阅读说明：本技术 一种含氟1,4-二烯化合物及衍生物、位点选择性合成方法 (Fluorine-containing 1, 4-diene compound, derivative and site selective synthesis method ) 是由 夏莹 曾雅鑫 朱毓雷 江忠涛 于 2021-10-13 设计创作，主要内容包括：本发明公开了一种含氟1,4-二烯化合物及衍生物、位点选择性合成方法,包括支链型化合物Ⅰ,直链型化合物Ⅱ和Ⅲ；制备方法包括以下步骤：步骤1：将烯烃、二氟环丙烷、金属铑催化剂、膦配体、添加剂和溶剂在氮气环境下充分混合溶解；步骤2：步骤1得到的混合物在100℃条件下,充分反应；步骤3：将步骤2得到的反应产物冷却后,分离提纯,即可得到含氟1,4-二烯化合物及其衍生物；本发明原料简单易得,合成路径简单,目标化合物产率较高,选择性好,在实验当中具有较高产率及优秀的选择性合成支链型和直链型含氟1,4-二烯化合物；可以应用到生物活性分子的修饰中,位点选择性合成复杂含氟1,4-二烯化合物,展现了其合成应用的潜在价值。(The invention discloses a fluorine-containing 1, 4-diene compound, a derivative thereof and a site selective synthesis method, which comprises a branched chain compound I, straight chain compounds II and III; the preparation method comprises the following steps: step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃; and step 3: cooling the reaction product obtained in the step 2, and then separating and purifying to obtain a fluorine-containing 1, 4-diene compound and a derivative thereof; the method has the advantages of simple and easily obtained raw materials, simple synthesis path, higher yield of the target compound, good selectivity, higher yield and excellent selectivity in experiments for synthesizing the branched-chain and straight-chain fluorine-containing 1, 4-diene compounds; can be applied to modification of bioactive molecules, and site-selectively synthesizes complex fluorine-containing 1, 4-diene compounds, thereby showing potential value of synthesis and application thereof.)

1. A fluorine-containing 1, 4-diene compound and derivatives thereof are characterized by comprising a branched-chain compound I, straight-chain compounds II and III;

the branched compound I has the following structure:

in the formula: r¹Is any one of the following groups: phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-tert-butylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-acetylmethoxybenzene groupPhenyl, 3-fluorophenyl, 3-chlorophenyl, 3-methoxyphenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-acetylmethoxyphenyl, 3-methoxyphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl, 1-naphthyl, n-hexyl;

the structure of the straight-chain compound II is as follows:

in the formula: r¹Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl;

the structure of the straight-chain compound III is as follows:

in the formula: r¹Is 4-methylphenyl; r³Is one of 1, 1-distyryl and indenyl.

2. The method for preparing fluorine-containing 1, 4-diene compounds and derivatives according to claim 1, wherein the method for preparing the branched compound I comprises the following steps:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetravinyldirhodium dichloride; the additive is a mixture of boric acid and 2, 6-di-tert-butyl-4-methylpyridine;

step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃;

and step 3: and (3) cooling the reaction product obtained in the step (2), and separating and purifying to obtain the fluorine-containing 1, 4-diene compound shown as the formula I and the derivative thereof.

3. The method for preparing a fluorine-containing 1, 4-diene compound and derivative according to claim 1, wherein the linear compound II or III is prepared by a method comprising the steps of:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetracarbonyl rhodium dichloride; the additive is one of silver tetrafluoroborate, bis (trifluoromethanesulfonyl) imide silver and silver trifluoromethanesulfonate;

step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃;

and step 3: and (3) cooling or separating and purifying the reaction product obtained in the step (2) to obtain the fluorine-containing 1, 4-diene compound shown as a formula II or III and derivatives thereof.

4. The method for preparing fluorine-containing 1, 4-diene compounds and derivatives according to claim 2, wherein the molar ratio of the olefin to the difluorocyclopropane in the step 1 is 1: 1.2.

5. The method for preparing fluorine-containing 1, 4-diene compounds and derivatives according to claim 2, wherein the molar ratio of the additive to the olefin is 1: 4.

6. The method for preparing fluorine-containing 1, 4-diene compounds and derivatives according to claim 3, wherein the molar ratio of the olefin to the difluorocyclopropane in the step 1 is 2:1 to 3: 1.

7. The method for preparing fluorine-containing 1, 4-diene compounds and derivatives according to claim 3, wherein the molar ratio of the additive to the olefin is 1: 20.

8. The process for producing a fluorine-containing 1, 4-diene compound or derivative according to claim 2 or 3, wherein the molar ratio of the metal rhodium catalyst to the olefin or difluorocyclopropane is 1: 50.

9. The process for producing a fluorine-containing 1, 4-diene compound or derivative according to claim 2 or 3, wherein the solvent is 1, 4-dioxane, and the reaction concentration of the olefin or the difluorocyclopropane is 0.1 to 2 mol/L.

10. The process for producing a fluorine-containing 1, 4-diene compound or derivative according to claim 2 or 3, wherein the phosphine ligand is diphenylcyclohexylphosphine, and the molar ratio of the phosphine ligand to the metal rhodium catalyst is 2: 1.

Technical Field

The invention relates to the technical field of fluorine-containing compounds and synthesis, in particular to a fluorine-containing 1, 4-diene compound, a derivative and a site selective synthesis method.

Background

Fluorine atoms are the elements with the strongest electronegativity in the periodic table of elements, have small atomic radii, and introduce fluorine or fluorine-containing groups into organic molecules to show electronic effects, osmotic effects, barrier effects and simulation effects, and are called as "fluorine effects". Fluorine atoms change the physical and chemical properties and biological activity of organic molecules, so that fluorine-containing organic compounds have very wide application in the fields of materials, pesticides and medicines. And also as potential bioisosteres of hydrogen atoms, carbonyl groups, sulfonyl groups and cyano groups, and as master keys in the field of pharmaceutical chemistry. The many changes in properties brought about by fluorine atoms have led to the perfusion of numerous chemists, and extensive and intensive research has been conducted on them. The development of fluorination reagents and methods for fluorine and fluorine-containing functionalization have been developed in a sequential study, and the development of organofluorine chemistry has been vigorously driven. At present, researchers focus on how to synthesize fluorine-containing organic compounds by using easily available raw materials and by using highly efficient and precise methods. In addition, in a specific compound (such as an alkenyl unit of an olefin), introduction of a fluorine-containing group at different sites can cause different property changes, so that precise site-specific fluorine-containing functionalization is also a focus and a challenge.

The importance of 1, 4-diene building blocks in a wide variety of natural products, pharmaceutical molecules, and the challenges associated with the preparation of such compounds has prompted the development of a variety of synthetic approaches. In view of the fact that introduction of fluorine atoms into organic molecules can change various properties thereof powerfully, no report has been made on the current synthesis method of fluorine-containing 1, 4-diene.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for selectively synthesizing branched fluorine-containing 1, 4-diene and straight-chain fluorine-containing 1, 4-diene by regulating and controlling the electrical site of metal rhodium in the center of a rhodium catalyst.

The technical scheme adopted by the invention is as follows:

a fluorine-containing 1, 4-diene compound and derivatives thereof comprise a branched-chain compound I, straight-chain compounds II and III;

the branched compound I has the following structure:

in the formula: r¹Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-acetylmethoxyphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-methoxyphenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-acetylmethoxyphenyl, 3-methoxyphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl, 1-naphthyl, n-hexyl;

the structure of the straight-chain compound II is as follows:

in the formula: r¹Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl;

the structure of the straight-chain compound III is as follows:

in the formula: r¹Is 4-methylphenyl; r³Is one of 1, 1-distyryl and indenyl.

A preparation method of fluorine-containing 1, 4-diene compounds and derivatives thereof is provided, wherein a preparation method of a branched-chain compound I comprises the following steps:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetravinyldirhodium dichloride; the additive is a mixture of boric acid and 2, 6-di-tert-butyl-4-methylpyridine;

step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃;

and step 3: and (3) cooling the reaction product obtained in the step (2), and separating and purifying to obtain the fluorine-containing 1, 4-diene compound shown as the formula I and the derivative thereof.

A method for preparing fluorine-containing 1, 4-diene compounds and derivatives thereof, wherein the method for preparing straight chain type compounds II or III comprises the following steps:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetracarbonyl rhodium dichloride; the additive is one of silver tetrafluoroborate, bis (trifluoromethanesulfonyl) imide silver and silver trifluoromethanesulfonate;

step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃;

and step 3: and (3) cooling or separating and purifying the reaction product obtained in the step (2) to obtain the fluorine-containing 1, 4-diene compound shown as a formula II or III and derivatives thereof.

Further, the molar ratio of the olefin to the difluorocyclopropane in the step 1 of preparing the branched compound is 1: 1.2.

Further, the molar ratio of the additive to the olefin is 1: 4.

Further, in the step 1 for preparing the linear compound, the molar ratio of the olefin to the difluorocyclopropane is 2: 1-3: 1.

Further, the molar ratio of the additive to the olefin is 1: 20.

Further, the molar ratio of the metal rhodium catalyst to the olefin or the difluorocyclopropane is 1: 50.

Further, the solvent is 1, 4-dioxane, and the reaction concentration of the olefin or the difluorocyclopropane is 0.1-2 mol/L.

Further, the phosphine ligand is diphenyl cyclohexyl phosphine, and the molar ratio of the phosphine ligand to the metal rhodium catalyst is 2: 1.

The invention has the beneficial effects that:

(1) according to the invention, the electrical property of the additive on the central metal of the catalyst is controlled, and the steric effect realizes the control of the branched chain selectivity during the catalytic reaction of the neutral rhodium catalyst; when the cationic rhodium catalyst reacts, the electronic effect realizes the control of linear chain selectivity;

(2) the method has the advantages of simple and easily obtained raw materials, simple synthesis path, higher yield of the target compound, good selectivity, higher yield and excellent selectivity in experiments for synthesizing the branched-chain and straight-chain fluorine-containing 1, 4-diene compounds;

(3) the invention solves the problem of high selectivity fluorine-containing functionalization of C-H in olefin and makes up the defects of the prior art;

(4) the method can be applied to modification of bioactive molecules, and the complex fluorine-containing 1, 4-diene compound is synthesized in a site selective manner, so that the potential value of the synthesis application of the compound is shown.

Drawings

FIG. 1 is a schematic diagram of the reaction process of the compound of the present invention.

FIG. 2 is a parameter diagram of the NMR spectrum of the product of example 1.

FIG. 3 is a parameter diagram of the NMR carbon spectrum of the product of example 1.

FIG. 4 is a parameter diagram of the NMR spectra of the product of example 1.

FIG. 5 is a parameter diagram of the NMR spectrum of the product of example 2.

FIG. 6 is a parameter diagram of the NMR carbon spectrum of the product of example 2.

FIG. 7 is a parameter diagram of the NMR spectra of the product of example 2.

FIG. 8 is a parameter diagram of the NMR spectrum of the product of example 3.

FIG. 9 is a parameter diagram of the NMR carbon spectrum of the product of example 3.

FIG. 10 is a parameter diagram of the NMR spectra of the product of example 3.

Detailed Description

The invention is further described with reference to the following figures and specific embodiments.

A fluorine-containing 1, 4-diene compound and derivatives thereof comprise a branched-chain compound I, straight-chain compounds II and III;

the branched compound I has the following structure:

in the formula: r¹Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-acetylmethoxyphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-methoxyphenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 4-acetylmethoxyphenyl, 3-methoxyphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl, 1-naphthyl, n-hexyl;

the structure of the straight-chain compound II is as follows:

in the formula: r¹Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenylphenyl, 4-fluorophenyl, 4-chlorophenyl, 2-naphthyl; r²Is any one of the following groups: phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 3-chlorophenyl, 2-naphthyl;

the structure of the straight-chain compound III is as follows:

in the formula: r¹Is 4-methylphenyl; r³Is one of 1, 1-distyryl and indenyl.

The preparation method of the branched compound I comprises the following steps:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetravinyldirhodium dichloride; the additive is a mixture of boric acid and 2, 6-di-tert-butyl-4-methylpyridine; the molar ratio of the olefin to the difluorocyclopropane is 1: 1.2; the molar ratio of additive to olefin was 1: 4. The solvent is 1, 4-dioxane, and the reaction concentration of the solvent is 2 mol/L. The phosphine ligand is diphenyl cyclohexyl phosphine, and the molar ratio of the phosphine ligand to the metal rhodium catalyst is 2: 1.

Step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃; the reaction can be carried out under magnetic stirring.

And step 3: and (3) cooling the reaction product obtained in the step (2), and separating and purifying by silica gel column chromatography to obtain the fluorine-containing 1, 4-diene compound shown as the formula I and the derivative thereof.

The reaction equation is shown in the following chart:

the preparation method of the straight-chain compound II or III comprises the following steps:

step 1: fully mixing and dissolving olefin, difluorocyclopropane, a metal rhodium catalyst, a phosphine ligand, an additive and a solvent in a nitrogen environment; the catalyst is tetracarbonyl rhodium dichloride; the additive is one of silver tetrafluoroborate, silver bistrichloromethanesulfonate and silver trifluoromethanesulfonate; the mol ratio of the olefin to the difluorocyclopropane is 2: 1-3: 1; the molar ratio of the metal rhodium catalyst to the difluorocyclopropane was 1: 50. The solvent is 1, 4-dioxane, and the reaction concentration of difluorocyclopropane is 0.1 mol/L. The phosphine ligand is diphenyl cyclohexyl phosphine, and the molar ratio of the phosphine ligand to the metal rhodium catalyst is 2: 1.

Step 2: fully reacting the mixture obtained in the step 1 at the temperature of 100 ℃;

and step 3: and (3) cooling the reaction product obtained in the step (2) or separating and purifying the reaction product by using a silica gel column chromatography to obtain the fluorine-containing 1, 4-diene compound shown as a formula II or III and derivatives thereof.

The reaction equation is shown in the following chart:

example 1

Synthesizing fluorine-containing 1, 4-diene compounds and derivatives according to the following steps:

step 1: a4 mL screw-top vial was charged sequentially with magnetic stirrer, 0.24mmol of phenyldifluorocyclopropane, 0.2mmol of styrene, 0.004mmol of tetravinyldichlororhodium, 0.008mmol of diphenylcyclohexylphosphine, 0.05mmol of boric acid, 0.05mmol of 2, 6-di-t-butyl-4-methylpyridine, and 0.1mL of 1, 4-dioxane in a nitrogen atmosphere glove box, sealed with a screw cap, and removed from the glove box.

Step 2: placing the mixture obtained in the step 1 on a magnetic stirrer at 100 ℃, and heating and stirring for 48 hours;

and step 3: after completion of the stirring reaction, the organic phase was concentrated by a rotary evaporator, and the residue was separated and purified by silica gel column chromatography to obtain the objective product (Rf ═ 0.3, PE) in a yield of 75% as a colorless oil.

The resulting compound has the structure:

the hydrogen nuclear magnetic resonance spectrum of the product is shown in figure 2:¹H NMR(400MHz,CDCl₃)δ7.48–7.41(m,4H),7.36–7.24(m,5H),7.20–7.15(m,1H),5.54(s,1H),5.54(d,J＝39.1Hz,1H),5.29(s,1H),3.50(d,J＝15.3Hz,2H)。

the nuclear magnetic resonance carbon spectrum of the product is shown in figure 3:¹³C NMR(101MHz,CDCl₃)δ158.4(d,J＝267.3Hz),142.5(d,J＝2.2Hz),140.1,133.6(d,J＝2.6Hz),128.4,128.4,128.3(d,J＝7.3Hz),127.8,126.9(d,J＝2.3Hz),125.9,115.7,107.8(dd,J＝8.1,2.6Hz),39.2(d,J＝27.9Hz)。

the NMR spectrum of the product is shown in FIG. 4:¹⁹F NMR(376MHz,CDCl₃)δ-99.60。

the high resolution mass spectrum of the product was: HRMS (ESI, m/z): calcd for C₁₇H₁₅F[M+H]⁺239.1231,found239.1231。

Example 2

Synthesizing fluorine-containing 1, 4-diene compounds and derivatives according to the following steps:

step 1: a4 mL screw-top vial was charged sequentially with a magnetic stirrer, (4-methylphenyl) difluorocyclopropane 0.2mmol, styrene 0.4mmol, dicarbonyl dirhodium dichloride 0.004mmol, diphenylcyclohexylphosphine 0.008mmol, silver tetrafluoroborate 0.01mmol, and 1, 4-dioxane 2mL in a glove box under nitrogen. Sealed with a screw cap and removed from the glove box.

Step 2: placing the mixture obtained in the step 1 on a magnetic stirrer at 100 ℃, and heating and stirring for 12 hours;

and step 3: after completion of the stirring reaction, the organic phase was concentrated by a rotary evaporator, and the residue was separated and purified by silica gel column chromatography to obtain the objective product (Rf ═ 0.25, PE) in a colorless oily state at a yield of 70%.

The resulting compound has the structure:

the nmr spectrum of the product is shown in fig. 5:¹H NMR(400MHz,CDCl₃)δ7.40–7.35(m,4H),7.31(t,J＝7.7Hz,2H),7.22(dd,J＝6.9,1.9Hz,1H),7.12(d,J＝7.9Hz,2H),6.54(d,J＝15.8Hz,1H),6.25(dt,J＝15.8,6.9Hz,1H),5.51(d,J＝39.4Hz,1H),3.22(dd,J＝14.9,6.8Hz,2H),2.32(s,3H)。

the nuclear magnetic resonance carbon spectrum of the product is shown in FIG. 6:¹³C NMR(101MHz,CDCl₃)δ158.4(d,J＝266.3Hz),137.0,136.6(d,J＝2.3Hz),133.3,130.8(d,J＝2.6Hz),129.2,128.6,128.3(d,J＝7.2Hz),127.5,126.3,123.7(d,J＝3.4Hz),106.5(dd,J＝8.2,2.5Hz),36.7(d,J＝28.2Hz),21.2(d,J＝2.0Hz)。

the NMR spectrum of the product is shown in FIG. 7:¹⁹F NMR(376MHz,CDCl₃)δ-100.67。

the high resolution mass spectrum of the product was: HRMS (ESI, M/z), calcd for C18H17F [ M + H ] +253.1387, found 253.1387.

Example 3

Synthesizing fluorine-containing 1, 4-diene compounds and derivatives according to the following steps:

step 1: sequentially adding a magnetic stirrer, 0.2mmol of (4-methylphenyl) difluorocyclopropane, and a solvent into a 4mL screw-mouth small bottle in a glove box in a nitrogen environment,0.4mmol, 0.004mmol of dicarbonyl dirhodium dichloride, 0.008mmol of diphenyl cyclohexyl phosphine, 0.01mmol of silver tetrafluoroborate and 2mL of 1, 4-dioxane. Sealed with a screw cap and removed from the glove box.

Step 2: placing the mixture obtained in the step 1 on a magnetic stirrer at 100 ℃, and heating and stirring for 12 hours;

and step 3: after completion of the stirring reaction, the organic phase was concentrated by a rotary evaporator, and the residue was separated and purified by silica gel column chromatography to obtain the objective product (Rf 0.6, PE: EA 100:1) in 54% yield as a colorless oil.

The resulting compound has the structure:

the NMR spectrum of the product is shown in FIG. 8:¹H NMR(400MHz,CDCl₃)δ7.37(t,J＝6.9Hz,3H),7.30(d,J＝7.4Hz,1H),7.23(t,J＝7.7Hz,1H),7.16–7.09(m,3H),6.70(s,1H),5.53(d,J＝38.9Hz,1H),3.48(d,J＝18.0Hz,2H),3.41(s,2H),2.32(s,3H)。

the nuclear magnetic resonance carbon spectrum of the product is shown in FIG. 9:¹³C NMR(101MHz,CDCl₃)δ158.0(d,J＝266.9Hz),145.0,143.8,143.3,136.7(d,J＝2.3Hz),130.6(d,J＝2.6Hz),129.4(d,J＝2.3Hz),129.1,128.2(d,J＝7.3Hz),126.3,124.2,123.5,120.4,107.0(dd,J＝8.3,3.8Hz),40.9,35.3(d,J＝28.8Hz),21.2(d,J＝3.2Hz)。

the NMR spectrum of the product is shown in FIG. 10:¹⁹F NMR(376MHz,CDCl₃)δ-100.69。

the high resolution mass spectrum of the product was: HRMS (ESI, m/z): calcd for C₁₉H₁₈F[M+H]⁺265.1387,found265.1387。

The invention has simple synthesis path, simple and easily obtained raw materials of the preparation method, higher yield of target products and good site selectivity, and can synthesize the novel fluorine-containing 1, 4-diene compound in site selectivity by simply changing the electrical property of the central metal of the catalyst, technically solves the high-selectivity fluorine-containing functionalization of C-H in olefin and makes up the defects of the prior art. In gram-scale experiments, branched-chain type and straight-chain type fluorine-containing 1, 4-diene are synthesized with high yield and excellent selectivity, and the strategy can be successfully applied to modification of bioactive molecules to synthesize complex fluorine-containing 1, 4-diene compounds, thereby showing potential value of synthesis and application thereof.