δ 8.05 - 7.88 (m, 2H), 7.52 - 7.43 (m, 1H), 7.37 (ddd, J = 8.2, 6.7, 1.4 Hz, 2H), 7.28 (d, J = 5.0 Hz, 4H), 7.20 (ddd, J = 6.5, 4.7, 3.4 Hz, 1H), 4.69 (t, J = 7.2 Hz, 1H), 2.73 - 2.30 (m, 4H), 2.12 (dd, J = 7.0, 5.6 Hz, 1H), 1.03 (dd, J = 7.0, 6.0 Hz, 6H); C NMR (101 MHz, chloroform-d) δ 214.41, 199.72, 139.09, 136.76, 132.90, 128.97, 128.73, 128.52, 128.36, 127.19, 52.19, 40.83, 37.55, 27.70, 18.29, 18.23.

[0665] Infrared spectrum (thin film, cm -1 ) 3360, 3184, 2964, 2921, 2851, 2361, 2340, 1707, 1678, 1597, 1468, 1447, 1324, 1274, 1176, 1073, 1011, 957, 753, 697, 582, 515.

[0666] High resolution mass spectrum (APCI source) calcd for C 20 H 22 O2: 294.1620, found 194.1613.

[0667] Example 81

[0668] This example is essentially the same as Example 34, except that:

[0669]

[0670] The 1,3-dicarbonyl compound is of the structure of formula (VI)-12, the olefin compound is of the structure of formula (VII)-37, and the 1,5-dicarbonyl compound is of the structure of formula (VIII)-47; the reaction time is 2.5 h, and the target product obtained is (VIII)-47, with a yield of 93%.

[0671] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 7.87 (d, J = 7.7 Hz, 2H), 7.38 (t, J = 7.9 Hz, 3H), 7.32-7.18 (m, 9H), 7. (dq, J = 6.2, 2.7 Hz, 1H), 7.01 (t, J = 7.4 Hz, 1H), 4.69 (t, J = 7.2 Hz, 1H), 2.53-2.41 (m, 1H), 2.31-2.15 (m, 3H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 198.71, 169.69, 137.85, 136.80, 135.47, 132.02, 128.05, 127.95, 127.77, 127.53, 127.32, 126.28, 123.22, 118.84, 51.34, 33.87, 28.31.

[0672] Infrared spectrum (thin film, cm -1 ) 3084, 3027, 2961, 2933, 1713, 1680, 1597, 1580, 1490, 1369, 1269, 1176, 1160, 1072, 1001, 756, 699.

[0673] High resolution mass spectrum (APCI source) calcd for C 23 H 21 NO2: 343.1572, found 343.1564.

[0674] Example 82

[0675] This example is basically the same as Example 34, except that:

[0676]

[0677] 1,3-dicarbonyl compound is formula (VI)-13, olefin compound structure is formula (VII)-37, 1,5-dicarbonyl compound structure formula is (VIII)-48; reaction time is 20 h, and the obtained target product is (VIII)-48, and the yield is 49%.

[0678] Nuclear magnetic resonance hydrogen spectrum (400 megahertz, deuterated chloroform) δ 8.06-7.87 (m, 2H), 7.50-7.43 (m, 1H), 7.41-7.26 (m, 8H), 7.21 (dq, J = 7.8, 2.7 Hz, 1H), 7.10 (d, J = 7.9 Hz, 3H), 4.77 (t, J = 7.0 Hz, 1H), 2.54 (d, J = 7.2 Hz, 1H), 2.44-2.15 (m, 6H); nuclear magnetic resonance carbon spectrum (101 megahertz, deuterated chloroform) δ 199.74, 170.52, 138.93, 136.61, 135.24, 133.93, 133.00, 129.48, 129.07, 128.80, 128.55, 128.39, 127.30, 120.00, 52.39, 34.90, 29.40, 20.84.

[0679] Infrared spectrum (thin film, cm -1 ) 3305, 3124, 3060, 2923, 2854, 2361, 2341, 1678, 1659, 1598, 1531, 1448, 1405, 1311, 1260, 1178, 968, 817, 750, 698, 573, 507.

[0680] High resolution mass spectrum (APCI source) calcd for C 24 H 23 NO2: 357.1729, found 357.1722.

[0681] Example 83

[0682] This example is basically the same as Example 34, except that:

[0683] 1,3-dicarbonyl compound is formula (VI)-14, olefin compound structure is formula (VII)-37, 1,5-dicarbonyl compound structural formula is (VIII)-49; reaction time is 20 h, and the obtained target product is (VIII)-49, and the yield is 60%.

[0684]

[0685] H NMR (400 MHz, chloroform-d) δ 8.01 - 7.94 (m, 2H), 7.69 - 7.56 (m, 4H), 7.55 - 7.46 (m, 2H), 7.40 (dd, J = 8.4, 7.1 Hz, 2H), 7.32 (d, J = 4.4 Hz, 4H), 7.25 (q, J = 4.5 Hz, 1H), 4.78 (t, J = 7.1 Hz, 1H), 2.60 - 2.50 (m, 1H), 2.41 (dt, J = 10.4, 6.8 Hz, 2H), 2.34 - 2.25 (m, 1H); C NMR (101 MHz, chloroform-d) δ 199.71, 170.99, 140.90, 138.80, 136.47, 133.15, 129.16, 128.80, 128.60, 128.28, 127.43, 126.28, 126.24, 119.31, 52.50, 35.13, 29.70, 29.26.

[0686] Infrared spectrum (thin film, cm -1 ) 3307, 3063, 2924, 2854, 1359, 2341, 1667, 1604, 1533, 1448, 1408, 1320, 1259, 1162, 1112, 1066, 1016, 841, 750, 697, 594, 509, 414.

[0687] High resolution mass spectrum (APCI source) calcd for C 24 H 20 F3NO2: 411.1446, found 411.1438.

[0688] Example 84

[0689] This example is essentially the same as Example 34, except that:

[0690]

[0691] 1,3-dicarbonyl compound is formula (VI)-15, olefin compound structure is formula (VII)-37, 1,5-dicarbonyl compound structure formula is (VIII)-50; reaction time is 20 h, the obtained target product is (VIII)-50, and the yield is 85%.

[0692] H NMR (400 MHz, chloroform-d) δ 7.96 (d, J = 7.5 Hz, 2H), 7.49 (d, J = 7.6 Hz, 1H), 7.40 (t, J = 7.7 Hz, 2H), 7.35 - 7.27 (m, 9H), 7.25 - 7.20 (m, 1H), 5.71 (d, J = 6.3 Hz, 1H), 4.75 (t, J = 6.7 Hz, 1H), 4.44 (dd, J = 8.9, 5.7 Hz, 2H), 2.50 (dd, J = 9.1, 4.9 Hz, 1H), 2.35 - 2.09 (m, 3H);13C NMR (101 MHz, chloroform-d) δ 199.76, 172.27, 139.07, 138.44, 136.78, 133.09, 129.15, 128.90, 128.87, 128.67, 128.50, 128.00, 127.69, 127.37, 52.49, 43.77, 34.10, 29.68.

[0693] Infrared spectrum (thin film, cm -1 ) 3292, 3062, 3005, 2922, 2853, 2361, 2340, 1676, 1644, 1597, 1579, 1539, 1493, 1448, 1356, 1301, 1275, 1260, 1228, 1158, 1077, 1029, 750, 695, 573, 504.

[0694] High resolution mass spectrum (APCI source) calcd for C 24 H 23 NO2: 357.1729, found 357.1720.

[0695] In this application, the terms "one embodiment," "some embodiments," "an example," "specific examples," or "examples" mean that a particular feature, structure, material, or characteristic is included in at least one embodiment or example of the present application. The illustrative appearances herein can not be necessary to all embodiments or examples. Moreover, descriptions of a particular feature, structure, material, or characteristic in relation to one embodiment or example does not indicate that it is absent from an additional embodiment or example of the present application, and that particular feature, structure, material, or characteristic can be present in one or more embodiments or examples. In addition, it is within the applicant's intent that all embodiments and examples appearing in the present application and any equivalents thereof are covered by the present application, in the context of the descriptions.

[0696] Although the embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary, and are not to be interpreted as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A method for synthesizing a 1,5-dicarbonyl compound, characterized by, The application relates to a synthesis method of a chiral 1,5-dicarbonyl compound. The 1,5-dicarbonyl compound is a chiral 1,5-dicarbonyl compound; The zirconium-containing catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst is one or more of ZrCl4, ZrBr4 and ZrF4; and the second catalyst is a chiral phosphoric acid; The chiral phosphoric acid has a structure of formula (I); The 1,3-dicarbonyl compound has a structure of formula (III), wherein R 1 , R 2 are The olefin compound has a structure of formula (IV), In formula (III), R 5 is phenyl or phenyl containing a substituent, R 6 is one of phenyl, phenyl containing a substituent, and C1-4 alkyl; The 1,5-dicarbonyl compound has a structure of formula (V), In formula (IV), R 7 is a phenyl group or a phenyl group having a substituent; The substituent in the phenyl group containing a substituent is halogen, C1-4 alkyl, C1-4 alkoxy or C1-4 haloalkyl. In formula (V), R 8 is phenyl or phenyl having a substituent, R 9 is one of phenyl, phenyl having a substituent, and C1-4 alkyl, R 10 is phenyl or phenyl having a substituent; The synthesis method of the 1,5-dicarbonyl compound further comprises:

2. The method of synthesis of claim 1, wherein, Before the 1,3-dicarbonyl compound and the olefin compound are reacted, the 1,3-dicarbonyl compound is first reacted with the first catalyst and the second catalyst to generate an intermediate shown in formula (II), and then the intermediate shown in formula (II) is mixed with the olefin compound in the organic solvent in an inert atmosphere and reacted under stirring and light source irradiation to generate the 1,5-dicarbonyl compound; Alternatively, before the 1,3-dicarbonyl compound and the olefin compound are reacted, part of the 1,3-dicarbonyl compound is first reacted with the first catalyst and the second catalyst to generate an intermediate shown in formula (II), and then the intermediate shown in formula (II), another part of the 1,3-dicarbonyl compound and the olefin compound are mixed in the organic solvent in an inert atmosphere and reacted under stirring and light source irradiation to generate the 1,5-dicarbonyl compound; The organic solvent is one or more of chloroform, dichloromethane and 1,2-dichloroethane; In formula (II), R 3 is phenyl or a substituted phenyl group, R 4 is one of phenyl or a substituted phenyl group, C1-4alkyl, the substituent of the substituted phenyl group being halogen, C1-4alkyl, C1-4alkoxy or C1-4haloalkyl.

3. The method of synthesis according to claim 1 or 2, wherein, And / or, the light source is visible light. The organic solvent is chloroform; 4. The method of synthesis of claim 3, wherein, And / or, the light source is a 10W 400nm LED; And / or, the first catalyst is ZrCl4. The mole amount of the 1,3-dicarbonyl compound is a mol, the mole amount of the olefin compound is b mol, and the value of a / b is 1, 1 / 2, 1 / 3 or 2.

5. The method of synthesis of claim 1, wherein, ​

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