CN113683493A - Electron-rich conjugated diene compound, preparation method and application - Google Patents

Electron-rich conjugated diene compound, preparation method and application Download PDF

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CN113683493A
CN113683493A CN202111146599.6A CN202111146599A CN113683493A CN 113683493 A CN113683493 A CN 113683493A CN 202111146599 A CN202111146599 A CN 202111146599A CN 113683493 A CN113683493 A CN 113683493A
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夏莹
宁小琴
陈永柯
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Sichuan University
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Abstract

本发明公开了一种富电子共轭二烯类化合物、制备方法及应用，包括以下步骤：步骤1：将N‑(3‑(苄氧基)环丁基)‑4‑甲基苯磺酰腙、碱和催化剂混合；步骤2：加入膦配体、芳基卤化物和溶剂，在磁力搅拌、90℃温度、氮气气氛中充分反应；步骤3：冷却后，提纯即可得到所需富电子共轭二烯类化合物；或者通过一步法制备富电子共轭二烯类化合物；本发明中富电子的1,3‑丁二烯的制备方法，底物普适性好，官能团兼容性好；可在芳环上取代缺电子，富电子，杂环，萘环等基团，反应条件温和，所得到的产物结构单一且都为E型的富电子的1,3丁二烯；并且产物1,3共轭二烯能与烯烃和炔烃以较优的收率得到[4+2]环化的产物。

Figure 202111146599

The invention discloses an electron-rich conjugated diene compound, a preparation method and an application, comprising the following steps: Step 1: N-(3-(benzyloxy)cyclobutyl)-4-methylbenzenesulfonyl Hydrazone, base and catalyst are mixed; Step 2: Add phosphine ligand, aryl halide and solvent, fully react under magnetic stirring, 90°C temperature and nitrogen atmosphere; Step 3: After cooling, purify to obtain the desired electron-rich Conjugated diene compounds; or preparing electron-rich conjugated diene compounds by one-step method; the preparation method of electron-rich 1,3-butadiene in the present invention has good substrate universality and good functional group compatibility; Substitute electron-deficient, electron-rich, heterocyclic, naphthalene rings and other groups on the aromatic ring, the reaction conditions are mild, and the obtained products have a single structure and are all E-type electron-rich 1,3 butadiene; and the product 1, 3 Conjugated dienes can be combined with alkenes and alkynes to obtain [4+2] cyclized products in better yields.

Figure 202111146599

Description

Electron-rich conjugated diene compound, preparation method and application
Technical Field
The invention relates to the technical field of conjugated dienes, in particular to an electron-rich conjugated diene compound, and a preparation method and application thereof.
Background
The 1, 3-butadiene compound is used as an important skeleton in organic synthesis, has a conjugated system, and has wide application in cycloaddition and polymerization reactions. The conjugated diene rich in electrons is a common substrate for cyclization of [4+2], and can be used for constructing six-membered ring compounds by Diels-Alder reaction with dienophiles (olefins or alkynes), and is one of the very important means for forming carbon-carbon bonds in organic chemical synthesis reaction. Meanwhile, the naphthoquinone compound is also an important intermediate for synthesizing the bioactive compound, for example, the naphthoquinone compound generates [4+2] cyclization, so that a feasible method can be provided for the synthesis of the anthraquinone antibiotic. In addition, such electron-rich conjugated dienes have also been reported in the fields of polymerization and the like.
Currently, one method for synthesizing such electron-rich conjugated dienes is via intermolecular metathesis of enol ether-alkyne under ruthenium catalysis. The method mainly uses alkyl enol ether as a substrate and has the problem of stereoselectivity. Or through ylide reaction, firstly preparing a substrate into phosphorus ylide, and then reacting with corresponding ketene, the method has the defects that after the phosphorus triphenoxide is generated in the reaction process, the post-treatment is more complicated, if a single E isomer needs to be obtained, the reaction needs to be carried out at a lower temperature, the reaction time is long, and the reaction steps are multiple.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the electron-rich conjugated diene compound with better stereoselectivity, simple and convenient operation, the preparation method and the application.
The technical scheme adopted by the invention is as follows: an electron-rich conjugated diene compound has the following structure:
Figure BDA0003285723710000011
in the formula: ar is one of phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenyl, 4-fluorophenyl, 4-chlorobenzene, 4-trifluoromethylphenyl, 3-methoxyphenyl, 2-methylphenyl, 2-methoxyphenyl, 1, 2-methylenedioxyphenyl, 2-naphthyl and 3-thienyl.
The preparation method of the electron-rich conjugated diene compound comprises the following steps:
step 1: mixing N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone, a base and a catalyst;
step 2: adding a phosphine ligand, aryl halide and a solvent, and fully reacting under magnetic stirring at 90 ℃ in a nitrogen atmosphere;
and step 3: cooling and purifying to obtain the required electron-rich conjugated diene compound.
The preparation method of the electron-rich conjugated diene compound comprises the following steps:
step 1: mixing 3- (benzyloxy) cyclobutane-1-ketone, p-toluenesulfonyl hydrazide and a solvent, and fully reacting under the conditions of magnetic stirring and 60 ℃;
step 2: after cooling, adding an alkali, metal palladium, a phosphine ligand, an aryl halide and a solvent into the reaction mixture obtained in the step 1; fully reacting under the condition of magnetic stirring at 90 ℃ in nitrogen atmosphere;
and step 3: cooling and purifying to obtain the required electron-rich conjugated diene compound.
Further, the alkali is cesium carbonate, the catalyst is metal palladium, the phosphine ligand is diphenyl cyclohexyl phosphine, and the solvent is 1,4 dioxane.
Further, the catalyst is one of palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) palladium (II) dichloride and allyl palladium (II) chloride dimer.
Further, the molar ratio of the aryl halide to the N- (3- (benzyloxy) cyclobutyl) -4-methyl benzenesulfonylhydrazone or the p-toluenesulfonylhydrazide is 1: 1-1.5.
Further, the molar ratio of the catalyst to the phosphine ligand is 1: 2-4, the molar ratio of the aromatic halide to the catalyst is 1:0.04, and the molar ratio of the aromatic halide to the base is 1: 2.5-3.
Further, the molar ratio of the 3- (benzyloxy) cyclobutane-1-one to the aryl halide is 6: 5.
An application of an electron-rich conjugated diene compound, wherein the electron-rich conjugated diene compound is used as a substrate for [4+2] cyclization and reacts with a dienophile to construct a six-membered ring compound.
The invention has the beneficial effects that:
(1) the preparation method has Z/E selectivity, and the obtained electron-rich conjugated diene is E type 1, 3-butadiene with a single structure;
(2) the electron-rich conjugated diene is synthesized in one step by the simple and easily-obtained bromobenzene and p-toluenesulfonylhydrazone derived from cyclobutanone, and the preparation method is simple and convenient to operate;
(3) the electron-rich conjugated diene obtained by the invention is a common substrate for [4+2] cyclization, and can construct a six-membered ring compound with a yield of more than 85%.
Drawings
FIG. 1 is a schematic view of the preparation process of examples 1 to 3.
FIG. 2 is a schematic diagram of the preparation process of example 4.
FIG. 3 is a schematic diagram of the preparation process of example 5.
FIG. 4 is a NMR spectrum of the product of example 1.
FIG. 5 is a NMR carbon spectrum of the product of example 1.
FIG. 6 is a high resolution mass spectrum of the product of example 1.
FIG. 7 is a NMR spectrum of the product of example 5.
FIG. 8 is a NMR carbon spectrum of the product of example 5.
FIG. 9 is a high resolution mass spectrum of the product of example 5.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
An electron-rich conjugated diene compound has the following structure:
Figure BDA0003285723710000031
in the formula: ar is one of phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenyl, 4-fluorophenyl, 4-chlorobenzene, 4-trifluoromethylphenyl, 3-methoxyphenyl, 2-methylphenyl, 2-methoxyphenyl, 1, 2-methylenedioxyphenyl, 2-naphthyl and 3-thienyl.
The preparation method of the electron-rich conjugated diene compound is shown in figure 1 and comprises the following steps:
step 1: mixing N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone, a base and a catalyst;
step 2: adding a phosphine ligand, aryl halide and a solvent, and fully reacting under magnetic stirring at 90 ℃ in a nitrogen atmosphere;
and step 3: cooling and purifying to obtain the required electron-rich conjugated diene compound.
The preparation method of the electron-rich conjugated diene compound is shown in figure 2 and comprises the following steps:
step 1: mixing 3- (benzyloxy) cyclobutane-1-ketone, p-toluenesulfonyl hydrazide and a solvent, and fully reacting under the conditions of magnetic stirring and 60 ℃;
step 2: after cooling, adding an alkali, metal palladium, a phosphine ligand, an aryl halide and a solvent into the reaction mixture obtained in the step 1; fully reacting under the condition of magnetic stirring at 90 ℃ in nitrogen atmosphere;
and step 3: cooling and purifying to obtain the required electron-rich conjugated diene compound. Purification is carried out by using a silica gel column layer.
The alkali is cesium carbonate, the catalyst is metal palladium, the phosphine ligand is diphenyl cyclohexyl phosphine, and the solvent is 1,4 dioxane. The catalyst is one of palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) palladium dichloride (II) and allyl palladium chloride (II) dimer. The molar ratio of aryl halide to N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone or p-toluenesulfonylhydrazide is 1:1 to 1.5. The molar ratio of the catalyst to the phosphine ligand is 1: 2-4, the molar ratio of the aromatic halide to the catalyst is 1:0.04, and the molar ratio of the aromatic halide to the base is 1: 2.5-3. The molar ratio of 3- (benzyloxy) cyclobutane-1-one to aryl halide is 6: 5.
The electron-rich conjugated diene compound is used as a substrate for cyclization of [4+2], and reacts with dienophile to construct a six-membered ring compound.
The aromatic halide is aryl bromide and is any compound in the following structure:
Figure BDA0003285723710000041
the electron-rich conjugated diene compound is any one of the following structures:
Figure BDA0003285723710000042
example 1
Electron rich 1,3 butadiene was prepared as follows:
step 1: to an 8mL vial equipped with a magnetic stir bar were added 0.5mmol cesium carbonate, 0.24mmol N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone, 0.004mmol tris (dibenzylideneacetone) dipalladium, and the vial was sealed with a screw cap and transferred to a glove box.
Step 2: a vial was charged with 0.008mmol diphenylcyclohexylphosphine, 2.0mL 1, 4-dioxane, and 0.2mmol bromobenzene, capped with a screw cap and removed from the glove box. The mixture was stirred for 16 hours on a magnetic stirrer at 90 ℃.
And step 3: the reaction mixture was cooled to room temperature, filtered through celite, eluted with ethyl acetate, dried in vacuo, and transferred to a silica gel column, which was then eluted with an eluent (PE/EA 100:1) to obtain the desired product (Rf 0.5(PE EA 40:1)) as a colorless oil in 79% yield.
The structure is as follows:
Figure BDA0003285723710000051
the reaction process is as follows:
Figure BDA0003285723710000052
the NMR spectrum of the product is shown in FIG. 4:
1H NMR(400MHz,CDCl3)δ7.45-7.23(m,10H),6.55(d,J＝12.6Hz,1H),5.90(d,J＝12.6Hz,1H),5.09(d,J＝1.7Hz,1H),4.91(d,J＝1.8Hz,1H),4.80(s,2H)。
the nuclear magnetic resonance carbon spectrum of the product is shown in FIG. 5:
13C NMR(101MHz,CDCl3)150.4,145.4,140.8,136.7,128.5,128.1,128.0,128.0,127.5,127.4,111.9,108.8,71.9。
the high resolution mass spectrum of the product is shown in fig. 6:
the high resolution mass spectrum is as follows: HRMS (ESI, m/z): calcd for C17H17O[M+H]+237.1274,found 237.1274。
Example 2
Electron rich 1,3 butadiene was prepared as follows:
step 1: to an 8mL vial equipped with a magnetic stir bar were added 0.5mmol cesium carbonate, 0.24mmol N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone, 0.004mmol tris (dibenzylideneacetone) dipalladium, and the vial was sealed with a screw cap and transferred to a glove box.
Step 2: a vial was charged with 0.008mmol diphenylcyclohexylphosphine, 2.0mL 1, 4-dioxane, and 0.2mmol aryl bromide (Ar is naphthyl), capped and removed from the glove box. The mixture was stirred for 16 hours on a magnetic stirrer at 90 ℃.
And step 3: the reaction mixture was cooled to room temperature, filtered through celite, eluted with ethyl acetate, dried in vacuo, and transferred to a silica gel column, which was then eluted with an eluent (PE/EA 100:1) to obtain the desired product (Rf 0.5(PE EA 40:1)) as a colorless oil with a yield of 60%.
The reaction process is as follows:
Figure BDA0003285723710000053
the nuclear magnetic resonance hydrogen spectrum of the product is as follows:1H NMR(400MHz,CDCl3)δ7.83-7.76(m,4H),7.50-7.44(m,3H),7.39-7.28(m,5H),6.58(d,J＝12.7Hz,1H),5.98(d,J＝12.7Hz,1H),5.18(s,1H),5.04(s,1H),4.81(s,2H)。
the nuclear magnetic resonance carbon spectrum of the product is as follows:13C NMR(101MHz,CDCl3)δ150.7,145.4,138.3,136.8,133.4,132.9,128.6,128.1,128.1,127.6,127.6,126.7,126.5,126.1,125.9,112.5,108.9,72.0.
the high resolution mass spectrum of the product was: HRMS (ESI, m/z) C21H19O[M+H]+287.1430,calcd for 287.1429。
Example 3
Electron rich 1,3 butadiene was prepared as follows:
step 1: to an 8mL vial equipped with a magnetic stir bar were added 0.5mmol cesium carbonate, 0.24mmol N- (3- (benzyloxy) cyclobutyl) -4-methylbenzenesulfonylhydrazone, 0.004mmol tris (dibenzylideneacetone) dipalladium, and the vial was sealed with a screw cap and transferred to a glove box.
Step 2: a vial was charged with 0.008mmol diphenylcyclohexylphosphine, 2.0mL 1, 4-dioxane, and 0.2mmol aryl bromide (Ar is thiophene), capped, and removed from the glove box. The mixture was stirred for 16 hours on a magnetic stirrer at 90 ℃.
And step 3: the reaction mixture was cooled to room temperature, filtered through celite, eluted with ethyl acetate, dried in vacuo, and transferred to a silica gel column, which was then eluted with an eluent (PE/EA 100:1) to obtain the desired product (Rf 0.5(PE EA 40:1)) as a colorless oil in 73% yield.
The nuclear magnetic resonance hydrogen spectrum of the product is as follows:1H NMR(400MHz,CDCl3)δ7.87-7.74(m,2H),7.38-7.23(m,8H),6.39(d,J＝12.6Hz,1H),5.99(d,J＝12.7Hz,1H),5.27(d,J＝2.0Hz,1H),5.00(d,J＝2.1Hz,1H),4.73(s,2H)。
the reaction process is as follows:
Figure BDA0003285723710000061
the nuclear magnetic resonance carbon spectrum of the product is as follows:
13C NMR(101MHz,CDCl3)δ150.8,140.0,139.5,138.4,136.6,136.4,128.5,128.0,127.4,124.2,124.0,123.8,123.5,122.6,114.1,109.0,72.0。
the high resolution mass spectrum is: HRMS (ESI, m/z): calcd for C19H17OS[M+H]+293.0995,found 293.0995。
Example 4
Electron rich 1,3 butadiene was prepared as follows:
step 1: to an 8mL vial equipped with a magnetic stir bar were added 0.24mmol of 3- (benzyloxy) cyclobutane-1-one, 0.24mmol of p-toluenesulfonylhydrazide, and 1.0mL of 1, 4-dioxane. The resulting solution was sealed and stirred on a magnetic stirrer at 60 ℃ for 1 hour.
Step 2: after the reaction solution was cooled to room temperature, 0.5mmol of cesium carbonate, 0.004mmol of tris (dibenzylideneacetone) dipalladium, 0.008mmol of diphenylcyclohexylphosphine, 1.0mL of 1, 4-dioxane, and 0.2mmol of bromobenzene were added to the reaction mixture. The screw cap was closed and removed from the glove box and placed on a magnetic stirrer at 90 ℃ for 16 hours.
And step 3: the reaction mixture was cooled to room temperature, filtered through celite, eluted with ethyl acetate, dried in vacuo, transferred to a silica gel column, and eluted with an eluent (PE/EA 100:1) to give the desired product (Rf 0.5(PE EA 40:1)) as a colorless oil in 67% yield.
The reaction process is as follows:
Figure BDA0003285723710000071
the [4+2] cyclization reaction of partial compounds is explored, wherein the conjugated diene rich in electrons is a common substrate for [4+2] cyclization, and the conjugated diene and a dienophile (olefin or alkyne) can be subjected to Diels-Alder reaction to construct a six-membered ring compound, so that the conjugated diene is one of the very important means for forming carbon-carbon bonds in organic chemical synthesis reaction. The description will be made by taking example 5 as an example.
Example 5
The method comprises the following steps:
0.2mmol of 1-phenyl-1H-pyrrole-2, 5-dione was charged in a 4mL vial equipped with a magnetic stir bar, and 0.6mL of toluene was added. Then, 0.2mmol of conjugated diene was added. The resulting reaction mixture was stirred at 80 ℃ for 15 hours under nitrogen atmosphere. After cooling to room temperature, the reaction mixture was concentrated in vacuo. The crude mixture was purified by column chromatography on silica gel (PE: EA ═ 5:1) to afford the product as a white solid in 88% yield. The product structure is as follows:
Figure BDA0003285723710000072
the reaction process is as follows:
Figure BDA0003285723710000073
the nmr spectrum of the product is shown in fig. 7:1H NMR(400MHz,CDCl3)δ7.48-7.25(m,12H),7.24(s,1H),7.20-7.12(m,2H),6.45(dd,J＝5.5,2.3Hz,1H),4.77-4.70(m,1H),4.58(d,J＝11.4Hz,1H),4.50(d,J＝11.4Hz,1H),3.37(td,J＝9.4,7.1Hz,1H),3.25(dd,J＝9.8,4.5Hz,1H),3.19-3.04(m,2H)。
the nuclear magnetic resonance carbon spectrum of the product is shown in FIG. 8:13C NMR(101MHz,CDCl3)δ179.0,175.8,143.2,139.7,137.8,132.1,129.0,128.5,128.4,128.3,128.2,127.6,127.5,126.7,125.6,123.2,123.1,70.7,70.6,45.0,37.6,25.4。
the high resolution mass spectrum of the product is shown in fig. 9: HRMS (ESI, m/z): calcd for C27H23NNaO3[M+Na]+432.1570,found 432.1574。
Compared with the prior art, the preparation method of the electron-rich conjugated diene compound provided by the invention has the advantages that the electron-rich conjugated diene compound is mainly obtained through ring opening isomerization of a four-membered ring, the stereospecificity is good, and an E-type product can be selectively obtained. The 1, 3-butadiene obtained by the method is obtained by thermal ring-opening isomerization of four-membered rings, and the thermal ring-opening of the four-membered rings can obtain products of Z type or E type or a mixture of the two by inward and outward rotation. One factor affecting the thermal ring opening of the four-membered ring is the substituent at the 3-position of cyclobutene, which increases its outward preference for substituents in the ring-opening isomerized product as the pi-donor properties of its substituents increase.
The raw materials adopted by the invention are beneficial to generating the product with the E-type structure.
Figure BDA0003285723710000081
The invention has the advantages of simple raw material preparation, mild reaction conditions, few reaction steps and simple reaction operation. The preparation method of the electron-rich 1,3 butadiene has good substrate universality and good functional group compatibility, can substitute groups such as electron-deficient groups, electron-rich groups, heterocyclic groups, naphthalene rings and the like on aromatic rings, has mild reaction conditions, and obtains products which have single structures and are E-type 1,3 butadiene.

Claims (9)

1.一种富电子共轭二烯类化合物，其特征在于，其结构如下：1. an electron-rich conjugated diene compound, is characterized in that, its structure is as follows:
Figure FDA0003285723700000011
Figure FDA0003285723700000011
 式中：Ar为苯基，4-甲基苯基，4-叔丁基苯基，4-甲氧基苯基，4-苯基，4-氟苯基，4-氯苯，4-三氟甲基苯基，3-甲氧基苯基，2-甲基苯基，2-甲氧基苯基，1,2-亚甲二氧基苯基，2-萘基，3-噻吩基中的一种。In the formula: Ar is phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-phenyl, 4-fluorophenyl, 4-chlorobenzene, 4-tris Fluoromethylphenyl, 3-methoxyphenyl, 2-methylphenyl, 2-methoxyphenyl, 1,2-methylenedioxyphenyl, 2-naphthyl, 3-thienyl one of the. 2.如权利要求1所述富电子共轭二烯类化合物的制备方法，其特征在于，包括以下步骤：2. the preparation method of electron-rich conjugated diene compound as claimed in claim 1, is characterized in that, comprises the following steps: 步骤1：将N-(3-(苄氧基)环丁基)-4-甲基苯磺酰腙、碱和催化剂混合；Step 1: Mix N-(3-(benzyloxy)cyclobutyl)-4-methylbenzenesulfonylhydrazone, base and catalyst; 步骤2：加入膦配体、芳基卤化物和溶剂，在磁力搅拌、90℃温度、氮气气氛中充分反应；Step 2: Add phosphine ligand, aryl halide and solvent, and fully react under magnetic stirring, 90°C temperature and nitrogen atmosphere; 步骤3：冷却后，提纯即可得到所需富电子共轭二烯类化合物。Step 3: After cooling, the desired electron-rich conjugated diene compound can be obtained by purification. 3.如权利要求1所述的富电子共轭二烯类化合物的制备方法，其特征在于，包括以下步骤：3. the preparation method of electron-rich conjugated diene compound as claimed in claim 1, is characterized in that, comprises the following steps: 步骤1：将3-(苄氧基)环丁烷-1-酮、对甲苯磺酰肼和溶剂混合，在磁力搅拌、60℃温度条件下，充分反应；Step 1: Mix 3-(benzyloxy)cyclobutan-1-one, p-toluenesulfonyl hydrazide and solvent, and fully react under magnetic stirring and 60°C temperature; 步骤2：冷却后，向步骤1得到的反应混合物中加入碱、金属钯、膦配体、芳基卤化物和溶剂；在磁力搅拌条件、90℃温度、氮气气氛中充分反应；Step 2: After cooling, add alkali, metal palladium, phosphine ligand, aryl halide and solvent to the reaction mixture obtained in step 1; fully react under magnetic stirring conditions, 90°C temperature, and nitrogen atmosphere; 步骤3：冷却后，提纯即可得到所需富电子共轭二烯类化合物。Step 3: After cooling, the desired electron-rich conjugated diene compound can be obtained by purification. 4.根据权利要求2或3所述一种富电子共轭二烯类化合物的制备方法，其特征在于，所述碱为碳酸铯，催化剂为金属钯，膦配体为二苯基环己基膦，溶剂为1,4二氧六环。4. the preparation method of a kind of electron-rich conjugated diene compound according to claim 2 or 3, is characterized in that, described base is cesium carbonate, catalyzer is metal palladium, and phosphine ligand is diphenylcyclohexylphosphine , the solvent is 1,4 dioxane. 5.根据权利要求2或3所述一种富电子共轭二烯类化合物的制备方法，其特征在于，所述催化剂为醋酸钯、三(二亚苄基丙酮)二钯、双(乙腈)二氯化钯(Ⅱ)、氯化烯丙基钯(Ⅱ)二聚物中的一种。5. the preparation method of a kind of electron-rich conjugated diene compound according to claim 2 or 3, is characterized in that, described catalyzer is palladium acetate, tris(dibenzylideneacetone) dipalladium, bis(acetonitrile) A kind of dimer of palladium(II) dichloride and allylpalladium(II) chloride. 6.根据权利要求2或3所述一种富电子共轭二烯类化合物的制备方法，其特征在于，所述芳基卤化物和N-(3-(苄氧基)环丁基)-4-甲基苯磺酰腙或对甲苯磺酰肼的摩尔比均为1:1～1.5。6. the preparation method of a kind of electron-rich conjugated diene compound according to claim 2 or 3, is characterized in that, described aryl halide and N-(3-(benzyloxy) cyclobutyl)- The molar ratio of 4-methylbenzenesulfonylhydrazone or p-toluenesulfonylhydrazide is 1:1-1.5. 7.根据权利要求2或3所述一种富电子共轭二烯类化合物的制备方法，其特征在于，所述催化剂和膦配体的摩尔比1:2～4，芳香卤化物和催化剂的摩尔比为1:0.04，芳香卤化物和碱的摩尔比1:2.5～3。7. The preparation method of an electron-rich conjugated diene compound according to claim 2 or 3, wherein the molar ratio of the catalyst and the phosphine ligand is 1:2 to 4, and the ratio of the aromatic halide to the catalyst is 1:2-4. The molar ratio is 1:0.04, and the molar ratio of aromatic halide and base is 1:2.5-3. 8.根据权利要求3所述一种富电子共轭二烯类化合物的制备方法，其特征在于，所述3-(苄氧基)环丁烷-1-酮和芳基卤化物的摩尔比为6:5。8. the preparation method of a kind of electron-rich conjugated diene compound according to claim 3, is characterized in that, the mol ratio of described 3-(benzyloxy) cyclobutan-1-one and aryl halide 6:5. 9.如权利要求1所述一种富电子共轭二烯类化合物的应用，其特征在于，富电子共轭二烯类化合物作为[4+2]环化的底物，与亲双烯体反应构建六元环类化合物。9 . The application of an electron-rich conjugated diene compound according to claim 1 , wherein the electron-rich conjugated diene compound is used as a substrate for [4+2] cyclization to interact with a dienophile. 10 . The reaction builds six-membered ring compounds.
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