阅读说明：本技术 一种取代单氟联烯类化合物、其制备方法及应用 (Substituted monofluoroallene compound, preparation method and application thereof ) 是由 吴涛 杨丽鑫 于 2021-07-09 设计创作，主要内容包括：本发明公开一种取代单氟联烯类化合物、其制备方法及应用。本发明以二氟联烯化合物和格氏试剂为原料,CuCl为催化剂,THF为反应溶剂,在N-(2)氛围下搅拌进行偶联反应。反应结束后,0℃加入甲醇和饱和氯化铵淬灭反应,经过滤除去固体不溶物、干燥除水、再过滤得到粗产物,最后经由柱层析分离得到纯品。本发明使用廉价Cu作为C-F键活化反应的催化剂,反应体系反应条件温和,实现了含氟联烯类化合物与格氏试剂的选择性的C-F键烷基化及芳基化反应,为含氟化合物的进一步衍生化提供了新颖的中间体。(The invention discloses a substituted monofluoroallene compound, a preparation method and application thereof. The invention takes difluoro allene compound and Grignard reagent as raw materials, CuCl as catalyst, THF as reaction solvent, and the reaction is carried out in N 2 Stirring the mixture under the atmosphere to perform coupling reaction. After the reaction is finished, adding methanol and saturated ammonium chloride at 0 ℃ to quench the reaction, filtering to remove solid insoluble substances, drying to remove water, filtering again to obtain a crude product, and finally separating by column chromatography to obtain a pure product. The invention uses cheap Cu as a catalyst for C-F bond activation reaction, the reaction condition of the reaction system is mild, the selective C-F bond alkylation and arylation reaction of fluorine-containing allene compounds and Grignard reagents is realized, and a novel intermediate is provided for further derivatization of fluorine-containing compounds.)

1. A substituted monofluoroallene compound characterized by the general structure:

in the formula, R₁Long carbon chain or cyclic alkyl, including pyridine and thiophene heterocycle; r₂Is hydrogen or methyl;

r is aliphatic or aromatic hydrocarbon radical derived from Grignard reagent comprising aryl Grignard reagent and alkyl Grignard reagent, and alkyl Grignard reagent comprising long carbon chain alkyl Grignard reagent, branched chain alkyl Grignard reagent, cyclic alkyl Grignard reagent, alkyl Grignard reagent with heterocyclic ring on carbon chain.

2. A substituted monofluoroallene compound according to claim 1, characterized in that: the substituted monofluoroallenes have the following general structure:

in the formula, R₃The substituents are ortho, meta and para electron-donating substituents and electron-withdrawing substituents on a benzene ring and bromine as substituents, and in addition, the benzene ring can contain two substituents; r₃In addition to the substitution of the phenyl ring, the number of carbons between the phenyl ring and the allene may also be varied.

3. Use of substituted monofluoroallenes according to claim 1 or 2, characterized in that: the substituted monofluoroallene compound is used as an important intermediate for further derivatization, and the substituted monofluoroallene compound can react with phenyl magnesium bromide under standard conditions to obtain an alkynyl product containing a chiral center; the substituted monofluoroallenes can be hydrogenated by reacting the standard product with hydrogen to give a perhydrogenated fluorine-containing product in high yield.

4. The process for producing a substituted monofluoroallene compound according to claim 1 or 2, characterized in that: the method uses a difluoroallene compoundAnd Grignard reagent as raw material, CuCl as catalyst, THF as reaction solvent, in N₂Stirring under atmosphere to carry out coupling reaction; after the coupling reaction is finished, adding methanol and saturated ammonium chloride at 0 ℃ to quench the reaction, filtering to remove solid insoluble substances, drying to remove water, filtering again to obtain a crude product, and finally separating by column chromatography to obtain a pure product.

5. The process for producing a substituted monofluoroallene compound according to claim 4, characterized in that: the grignard reagent is added at-60 ℃; the coupling reaction time is 5 h; the coupling reaction temperature is-30 ℃ to rt.

6. The process for producing a substituted monofluoroallene compound according to claim 4, characterized in that: the molar equivalent ratio of the difluoroallene compound to the Grignard reagent is 1: 1.1-1.5, and the molar equivalent ratio of the difluoroallene compound to the CuCl is 1: 0.1.

7. The process for producing a substituted monofluoroallene compound according to claim 6, characterized in that: the molar equivalent ratio of the difluoroallene compound to the Grignard reagent is 1: 1.1.

Technical Field

The invention belongs to the technical field of pharmaceutical chemicals, and particularly relates to a substituted monofluoroallene compound, and a preparation method and application thereof.

Background

Research shows that the introduction of fluorine atoms into organic compound molecules can generate electronic effect, metabolism blocking effect and lipophilicity effect. With the continuous development of organic fluorine chemical synthesis methods and the continuous and deep understanding of the influence of fluorination on molecular biological characteristics, a plurality of fluorine-containing medicaments with complex structures and unique effects appear. Fluorine-containing drugs have the advantages of higher biological activity, stronger stability, difficult generation of drug resistance and the like, so that introduction of fluorine atoms into organic compound molecules becomes an important means for developing new anti-tumor drugs, antiviral drugs, anti-inflammatory drugs, central nervous system drugs and the like. And the breakage, activation and functionalization of inert C-F bonds in fluorine-containing compounds are important hot research fields in organic fluorine chemistry and metal organic chemistry. Therefore, fluorine has been receiving a great deal of attention as an important element.

Allenes are ubiquitous in organic chemistry as intermediates and targets, with allene structures being present in 2900 a variety of natural metabolites and synthetic compounds, and have been studied for over 40 years for their biological activity. However, only a few fluorinated allene structures have been published. Therefore, the research on the activation of C-F bonds containing the fluoroallene is of great significance.

Disclosure of Invention

Aiming at the development trend and vacancy of the prior organic fluorine compound, the invention aims to provide a substituted monofluorodiene compound, a preparation method and application thereof.

The invention is realized by the following technical scheme:

the invention provides a substituted monofluoroallene compound which has the following general structure,

R₁can be long carbon chain or cyclic alkyl, and comprises heterocyclic rings such as pyridine, thiophene and the like; r₂May be hydrogen or methyl;

r is aliphatic hydrocarbon or aromatic hydrocarbon, which is derived from Grignard reagent and comprises aryl Grignard reagent and alkyl Grignard reagent, the alkyl Grignard reagent comprises long-chain alkyl Grignard reagent, branched-chain alkyl Grignard reagent, cyclic alkyl Grignard reagent and alkyl Grignard reagent with heterocyclic ring on carbon chain, and R substituent in the alkyl Grignard reagent can be long-chain alkyl, branched-chain alkyl, cyclic alkyl and alkyl with heterocyclic ring on carbon chain.

Further, the substituted monofluoroallenes have the following general structure:

wherein R is₃Is ortho, meta and para electron-donating substituent (such as methyl, tertiary butyl and methoxy) and electron-withdrawing substituent (such as fluorine, chlorine and trifluoromethyl) on a benzene ring and substituent bromine; in addition, the benzene ring may contain two substituents, and the number of carbons between the benzene ring and the allene may be changed in addition to the substitution of the benzene ring.

The second invention provides the application of the substituted monofluoroallene compound, which can react with phenyl magnesium bromide under standard conditions to obtain an alkynyl product containing a chiral center; the standard product can also be reacted with hydrogen to produce hydrogenation to give a fully hydrogenated fluorine-containing product in 85% yield.

The third invention provides a preparation method of the substituted monofluoroallene compound, which takes a difluoroallene compound and a Grignard reagent as raw materials, CuCl as a catalyst, THF as a reaction solvent and N₂Stirring under atmosphere to carry out coupling reaction; after the coupling reaction is finished, adding methanol and saturated ammonium chloride at 0 ℃ to quench the reaction, filtering to remove solid insoluble substances, drying to remove water, filtering again to obtain a crude product, and finally separating by column chromatography to obtain a pure product。

Further, the grignard reagent was added at-60 ℃; the coupling reaction time is 5 h; the coupling reaction temperature is from-30 ℃ to rt, preferably rt (room temperature).

Further, the molar equivalent ratio of the difluoroallene compound to the Grignard reagent is 1: 1.1-1.5, preferably 1: 1.1.

Further, the molar equivalent ratio of the difluoroallene compound to the CuCl is 1: 0.1.

Compared with the prior art, the invention has the beneficial effects that:

(1) the method adopts the Grignard reagent and the difluoroallene as raw materials, the Grignard reagent has strong activity, is cheap and easy to obtain, is environment-friendly, reduces the reaction cost and has the advantage of environmental friendliness. The Grignard reagent and the difluoro allene both have better universality, and the reactivity of the Grignard reagent and the difluoro allene is greatly expanded.

(2) The substituted monofluoroallene compound has low reaction cost and novel structure, and can be used as an important intermediate for further derivatization.

Detailed Description

The present invention will be further described with reference to the following examples.

The invention takes difluoro allene compound and Grignard reagent as raw materials, CuCl as catalyst, THF as reaction solvent, and the reaction is carried out in N₂The coupling reaction is carried out under stirring at room temperature under the atmosphere. After the reaction is finished, adding methanol and saturated ammonium chloride at 0 ℃ to quench the reaction, filtering to remove solid insoluble substances, drying to remove water, filtering again to obtain a crude product, and finally separating by column chromatography to obtain a pure product.

In specific implementation, the catalyst can adopt CuBr, CuTC, CuCl and CuCl₂In the examples of the present invention, CuCl is specifically used as a catalyst; as the solvent, toluene, acetone, TBME, DMF, 1, 4-dioxane, benzene, n-hexane, DME, THF, and particularly THF as a reaction solvent in the examples of the present invention can be used.

The reaction temperature of the difluoroallene compound with the Grignard reagent ranges from-30 ℃ to rt, and in the examples, rt (room temperature) is specific.

The molar equivalent ratio of the difluoroallene compound to the Grignard reagent is 1: 1.1-1.5, specifically 1: 6 in the embodiment of the invention; the molar equivalent ratio of the difluoroallene compound to CuCl was 1: 0.1.

In specific implementation, the Grignard reagent is added at-60 ℃; the coupling reaction time was 5 h.

The present invention will be further described with reference to examples without departing from the spirit or essential characteristics thereof.

Example 1: synthesis of (5-fluoroheptata-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at a low temperature, and finally purified by silica gel column chromatography to obtain 33.4mg of the product (5-fluoroheptata-3, 4-dien-1-yl) bezene with an isolated yield of 88%.

1H NMR(400MHz，CDCl3)δ＝7.30(t，J＝8Hz，2H)，7.20(d，J＝8Hz，3H)，5.98-5.92(m，1H)，2.79(t，J＝8Hz，2H)，2.51-2.43(m，2H)，2.34-2.25(m，2H)，0.98(t，J＝8Hz，3H).

19F NMR(376MHz，CDCl3)δ＝-132.81(m，1F).

13C NMR(100MHz，CDCl3)δ＝189.67(d，J＝26Hz)，143.37(d，J＝235Hz)，141.42，128.57，128.50，128.12，108.77(d，J＝11Hz)，34.60(d，J＝3Hz)，32.65，23.89(d，J＝32Hz)，10.49(d，J＝3Hz).

Example 2: synthesis of 1-fluoro-4- (5-fluorohepta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difluoropta-3, 4-dien-1-yl) -4-fluorobenezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 36.6mg of 1-fluoro-4- (5-fluorohepta-3, 4-dien-1-yl) bezene, isolated in 88% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.14(t，J＝6Hz，2H)，6.97(t，J＝8Hz，2H)，5.94-5.89(m，1H)，2.75(t，J＝8Hz，2H)，2.47-2.39(m，2H)，2.33-2.24(m，2H)，0.97(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-117.60(m，1F)，-132.82(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.84(d，J＝25Hz)，161.47(d，J＝242Hz)，143.46(d，J＝235Hz)，136.99(d，J＝3Hz)，129.91(d，J＝8Hz)，115.23(d，J＝11Hz)，108.49(d，J＝11Hz)，33.74(d，J＝4Hz)，32.72，23.89(d，J＝33Hz)，10.47(d，J＝3Hz).

Example 3: synthesis of 4- (5-fluoroheptata-3, 4-dien-1-yl) -1, 1' -biphenyl

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 4- (5, 5-difluoropta-3, 4-dien-1-yl) -1, 1' -biphenol-allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give the product 4- (5-fluoroheptata-3, 4-dien-1-yl) -1, 1' -biphenol 43mg with an isolated yield of 81%.

¹H NMR(400MHz，CDCl₃)δ＝7.56(d，J＝4Hz，2H)，7.51(d，J＝8Hz，2H)，7.42(t，J＝8Hz，2H)，7.33(t，J＝8Hz，1H)，7.26(d，J＝8Hz，2H)，5.97-5.92(m，1H)，2.81(t，J＝6Hz，2H)，2.52-2.44(m，2H)，2.32-2.23(m，2H)，0.95(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.73(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.76(d，J＝25Hz)，286.85(d，J＝235Hz)，141.17，140.55，139.11，129.01，128.87，127.25，127.20，127.14，108.73(d，J＝11Hz)，34.22(d，J＝4Hz)，32.62，23.91(d，J＝33Hz)，10.47(d，J＝4Hz).

Example 4: synthesis of 1- (5-fluoroheptata-3, 4-dien-1-yl) -4- (trifluoromethylphenyl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difluoropta-3, 4-dien-1-y1) -4- (triflomethyl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at a low temperature, and finally purified by silica gel column chromatography to obtain 34.6mg of 1- (5-fluoroheptata-3, 4-dien-1-y1) -4- (trifluoromethyl) bezene, which was isolated in a yield of 67%.

¹H NMR(400MHz，CDCl₃)δ＝7.54(d，J＝8Hz，2H)，7.31(d，J＝8Hz，2H)，5.95-5.90(m，1H)，2.84(t，J＝8Hz，2H)，2.52-2.43(m，2H)，2.31-2.22(m，2H)，0.94(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-62.39(s，3F)，-132.62(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.07(d，J＝25Hz)，145.52，143.65(d，J＝236Hz)，128.92，125.41(d，J＝4Hz)，125.41(d，J＝12Hz)，108.11(d，J＝11Hz)，34.29(d，J＝3Hz)，32.20，24.02，23.70，10.37(d，J＝4Hz).

Example 5: synthesis of 1-bromo-2- (5-fluorohepta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1-bromoo-2- (5, 5-difluoroenta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 37.5mg of 1-bromo-2- (5-fluoroheptata-3, 4-dien-1-yl) bezene, isolated in 70% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.53(d，J＝8Hz，1H)，7.23(s，2H)，7.09-7.05(m，1H)，5.99-5.93(m，1H)，2.95-2.87(m，2H)，2.50-2.42(m，2H)，2.35-2.26(m，2H)，0.98(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.47(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.76(d，J＝26Hz)，143.51(d，J＝235Hz)，140.64，132.96,130.57,127.92,127.56，124.58，108.42(d，J＝11Hz)，34.89(d，J＝4Hz)，31.04，23.88(d，J＝32Hz)，10.50(d，J＝3Hz).

Example 6: synthesis of 1- (5-fluoroheptata-3, 4-dien-1-yl) -3-methylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and ethylmegnesiumbromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difluoropta-3, 4-dien-1-yl) -3-methyllbenzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to obtain 35.5mg of 1- (5-fluoroheptata-3, 4-dien-1-y1) -3-methylbenzene, isolated in 87% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.19(t，J＝8Hz，1H)，7.01(t，J＝6Hz，3H)，5.97-5.92(m，1H)，2.74(t，J＝8Hz，2H)，2.49-2.41(m，2H)，2.34-2.25(m，5H)，0.98(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.76(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.62(d，J＝25Hz)，143.33(d，J＝235Hz)，141.37，138.04，129.42，128.40，126.85，125.56，108.86(d，J＝12Hz)，34.55(d，J＝3Hz)，32.71，23.9(d，J＝33Hz)，21.53，10.49(d，J＝4Hz).

Example 7: synthesis of 1- (5-fluoroheptata-3, 4-dien-1-yl) -2-methylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difiuoro penta-3, 4-dien-1-yl) -2-methyllbenzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature and finally purified by silica gel column chromatography to give 30.2mg of 1- (5-fluoroheptata-3, 4-dien-1-yl) -2-methylbenezene, isolated in 74% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.15(t，J＝4Hz，4H)，6.01-5.96(m，1H)，2.77(t，J＝8Hz，2H)，2.46-2.39(m，2H)，2.37-2.28(m，5H)，1.01(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.61(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.56(d，J＝26Hz)，143.37(d，J＝235Hz)，139.57，136.04，130.33，128.89，126.27，126.11，108.92(d，J＝12Hz)，31.97(d，J＝3Hz)，31.45，23.90(d，J＝33Hz)，19.41，10.53(d，J＝3Hz).

Example 8: synthesis of 1- (5-fluorohepta-3, 4-dien-1-yl) -4-methoxybenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difluoropta-3, 4-dien-1-yl) -4-methoxybenzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at a low temperature, and finally purified by silica gel column chromatography to give 35.2mg of 1- (5-fluoroheptata-3, 4-dien-1-yl) -4-methoxybenzene, which was isolated in a yield of 80%.

¹H NMR(400MHz，CDCl₃)δ＝7.12(d，J＝8Hz，2H)，6.84(d，J＝8Hz，2H)，5.96-5.91(m，1H)，3.79(s，3H)，2.72(t，J＝8Hz，2H)，2.46-2.38(m，2H)，2.34-2.25(m，2H)，0.98(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.83(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.64(d，J＝26Hz)，158.02，143.28(d，J＝234Hz)，133.51，129.46，113.90，107.32(d，J＝12Hz)，55.39，33.75(d，J＝3Hz)，32.93，23.91(d，J＝33Hz)，10.50(d，J＝4Hz).

Example 9: synthesis of 1- (5-fluoroheptata-3, 4-dien-1-yl) -4-methylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-dif luoropronta-3, 4-dien-1-yl) -4-methyllbenzene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature and finally purified by silica gel column chromatography to give 35.5mg of 1- (5-fluoroheptata-3, 4-dien-1-yl) -4-methylbenezene, isolated in 87% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.11(s，4H)，5.98-5.93(m，1H)，2.75(t，J＝8Hz，2H)，2.49-2.41(m，2H)，2.34-2.27(m，5H)，1.00(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.81(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.62(d，J＝26Hz)，143.30(d，J＝235Hz)，138.35，135.57，129.17，128.44，108.86(d，J＝12Hz)，34.20(d，J＝3Hz)，32.82，23.91(d，J＝32Hz)，21.13，10.49(d，J＝3Hz).

Example 10: synthesis of 1-chloro-4- (5-fluoroheptata-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1-chloro-4- (5, 5-difluoroenta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at a low temperature, and finally purified by silica gel column chromatography to obtain 30.5mg of 1-chloro-4- (5-fluoroheptata-3, 4-dien-1-yl) bezene, which was isolated in a yield of 68%.

¹H NMR(400MHz，CDCl₃)δ＝7.25(d，J＝8Hz，2H)，7.12(d，J＝8Hz，2H)，5.94-5.89(m，1H)，2.74(t，J＝8Hz，2H)，2.46-2.39(m，2H)，2.32-2.24(m，2H)，0.97(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.75(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.88(d，J＝26Hz)，143.5(d，J＝236Hz)，139.82，131.82，129.92，128.56，108.35(d，J＝11Hz)，33.86(d，J＝3Hz)，32.45，23.88(d，J＝33Hz)，10.44(d，J＝4Hz).

Example 11: synthesis of 4- (5-fluoroheptata-3, 4-dien-1-yl) -1, 2-dimethylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 4- (5, 5-difluorophenyl a-3, 4-dien-1-yl) -1, 2-dimethyllbenzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give the product 4- (5-fluoroheptata-3, 4-dien-1-yl) -1, 2-dimethylbenzene 34.9mg, isolated in 80% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.07(d，J＝8Hz，1H)，7.00(s，1H)，6.95(d，J＝8Hz，1H)，5.99-5.93(m，1H)，2.73(t，J＝8Hz，2H)，2.49-2.41(m，2H)，2.35-2.25(m，8H)，1.01(t，J＝8Hz，3H).

¹⁹FNMR(376MHz，CDCl₃)δ＝-132.78(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.53(d，J＝25Hz)，143.27(d，J＝235Hz)，138.86，136.57，134.21，129.95，129.73，125.87，108.97(d，J＝12Hz)，34.17(d，J＝4Hz)，32.88，23.91(d，J＝33Hz)，19.88，19.45，10.49(d，J＝4Hz).

Example 12: synthesis of 1- (5-fluoroheptata-3, 4-dien-1-yl) -3, 5-dimethylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (5, 5-difluorophenyl a-3, 4-dien-1-yl) -3, 5-dimethyllbenzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction is finished, the reaction is quenched by methanol and saturated aqueous NH4C1 solution at low temperature, and finally the product 1- (5-fluoroheptata-3, 4-dien-1-y1) -3, 5-dimethyllbenzene 37.9mg is obtained by silica gel column chromatography, and the isolation yield is 87%.

¹H NMR(400MHz，CDCl₃)δ＝6.84(d，J＝4Hz，3H)，5.98-5.93(m，1H)，2.71(t，J＝8Hz，2H)，2.49-2.41(m，2H)，2.31(s，8H)，1.00(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.77(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.56(d，J＝26Hz)，143.28(d，J＝235Hz)，141.35，137.95，127.73，126.43，108.94(d，J＝12Hz)，34.47(d，J＝3Hz)，32.76,23.91(d，J＝33Hz)，21.39，10.49(d，J＝3Hz).

Example 13: synthesis of 2-fluoro-4- (5-fluorohepta-3, 4-dien-1-yl) -1-methylbenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 4- (5, 5-difluorophenyl a-3, 4-dien-1-yl) -2-fluoroo-1-methylbenezene allenyl substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 33.7mg of 2-fluoro-4- (5-fluorohepta-3, 4-dien-1-yl) -1-methylbenzene, isolated in 76% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.08(t，J＝8Hz，1H)，6.85(t，J＝8Hz，2H)，5.95-5.90(m，1H)，2.73(t，J＝8Hz，2H)，2.47-2.40(m，2H)，2.34-2.27(m，2H)，2.24(s，3H)，0.98(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-118.20(t，J＝9.4Hz，1F)，-132.78(t，J＝9.4Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.80(d，J＝26Hz)，161.37(d，J＝242Hz)，143.47(d，J＝235Hz)，141.06(d，J＝7Hz)，131.34(d，J＝6Hz)，123.90(d，J＝4Hz)，122.30(d，J＝17Hz)，115.01(d，J＝22Hz)，108.48(d，J＝12Hz)，33.93(q，J＝3Hz)，32.43，23.89(d，J＝33Hz)，14.31(d，J＝3Hz)，10.45(d，J＝3Hz).

Example 14: synthesis of 4- (5-fluoroheptata-3, 4-dien-1-yl) pyridine

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 4- (5, 5-difluoropta-3, 4-dien-1-y1) pyridine allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 19.9mg of 4- (5-fluoroheptata-3, 4-dien-1-yl) pyridine, isolated in 52% yield.

¹H NMR(400MHz，CDCl₃)δ＝8.50(s，2H)，7.12(s，2H)，5.94-5.89(m，1H)，2.77(t，J＝8Hz，2H)，2.51-2.43(m，2H)，2.30-2.21(m，2H)，0.94(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.55(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.20(d，J＝26Hz)，150.28，149.86，143.81(d，J＝236Hz)，124.01，107.83(d，J＝12Hz)，33.65(d，J＝3Hz)，31.18，23.88(d，J＝33Hz)，10.42(d，J＝3Hz).

Example 15: synthesis of 2- (5-fluorohepta-3, 4-dien-1-yl) thiophene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and ethylmegnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 2- (5, 5-difluoropta-3, 4-dien-1-yl) thiolene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction is finished, the reaction is quenched by methanol and saturated aqueous solution of NH4C1 at low temperature, and finally the product 2- (5-fluoroheptata-3, 4-dien-1-yl) thiophene25.9mg is obtained after the purification by silica gel column chromatography, and the isolation yield is 66%.

¹H NMR(400MHz，CDCl₃)δ＝7.14(d，J＝4Hz，1H)，6.93(t，J＝4Hz，1H)，6.82(s，1H)，5.99-5.93(m，1H)，3.00(t，J＝8Hz，2H)，2.56-2.48(m，2H)，2.36-2.27(m，2H)，1.00(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.74(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.95(d，J＝26Hz)，144.15，143.63(d，J＝236Hz)，126.88，124.58，123.33，108.15(d，J＝12Hz)，32.85，28.67(d，J＝4Hz)，23.92(d，J＝32Hz)，10.49(d，J＝3Hz).

Example 16: synthesis of 1- (tert-butyl) -4- (5-fluoro-2-methylhepta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1- (tert-butyl) -4- (5, 5-difiuoro-2-methylpenta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, leq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to obtain 43.7mg of 1- (tert-butyl) -4- (5-fluoro-2-methylhepta-3, 4-dien-1-y1) bezene, the isolated yield was 84%.

¹H NMR(400MHz，CDCl₃)δ＝7.31(d，J＝8Hz，2H)，7.11(d，J＝8Hz，2H)，5.98-5.84(m，1H)，2.77-2.51(m，3H)，2.32-2.20(m，2H)，1.32(s，9H)，1.09-1.03(dd，J＝8Hz，J＝4Hz，3H)，0.97-0.86(m，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.51(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝188.29(d，J＝26Hz)，148.93(d，J＝4Hz)，143.88(dd，J＝51Hz，J＝50Hz)，137.22(d，J＝30Hz)，128.97，125.23(d，J＝2Hz)，114.68(dd，J＝11Hz，J＝11Hz)，42.42(dd，J＝4Hz，J＝4Hz)，37.83，35.59(d，J＝218Hz)，31.54，23.88(d，J＝33Hz)，19.39(dd，J＝4Hz，J＝3Hz)，10.51(t，J＝4Hz).

Example 17: synthesis of 3-fluorootetracea-3, 4-diene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and ethylmegnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of 1, 1-difluoroodeca-1, 2-diene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction is finished, methanol and saturated NH4Cl aqueous solution are used for quenching reaction at low temperature, and finally, the product 3-fluorotetraceca-3, 4-diene 29.7mg is obtained after silica gel column chromatography purification, and the separation yield is 70%.

¹H NMR(400MHz，CDCl₃)δ＝5.91-5.87(m，1H)，2.36-2.27(m，2H)，2.19-2.08(m，2H)，1.48-1.40(m，2H)，1.26(s，12H)，1.03(t，J＝8Hz，3H)，0.88(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.07(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.09(d，J＝23Hz)，148.20，109.83(d，J＝12Hz)，32.03，31.12，29.69，29.58，29.45，29.19，28.42(d，J＝4Hz)，23.93(d，J＝33Hz)，22.83，14.28，10.61(d，J＝3Hz).

Example 18: synthesis of (5-fluoro-3-methylhepta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluro-3-methylpenta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 33mg of product (5-fluoro-3-methylhepta-3, 4-dien-1-y1) benzene in 81% isolated yield.

¹H NMR(400MHz，CDCl₃)δ＝7.30(t，J＝8Hz，2H)，7.21(d，J＝8Hz，3H)，2.82-2.72(m，2H)，2.47-2.38(m，2H)，2.33-2.25(m，2H)，1.88(d，J＝8Hz，3H)，0.97(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-129.10(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝184.48(d，J＝25Hz)，141.81，141.66(d，J＝234Hz)，134.67，128.46，126.01，118.74(d，J＝12Hz)，37.58，33.84(d，J＝2Hz)，24.13(d，J＝34Hz)，21.70，10.68(d，J＝3Hz).

Example 19: synthesis of (4-fluorohexa-2, 3-dien-1-yl) cyclohexane

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (4, 4-difluorouva-2, 3-dien-1-yl) cyclohexoxane allenyl substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 29.1mg of the product (4-fluorohexa-2, 3-dien-1-yl) cyclohexane in an isolated yield of 80%.

¹H NMR(400MHz，CDCl₃)δ＝5.86-5.80(m，1H)，2.36-2.27(m，2H)，2.09-1.95(m，2H)，1.78-1.67(m，6H)，1.47-1.37(m，1H)，1.29-1.14(m，3H)，1.03(t，J＝8Hz，3H)，0.90-0.84(m，2H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.84(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.82(d，J＝25Hz)，142.34(d，J＝234Hz)，108.28(d，J＝12Hz)，39.15，37.58(d，J＝4Hz)，33.15(d，J＝8Hz)，26.60，26.37，23.99(d，J＝33Hz)，10.62(d，J＝3Hz).

Example 20: synthesis of (5-fluorohepta-3, 4-dien-1-yl) cyclohexane

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) cyclohexoxane substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 32.1mg of the product (5-fluorohepta-3, 4-dien-1-yl) cyclohexane in an isolated yield of 82%.

¹H NMR(400MHz，CDCl₃)δ＝5.91-5.87(m，1H)，2.36-2.27(m，2H)，2.17-2.09(m，2H)，1.67(t，J＝16Hz，6H)，1.36-1.30(m，2H)，1.26-1.12(m，5H)，1.02(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.96(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.00(d，J＝25Hz)，142.87(d，J＝234Hz)，110.04(d，J＝12Hz)，37.17，36.00(d，J＝3Hz)，33.35(d，J＝11Hz)，28.55，26.79，26.49，23.94(d，J＝33Hz)，10.60(d，J＝3Hz).

Example 21: synthesis of (3-fluoropenta-1, 2-dien-1-yl) cyclohexane

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (3, 3-difluororopa-1, 2-dien-1-yl) cyclohexoxane substrate (0.1mmol/0.5mL, leq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 19.5mg of the product (3-fluoropenta-1, 2-dien-1-yl) cyclohexane in an isolated yield of 58%.

¹H NMR(400MHz，CDCl₃)δ＝5.89-5.85(m，1H)，2.37-2.28(m，2H)，2.12-2.03(m，1H)，1.81-1.72(m，4H)，1.33-1.08(m，6H)，1.02(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-131.07(t，J＝9.4Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝187.81(d，J＝25Hz)，143.65(d，J＝238Hz)，115.30(d，J＝11Hz)，39.38，32.41(d，J＝3Hz)，26.20，26.01，23.90(d，J＝33Hz)，10.67(d，J＝4Hz).

Example 22: synthesis of (4-fluorohexa-2, 3-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and ethylmegnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min, and a solution of (4, 4-difluorouva-2, 3-dien-1-y1) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to obtain 23.9mg of product (4-fluorohexa-2, 3-dien-1-yl) benzene with an isolated yield of 68%.

¹H NMR(400MHz，CDCl₃)δ＝7.32(t，J＝8Hz，2H)，7.24(t，J＝8Hz，3H)，6.05-6.00(m，1H)，3.48(t，J＝8Hz，2H)，2.36-2.27(m，2H)，1.01(t，J＝8Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.00(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.54(d，J＝25Hz)，143.23(d，J＝236Hz)，138.96(d，J＝4Hz)，128.78，128.62，126.58，108.32(d，J＝11Hz)，37.90，23.92(d，J＝32Hz)，10.48(d，J＝3Hz).

Example 23: synthesis of (5-fluoro-2-methylhepta-3, 4-dien-2-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Ethyl magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluro-2-methylpenta-3, 4-dien-2-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 20.4mg of the product (5-fluoro-2-methylhepta-3, 4-dien-2-yl) bezene, isolated in 50% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.37(d，J＝8Hz，2H)，7.31(t，J＝8Hz，2H)，7.22(t，J＝8Hz，1H)，6.08-6.06(m，1H)，2.43-2.34(m，2H)，1.45(s，6H)，1.07(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-131.05(s，1F).

¹³C NMR(100MHz，CDCl₃)δ＝187.12(d，J＝26Hz)，147.86，144.67(d，J＝237Hz)，128.40，126.31，126.12，119.29(d，J＝11Hz)，41.17，28.97(d，J＝3Hz)，28.74(d，J＝3Hz)，24.07(d，J＝33Hz)，10.65(d，J＝3Hz).

Example 24: synthesis of (5-fluorohexa-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and Methylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and a saturated aqueous solution of NH4C1 at a low temperature, and finally purified by silica gel column chromatography to give 27.8mg of the product (5-fluorohexa-3, 4-dien-1-yl) bezene with an isolated yield of 79%.

¹H NMR(400MHz，CDCl₃)δ＝7.29(t，J＝8Hz，2H)，7.19(d，J＝8Hz，3H)，5.88-5.83(m，1H)，2.77(t，J＝8Hz，2H)，2.48-2.40(m，2H)，1.97(dd，J＝4Hz，J＝4Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-128.27(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.54(d，J＝25Hz)，141.39，138.20(d，J＝233Hz)，128.58，128.48，126.10，107.42(d，J＝12Hz)，34.47(d，J＝4Hz)，32.46，17.19(d，J＝36Hz).

Example 25: synthesis of (5-fluorodeodeba-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and the heptaylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain the product (5-fluorodeodeba-3, 4-dien-1-yl) bezene 43.16mg, isolated in 83% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.29(t，J＝6Hz，2H)，7.21-7.18(m，3H)，5.94-5.88(m，1H)，2.78(t，J＝8Hz，2H)，2.50-2.42(m，2H)，2.29-2.22(m，2H)，1.44-1.28(m，10H)，0.90(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.30(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.18(d，J＝25Hz)，141.92(d，J＝235Hz)，141.43，128.57，128.49，126.12，108.14(d，J＝12Hz)，34.61(d，J＝3Hz)，32.66，31.93，30.73(d，J＝32Hz)，29.17，29.04，25.97(d，J＝2Hz)，22.79，14.24.

Example 26: synthesis of (5-fluoro-7-methylcta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and the isobutylmagnesiumBromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-y1) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to obtain 32.7mg of product (5-fluoro-7-methylcta-3, 4-dien-1-yl) bezene with an isolated yield of 75%.

¹H NMR(400MHz，CDCl₃)δ＝7.30(t，J＝6Hz，2H)，7.21(d，J＝4Hz，3H)，5.92-5.87(m，1H)，2.79(t，J＝8Hz，2H)，2.53-2.42(m，2H)，2.20-2.08(m，2H)，1.86-1.78(m，1H)，0.96(d，J＝8Hz，6H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.36(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.92(d，J＝26Hz)，141.41，140.73(d，J＝236Hz)，128.59，128.50，126.12，107.54(d，J＝12Hz)，40.20(d，J＝31Hz)，34.7(d，J＝4Hz)，32.80，25.83，22.40(d，J＝11Hz).

Example 27: synthesis of (5-fluoroundeca-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and hexylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoroona-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to give 34.4mg of the product (5-fluoroundeca-3, 4-dien-1-y1) benzene in an isolated yield of 70%.

¹H NMR(400MHz，CDCl₃)δ＝7.30(t，J＝8Hz，2H)，7.20(t，J＝4Hz，3H)，5.94-5.89(m，1H)，2.78(t，J＝8Hz，2H)，2.50-2.42(m，2H)，2.30-2.22(m，2H)，1.43-1.30(m，8H)，0.90(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.29(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.18(d，J＝25Hz)，141.91(d，J＝236Hz)，141.43，128.57，128.50，126.12，108.14(d，J＝12Hz)，34.62(d，J＝3Hz)，32.66，31.70，30.76(d，J＝31Hz)，28.75，25.93(d，J＝2Hz)，22.72，14.22.

Example 28: synthesis of (5-fluoro-6, 6-dimethylheptata-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and tert-butylmegnesiumbromolide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to give 39.7mg of the product (5-fluoro-6, 6-dimethylhepta-3, 4-dien-1-yl) bezene, isolated in 91% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.30(t，J＝8Hz，2H)，7.21(d，J＝4Hz，3H)，5.97-5.94(m，1H)，2.78(t，J＝8Hz，2H)，2.51-2.42(m，2H)，1.11(s，9H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-144.14(t，J＝9.4Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝188.16(d，J＝27Hz)，148.85(d，J＝241Hz)，141.47，128.57，126.53，126.14，108.74(d，J＝12Hz)，34.63(d，J＝4Hz)，33.89(d，J＝28Hz)，32.78，27.49.

Example 29: synthesis of 2- (3-fluoro-7-phenylheptata-3, 4-dien-1-yl) -1, 3-dioxane

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and (2- (1, 3-dioxan-2-yl) ethyl) magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-y1) bezene allenyl substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction is finished, the reaction is quenched by methanol and saturated NH4Cl aqueous solution at low temperature, and finally the product 2- (3-fluoro-7-phenylhepta-3, 4-dien-1-yl) -1, 3-dioxane 36.98mg is obtained after the purification by silica gel column chromatography, and the separation yield is 67%.

¹H NMR(400MHz，CDCl₃)δ＝7.29(t，J＝8Hz，2H)，7.20(t，J＝8Hz，3H)，5.96-5.91(m，1H)，4.58(t，J＝6Hz，1H)，4.11(dd，J＝4Hz，J＝4Hz，2H)，3.76(t，J＝12Hz，2H)，2.77(t，J＝8Hz，2H)，2.48-2.36(m，4H)，2.14-2.02(m，1H)，1.74-1.69(m，2H)，1.34(d，J＝12Hz，1H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-132.82(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.73(d，J＝25Hz)，141.35，141.27(d，J＝235Hz)，128.53，128.51，126.12，108.82(d，J＝11Hz)，101.18，67.02，34.55(d，J＝3Hz)，32.63，31.60(d，J＝3Hz)，25.88，25.20(d，J＝34Hz).

Example 30: synthesis of 1-fluoro-4- (1-fluoro-5-phenylpenta-1, 2-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and (4-fluorophenyl) magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction is finished, the reaction is quenched by methanol and saturated NH4Cl aqueous solution at low temperature, and finally the product 1-fluoro-4- (1-fluoro-5-phenylpenta-1, 2-dien-1-y1) bezene 31.2mg is obtained after silica gel column chromatography purification, and the isolation yield is 61%.

¹H NMR(400MHz，C₆D₆)δ＝7.08(t，J＝8Hz，2H)，7.03-7.00(m，3H)，6.88(d，J＝8Hz，2H)，6.73(t，J＝8Hz，2H)，5.80(t，J＝8Hz，1H)，2.54-2.39(m，2H)，2.20-2.11(m，2H).

¹⁹F NMR(376MHz，C₆D₆)δ＝-113.44(m，1F)，-145.85(t，J＝11.28Hz，1F).

¹³C NMR(100MHz，C₆D₆)δ＝191.33(d，J＝26Hz)，162.95(d，J＝6Hz)，140.99,140.12(d，J＝230Hz)，128.79，128.74，126.49(d，J＝4Hz)，126.43，126.38，115.74(d，J＝22Hz)，111.70(d，J＝11Hz)，34.45(d，J＝3Hz)，32.57.

Example 31: synthesis of (3-fluorohepta-3, 4-diene-1, 7-diyl) dibenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and the phenylethynylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 21.2mg of the product (3-fluoroheptata-3, 4-diene-1, 7-diyl) dibenzylene in an isolated yield of 40%.

¹H NMR(400MHz，CDCl₃)δ＝7.28(t，J＝8Hz，4H)，7.20-7.14(m，6H)，5.89-5.85(m，1H)，2.74-2.54(m，6H)，2.40-2.32(m，2H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-134.03(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.21(d，J＝24Hz)，141.13(d，J＝51Hz)，128.58，128.48，126.25，126.12，108.71(d，J＝12Hz)，34.38(d，J＝3Hz)，32.51(d，J＝32Hz)，32.47，32.12.

Example 32: synthesis of (5-fluoro-6-methylhepta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and isopyropymagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4C1 solution at low temperature, and finally purified by silica gel column chromatography to give the product (5-fluoro-6-methylhepta-3, 4-dien-1-yl) benzene27.3mg, isolated in 67% yield.

¹H NMR(400MHz，CDCl₃)δ＝7.26(d，J＝4Hz，2H)，7.19(d，J＝8Hz，3H)，5.96-5.92(m，1H)，2.76(t，J＝8Hz，2H)，2.54-2.40(m，3H)，1.02(d，J＝8Hz，6H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-137.85(q，J＝7.52Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝188.81(d，J＝25Hz)，146.78(d，J＝238Hz)，141.45，128.58，128.52，126.14，109.04(d，J＝11Hz)，34.64(d，J＝4Hz)，32.73，29.76(d，J＝31Hz)，19.69(d，J＝4Hz).

Example 33: synthesis of (5-fluoroonadececa-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and tetra decylmagnenium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and a saturated aqueous solution of NH4Cl at a low temperature, and finally purified by silica gel column chromatography to obtain 36.5mg of a product (5-fluoroonadececa-3, 4-dien-1-yl) bezene with an isolated yield of 51%.

¹H NMR(400MHz，CDCl₃)δ＝7.29(d，J＝8Hz，2H)，7.20(d，J＝12Hz，3H)，5.92-5.88(m，1H)，2.78(t，J＝6Hz，2H)，2.49-2.41(m，2H)，2.29-2.21(m，2H)，1.26(s，24H)，0.89(t，J＝6Hz，3H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-133.30(m，1F).

¹³C NMR(100MHz，CDCl₃)δ＝190.16(d，J＝25Hz)，141.93(d，J＝235Hz)，141.43，128.57，128.50，128.12，108.16(d，J＝12Hz)，34.63，34.59，32.68，32.07，30.88，30.57，29.85，29.84，29.83，29.81，29.73，29.52，29.09，25.97，22.85，14.29.

Example 34: synthesis of (5-cyclohexyl-5-fluoropenta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and cyclohexenylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-y1) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After completion of the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at a low temperature, and finally purified by silica gel column chromatography to give 37mg of the product (5-cyclohexyl-5-fluoropenta-3, 4-dien-1-yl) bezene in an isolated yield of 76%.

¹H NMR(400MHz，CDCl₃)δ＝7.30(d，J＝8Hz，2H)，7.21(d，J＝8Hz，3H)，5.97-5.93(m，1H)，2.78(t，J＝8Hz，2H)，2.53-2.40(m，2H)，2.26-2.18(m，1H)，1.83-1.72(m，4H)，1.30-1.05(m，6H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-138.73(q，J＝7.52Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.23(d，J＝25Hz)，145.83(d，J＝237Hz)，141.43，128.60，128.49，126.11，108.88(d，J＝12Hz)，38.81(d，J＝29Hz)，34.63(d，J＝3Hz)，32.78，29.87(d，J＝4Hz)，26.18，25.74.

Example 35: synthesis of (5-cyclopropyl-5-fluoropenta-3, 4-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and cyclopropylmegnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and a saturated aqueous solution of NH4Cl at a low temperature, and finally purified by silica gel column chromatography to give 24.6mg of a product (5-cyclopropy-5-ffluoropronta-3, 4-dien-1-yl) bezene with an isolated yield of 61%.

¹H NMR(400MHz，CDCl₃)δ＝7.29(t，J＝6Hz，2H)，7.20(t，J＝4Hz，3H)，5.93(t，J＝6Hz，1H)，2.77(t，J＝6Hz，2H)，2.49-2.41(m，2H)，1.53-1.44(m，1H)，0.76(d，J＝8Hz，2H)，0.58-0.54(m，2H).

¹⁹F NMR(376MHz，CDCl₃)δ＝-137.51(q，J＝7.52Hz，1F).

¹³C NMR(100MHz，CDCl₃)δ＝189.64(d，J＝29Hz)，143.4(d，J＝232Hz)，141.37，128.59，128.51，126.13，108.86(d，J＝11Hz)，34.58(d，J＝3Hz)，32.71，10.71(d，J＝40Hz)，5.71(d，J＝12Hz).

Example 36: synthesis of (1-fluoropenta-1, 2-diene-1, 5-diyl) dibenzene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and phenylmagnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoroona-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction was completed, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 23.3mg of the product (1-fluoropenta-1, 2-diene-1, 5-diyl) dibenzylene with an isolated yield of 49%.

¹H NMR(400MHz，C₆D₆)δ＝7.33(d，J＝8Hz，2H)，7.11-6.97(m，6H)，6.90(d，J＝8Hz，2H)，5.86(t，J＝8Hz，1H)，2.56-2.43(m，2H)，2.21-2.14(m，2H).

¹⁹F NMR(376MHz，C₆D₆)δ＝-146.67(t，J＝7.52Hz，1F).

¹³C NMR(100MHz，C₆D₆)δ＝191.66(d，J＝27Hz)，141.13，140.87(d，J＝230Hz)，131.93(d，J＝33Hz)，128.80，128.76，128.74，128.69，126.33，124.61(d，J＝4Hz)，111.48(d，J＝11Hz)，34.57(d，J＝3Hz)，32.59.

Example 37: synthesis of 1- (1-fluoro-5-phenylpenta-1, 2-dien-1-yl) -2-methylbenezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and o-tolylmegnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) bezene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to give 21.2mg of 1- (1-fluoro-5-phenylpenta-1, 2-dien-1-yl) -2-methyllbenzene, isolated in 42% yield.

¹H NMR(400MHz，C₆D₆)δ＝7.47(t，J＝12Hz，1H)，7.03(t，J＝8Hz，2H)，6.99-6.90(m，4H)，6.84(d，J＝8Hz，2H)，5.68(t，J＝4Hz，1H)，2.45(t，J＝8Hz，2H)，2.17(s，3H)，2.14-2.05(m，2H).

¹⁹F NMR(376MHz，C₆D₆)δ＝-131.74(t，J＝9.4Hz，1F).

¹³C NMR(100MHz，C₆D₆)δ＝193.92(d，J＝27Hz)，141.22，139.89(d，J＝231Hz)，135.88(d，J＝2Hz)，131.25，130.96(d，J＝31Hz)，128.94，128.73，128.66，127.40(d，J＝5Hz)，126.36，126.34，109.21(d，J＝13Hz)，34.62(d，J＝3Hz)，32.85，21.29.

Example 38: synthesis of 1-chloro-4- (1-fluoro-5-phenylpenta-1, 2-dien-1-yl) bezene

After adding the dried magneton to the dry Schlenk reaction tube, it was cooled to room temperature under vacuum, and it was transferred to a glove box under nitrogen atmosphere, added with CuCl (1mg, 0.1mmol), and taken out of the glove box hermetically. THF (0.4mL) was then added under a nitrogen atmosphere and (4-chlorophenyl) magnesium bromide Grignard reagent (1.1eq, 0.11mmol) was added at-60 deg.C, stirred at this temperature for 5min and a solution of (5, 5-difluoropta-3, 4-dien-1-yl) benzene allene substrate (0.1mmol/0.5mL, 1eq) in THF was added. The reaction was transferred to room temperature and stirred for 5 h. After the reaction, the reaction was quenched with methanol and saturated aqueous NH4Cl solution at low temperature, and finally purified by silica gel column chromatography to obtain 19.6mg of 1-chloro-4- (1-fluoro-5-phenylpenta-1, 2-dien-1-yl) bezene, isolated in 36% yield.

¹H NMR(400MHz，C₆D₆)δ＝7.09-7.01(m，5H)，6.94(d，J＝8Hz，2H)，6.87(d，J＝8Hz，2H)，5.77(t，J＝6Hz，1H)，2.52-2.36(m，2H)，2.18-2.09(m，2H).

¹⁹F NMR(376MHz，C₆D₆)δ＝-146.48(s，1F).

¹³C NMR(100MHz，C₆D₆)δ＝191.42(d，J＝26Hz)，140.91，139.89(d，J＝230Hz)，134.13，130.36(d，J＝33Hz)，128.95(d，J＝2Hz)，128.78，128.75，126.41，125.89(d，J＝4Hz)，111.81(d，J＝11Hz)，34.42(d，J＝3Hz)，32.46.

The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.