CN107434756B - Synthetic method containing non-end group double bond compound III - Google Patents

Synthetic method containing non-end group double bond compound III Download PDF

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CN107434756B
CN107434756B CN201610365055.1A CN201610365055A CN107434756B CN 107434756 B CN107434756 B CN 107434756B CN 201610365055 A CN201610365055 A CN 201610365055A CN 107434756 B CN107434756 B CN 107434756B
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CN107434756A (en
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鲍红丽
周焕
陈绍维
冯薇薇
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C07J1/0051—Estrane derivatives
    • C07J1/0059—Estrane derivatives substituted in position 17 by a keto group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/025—Sulfonic acids

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Abstract

This application discloses a kind of synthetic methods of compound containing non-end group double bond, which is characterized in that coupling reaction occurs for end group olefin(e) compound I and t-butyl peroxy ester type compound II in the presence of a catalyst, and production contains non-end group double bond compound III.This method is introduced into t-butyl peroxy ester type compound as efficient, controllable alkylating reagent in reaction, and the compound containing non-end group double bond is prepared；Have many advantages, such as that raw material and catalyst are cheap, reaction condition is mild, easy to operate, reaction is efficient.

Description

Synthetic method containing non-end group double bond compound III
Technical field
This application involves a kind of synthetic methods of non-end group double bond compound, belong to organic synthesis field.
Background technique
Olefin compound is extremely important and meaningful structure in natural products, drug, material and pesticide.Alkene The synthesis of substance also has been a concern in chemical field.In the method developed, the functional group of C-H bond in alkene Change is to introduce alkenyl most straightforward approach into organic molecule.The Heck of well-known palladium chtalyst reacts, it becomes synthesis The basic methods of conversion, are applied to every field.Transition metal-catalyzed Heck reaction has mainly handled the alkenyl of aromatic hydrocarbons With vinyl electrophilic reagent, realizes alkene insertion and β hydrogen is eliminated.
Add since in traditional Heck coupling reaction, the alkyl electrophilic reagent of the hydrogen containing β aoxidizes in alkylated reaction At rate it is slower, be easy to happen β hydrogen elimination reaction, therefore alkyl electrophilic reagent is want through traditional Heck response path come real Existing alkenyl is still a problem so far.Also need the noble metals such as palladium, nickel and cobalt to participate in the reaction in addition, it is not only expensive, And it is unfriendly to environment, great difficulty is brought to practical application.
Summary of the invention
This application provides a kind of synthetic methods of compound containing non-end group double bond, by t-butyl peroxy esters chemical combination Object is introduced into reaction as efficient, controllable alkylating reagent, and the compound containing non-end group double bond is prepared；This method Have many advantages, such as that raw material and catalyst are cheap, reaction condition is mild, easy to operate, reaction is efficient.
Synthetic method containing non-end group double bond compound III, which is characterized in that end group alkene in the presence of a catalyst Coupling reaction occurs for compound I and t-butyl peroxy ester type compound II, and production contains non-end group double bond compound III；
The end group olefin(e) compound I is selected from least one of compound with chemical structural formula shown in Formulas I -1, tool There is at least one of compound of chemical structural formula shown in Formulas I -2, in the compound with chemical structural formula shown in Formulas I -3 At least one of at least one or compound with chemical structural formula shown in Formulas I -4:
The t-butyl peroxy ester type compound II in the compound with chemical structural formula shown in Formula II at least It is a kind of:
It is described containing non-end group double bond compound III be in the compound for have chemical structural formula shown in formula III -1 extremely At least one of few a kind of, with chemical structural formula shown in formula III -2 compound has chemical structure shown in formula III -3 At least one of at least one of compound of formula, compound with chemical structural formula shown in formula III -4:
Wherein, R1, R2Independently selected from hydrogen, alkyl, substituted hydrocarbon radical, heteroaryl or substituted heteroaryl；R3Independently selected from hydrocarbon Base or substituted hydrocarbon radical；
M is selected from alkyl or substituted hydrocarbon radical, m=0,1,2,3 or 4；N be selected from alkyl or substituted hydrocarbon radical, n=0,1,2,3,4 or 5。
The method according to claim 1, wherein the t-butyl peroxy ester type compound II, which is selected from, to be had In at least one of compound of chemical structural formula shown in Formula II -1, the compound with chemical structural formula shown in Formula II -2 At least one of compound at least one, with chemical structural formula shown in Formula II -3 has chemical structure shown in Formula II -4 At least one of compound of formula, the compound with chemical structural formula shown in Formula II -5 have the knot of chemistry shown in Formula II -6 The compound of structure formula:
Wherein, R4, R5, R6Independently selected from alkyl or substituted hydrocarbon radical；
X is selected from alkyl or substituted hydrocarbon radical, x=0,1,2,3 or 4；
Y is selected from alkyl or substituted hydrocarbon radical, y=0,1,2,3,4 or 5；
Z is selected from alkyl or substituted hydrocarbon radical, z=0,1,2 or 3；
That is, the R in Formula II3Selected from one of following groups:
R4, R5, R6Independently selected from alkyl or substituted hydrocarbon radical；
X is selected from alkyl or substituted hydrocarbon radical, x=0,1,2,3 or 4；
Y is selected from alkyl or substituted hydrocarbon radical, y=0,1,2,3,4 or 5；
Z is selected from alkyl or substituted hydrocarbon radical, z=0,1,2 or 3；
Preferably, R1, R2Independently selected from hydrogen, C1~C10Alkyl, C1~C10Alkane substitute base, have formula (1) institute Show the group of chemical structural formula or the group with chemical structural formula shown in formula (2):
In formula (1), l=0,1,2,3,4 or 5；R11It is C selected from carbon atom number1~C10Alkyl, C1~C10Substitution alkane At least one of alkyl, non-hydrocarbons substituent group；
In formula (2), A is selected from N, O or S；P=0,1,2 or 3；R21It is C selected from carbon atom number1~C10Alkyl, C1~C10 Alkane substitute base, at least one of non-hydrocarbons substituent group.
It is further preferred that R1And R2In at least one be selected from group with chemical structural formula shown in formula (1), with formula (2) group of chemical structural formula shown in.
Preferably, the substituted hydrocarbon radical, alkane substitute base, substituted arene base, the substituent group in substituted heteroaryl are nonhydrocarbons Class substituent group；
The non-hydrocarbons substituent group is selected from oxygen, halogen, the group with structural formula shown in formula (3), has knot shown in formula (4) One of the group of structure formula, the group with structural formula shown in formula (5), group with structural formula shown in formula (6):
In formula (3), R31Selected from hydrogen, C1~C10Alkyl；
In formula (4), R41Selected from hydrogen, C1~C10Alkyl；
R51- O- formula (5)
In formula (5), R51Selected from hydrogen, C1~C10Alkyl；
R61-O-A62Formula (6)
In formula (6), R61Selected from hydrogen, C1~C10Alkyl；A62Selected from C1~C10Alkylene alkyl.
Preferably, R4, R5, R6Independently selected from C1~C10Alkyl, C2~C10Contain at least one carbon-carbon double bond or carbon The alkyl of three key of carbon.
The catalyst is selected from least one of metallic catalyst, trifluoromethanesulfonic acid.
As an implementation, the catalyst is selected from azochlorosulfonate acid anion metallic catalyst, trifluoromethanesulfonic acid root yin At least one of metallic catalysts.
As an implementation, the catalyst is selected from palladium metal catalyst, ferrous metal catalyst, copper metal catalysis Agent, indium catalyst, neodymium catalyst, yttrium catalyst, silver catalyst, lanthanum catalyst, cerium catalyst, at least one in trifluoromethanesulfonic acid Kind.
Preferably, the catalyst is selected from double acetonitrile palladium chloride, acid chloride, palladium trifluoroacetate, three (dibenzalacetones) Two palladiums, palladium chloride, cuprous bromide, copper acetate, copper chloride, frerrous chloride, ferrous acetate, p-methyl benzenesulfonic acid iron, trifluoro methylsulphur Sour ferrous iron, trifluoromethanesulfonic acid palladium, trifluoromethanesulfonic acid indium, trifluoromethanesulfonic acid neodymium, trifluoromethanesulfonic acid yttrium, trifluoromethanesulfonic acid iron, trifluoro At least one of methanesulfonic acid, copper trifluoromethanesulfcomposite, silver trifluoromethanesulfonate, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid cerium.Further Preferably, the catalyst is trifluoromethanesulfonic acid iron Fe (OTf)3And/or trifluoromethanesulfonic acid ferrous iron Fe (OTf)2。
Those skilled in the art can select suitable end group olefin(e) compound I, t-butyl peroxy ester according to specific needs The dosage of class compound II and catalyst.Preferably, the end group olefin(e) compound I and t-butyl peroxy ester type compound II Molar ratio is 1:1.5~3.It is further preferred that the end group olefin(e) compound I's and t-butyl peroxy ester type compound II rubs Your the proportional region upper limit is selected from 1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2, and lower limit is selected from 1:2.5,1:2.6,1: 2.7、1:2.8、1:2.9、1:3。
Preferably, the molar ratio of the catalyst and end group olefin(e) compound I are 0.5~10:100.Further preferably Ground, the molar ratio upper limit of the catalyst and end group olefin(e) compound I be selected from 10:100,9:100,8:100,7:100, 6:100, lower limit are selected from 0.5:100,1:100,2:100,3:100,4:100.
Those skilled in the art can select temperature and the reaction time of coupling reaction according to raw material and specific production requirement. Preferably, the reaction temperature of the coupling reaction is not more than 100 DEG C, and the reaction time is no more than 5 hours.It is further preferred that The reaction temperature lower limit of the coupling reaction is selected from 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, and the upper limit is selected from 70 DEG C, 80 DEG C, 90 ℃,100℃；The reaction time lower limit of the coupling reaction is selected from 6 minutes, 10 minutes, 20 minutes, 30 minutes, 1 hour, the upper limit Selected from 2.5 hours, 3 hours, 3.5 hours, 4 hours, 5 hours.It is further preferred that the reaction temperature of the coupling reaction is 20 DEG C~100 DEG C, the reaction time is 6 minutes~3.5 hours.
As an implementation, contain organic solvent in the coupling reaction system.Those skilled in the art can basis Raw material and specific production requirement select the type and dosage of organic solvent.Preferably, the organic solvent be selected from tetrahydrofuran, At least one of 1,4- dioxane, dimethylformamide, methyl pyrrolidone, p-methyl benzenesulfonic acid.
Preferably, the ratio of organic solvent (volume) and end group olefin(e) compound I (molal quantity) are 1mL/mmol~7mL/ mmol.It is further preferred that the ratio lower limit of organic solvent (volume) and end group olefin(e) compound I (molal quantity) are selected from 1mL/ mmol,2mL/mmol,3mL/mmol；The upper limit is selected from 4mL/mmol, 5mL/mmol, 6mL/mmol, 7mL/mmol.
As a preferred embodiment, the synthetic method containing non-end group double bond compound III, includes at least Following steps:
A) end group olefin(e) compound I, t-butyl peroxy ester type compound II, catalyst and organic solvent reaction is placed in hold In device, it is cooled to room temperature after being stirred 6 minutes~3.5 hours at 20 DEG C~100 DEG C；
B) it is filtered after ethyl acetate dilution is added with diatomite, removes solvent, pillar layer separation through vacuum distillation to get non- End group double bond compound III.
In the application, C1~C10、C2~C10Etc. referring both to included carbon atom number.To " substituted hydrocarbon radical ", " replace virtue The carbon atom of alkyl " and " substituted heteroaryl " limits, and refers to the contained carbon atom number of alkyl, aryl, heteroaryl itself, rather than Carbon atom number after substitution.Such as C1~C10Substituted hydrocarbon radical, refer to carbon atom number be 1~10 alkyl on, at least one hydrogen atom It is substituted with a substituent.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on hydrocarbon molecules；Institute Stating hydrocarbon compound includes alkane compound, olefin(e) compound, acetylene hydrocarbon compound and aromatic compound.As toluene loses on phenyl ring The hydrogen atom of methyl contraposition is formed by p-methylphenyl or toluene loses the benzyl that any one hydrogen atom is formed on methyl Deng.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on alkane compound molecule. The alkane compound includes linear paraffin, branched paraffin, cycloalkane, the cycloalkane with branch." alkylene alkyl " is by alkane Any two hydrogen atom is lost on hydrocarbon compound molecule is formed by group.
In the application, " aryl " is to lose a hydrogen atom on aromatic rings on aromatic compound molecule to be formed by base Group；P-methylphenyl is formed by as toluene loses the hydrogen atom that methyl aligns on phenyl ring.
In the application, " heteroaryl " is to contain the heteroatomic aromatic compound of O, N, S (abbreviation heteroaryl in aromatic rings Compound) any one hydrogen atom on aromatic rings is lost on molecule is formed by group；As lost any one hydrogen on piperazine ring The formed piperazinyl of atom.
In the application, " halogen " refers at least one of fluorine, chlorine, bromine, iodine.
In the application, the carbon atom of " substituted hydrocarbon radical ", " substituted arene base " and " substituted heteroaryl " is limited, is referred to The contained carbon atom number of alkyl, aryl, heteroaryl itself, and it is non-substituted after carbon atom number.Such as C1~C10Substituted hydrocarbon radical, Finger carbon atom number is C1~C10Alkyl on, at least one hydrogen atom is substituted with a substituent.Such as a hydrogen quilt-C on adamantyl ≡ N replaces the group for being 11 containing carbon atom number to be formed.
In the application, when the substituent group is oxygen, refer to that two H atoms in group on any one C atom are substituted by O, Form C=O key.
The beneficial effect of the application includes but is not limited to:
(1) preparation method of the compound containing non-end group double bond provided herein, for the first time by t-butyl peroxy ester Class compound is introduced into reaction as efficient, controllable alkylating reagent, and the compound containing non-end group double bond is prepared.
(2) preparation method of the compound containing non-end group double bond provided herein has raw material and catalyst honest and clean The advantages that valence, reaction condition are mild, easy to operate, reaction is efficient.
(3) preparation method of the compound containing non-end group double bond provided herein, compared with prior art, substantially Improve the yield of the compound containing non-end group double bond.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
In embodiment, nuclear magnetic resonance spectroscopy1400AVANCE III type spectroscope of the H-NMR in Brooker company (Bruker) (Spectrometer) it is measured on, 400MHz, CDCl3；Carbon spectrum13C-NMR, 100MHz, CDCl3。
Product separation uses the full-automatic combiflash companion system of RF+UV-VIS type of Teledyne Isco.
The additional amount of catalyst is indicated with molar ratio × 100% of itself and end group olefin(e) compound I；Such as " trifluoro methylsulphur Sour iron (5mol%) " indicates that the molar ratio of catalyst trifluoromethanesulfonic acid iron and end group olefin(e) compound I are 5:100.
The yield of non-end group double bond compound III is calculated on the basis of the amount of end group olefin(e) compound I by lower formula It obtains:
Yield %=(quality that the quality ÷ target product that target product actually obtains should theoretically obtain) × 100%.
Embodiment 1
It is added in reaction tube styrene 1-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 1-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 1-3, total 85mg, yield 84%.
The nuclear-magnetism detection data of Product samples 1-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.37 (d, J=8.0Hz, 2H), 7.29 (t, J=8.0Hz, 2H), 7.18 (t, J =8.0Hz, 1H), 6.34 (d, J=16.0Hz, 1H), 5.95 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 2.03-1.99 (m, 1H), 1.51-1.43 (m, 2H), 1.36-1.26 (m, 6H), 0.88 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ138.11,135.65,129.79,128.56,126.83,126.09,45.30, 35.02,29.78,28.36,23.02,14.24,11.98。
Embodiment 2
It is added in reaction tube styrene 2-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 2-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 2-3, total 54.0mg, yield 68%.
The nuclear-magnetism detection data of Product samples 2-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.36 (d, J=8.0Hz, 2H), 7.29 (t, J=8.0Hz, 2H), 7.17 (t, J =8.0Hz, 1H), 6.32-6.22 (m, 2H), 1.11 (s, 9H).
13C NMR(100MHz,CDCl3)δ141.87,138.09,128.53,126.80,126.07,124.62,33.41, 29.65。
Embodiment 3
It is added in reaction tube styrene 3-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 3-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 3-3, total 67.3mg, yield 78%.
The nuclear-magnetism detection data of Product samples 3-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.34 (d, J=8.0Hz, 2H), 7.27 (t, J=8.0Hz, 2H), 7.18 (t, J =8.0Hz, 1H), 6.38 (d, J=16.0Hz, 1H), 6.22 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 2.63-2.53 (m, 1H),1.86-1.81(m,2H),1.71-1.68(m,2H),1.62-1.59(m,2H),1.43-1.36(m,2H)。
13C NMR(100MHz,CDCl3)δ138.02,135.72,128.53,127.98,126.79,126.01,43.92, 33.32,25.33。
Embodiment 4
It is added in reaction tube styrene 4-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 4-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 4-3, total 47.4mg, yield 52%.
The nuclear-magnetism detection data of Product samples 4-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.36 (d, J=8.0Hz, 2H), 7.28 (t, J=8.0Hz, 2H), 7.18 (t, J =8.0Hz, 1H), 6.41 (d, J=16.0Hz, 1H), 6.26 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 5.71 (s, 2H), 2.43-2.11(m,4H),1.99-1.84(m,2H),1.54-1.46(m,2H),1.54–1.46(m,1H)。
13C NMR(100MHz,CDCl3)δ137.90,135.76,128.52,128.03,127.03,126.90, 126.07,126.03,37.15,31.44,28.79,24.87。
Embodiment 5
It is added in reaction tube styrene 5-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 5-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 5-3, total 82mg, yield 94%.
The nuclear-magnetism detection data of Product samples 5-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.37 (d, J=8.0Hz, 2H), 7.29 (t, J=8.0Hz, 2H), 7.18 (t, J =8.0Hz, 1H), 6.35 (d, J=16.0Hz, 1H), 5.96 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 1.97-1.90 (m, 1H), 154-1.47 (m, 2H), 1.37-1.29 (m, 2H), 0.88 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ138.01,135.32,129.87,128.50,126.76,125.99,46.92, 27.87,11.92。
Embodiment 6
It is added in reaction tube styrene 6-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 6-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, for crude product through pillar layer separation, products therefrom sample is denoted as 6-3, total 109.1mg, yield 92%.
The nuclear-magnetism detection data of Product samples 6-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.38 (d, J=8.0,2H), 7.32 (t, J=8.0Hz, 2H), 7.21 (t, J= 8.0Hz, 1H), 6.27 (d, J=16.0Hz, 1H), 6.14 (d, J=16.0Hz, 1H), 2.03 (s, 3H), 1.75-1.70 (m, 12H)。
13C NMR(100MHz,CDCl3)δ142.12,138.21,128.49,126.72,126.00,124.51,42.25, 36.92,35.19,28.50。
Embodiment 7
It is added in reaction tube p-methylstyrene 7-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 7-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil baths are reacted 3 hours.It is cooled to room temperature, is diluted with ethyl acetate, diatomite filters, it is dense to be evaporated under reduced pressure after reaction Contracting removes solvent, and for crude product through pillar layer separation, products therefrom sample is denoted as 7-3, total 105mg, yield 97%.
The nuclear-magnetism detection data of Product samples 7-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.26 (d, J=8.0Hz, 2H), 7.10 (d, J=4.0Hz, 2H), 6.30 (d, J =12.0Hz, 1H), 5.88 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 2.32 (s, 3H), 2.00-1.97 (m, 1H), 1.50- 1.45 (m, 2H), 1.35-1.26 (m, 6H), 0.87 (t, J=7.3Hz, 7H).
13C NMR(100MHz,CDCl3)δ136.42,135.26,134.62,129.45,129.18,125.88,45.19, 34.97,29.69,28.31,22.93,21.16,14.17,11.91。
Embodiment 8
It is added in reaction tube p-methylstyrene 8-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 8-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil baths are reacted 3 hours.It is cooled to room temperature, is diluted with ethyl acetate, diatomite filters, it is dense to be evaporated under reduced pressure after reaction Contracting removes solvent, and for crude product through pillar layer separation, products therefrom sample is denoted as 8-3, total 59.8mg, yield 46%.
The nuclear-magnetism detection data of Product samples 8-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.36 (d, J=8.0Hz, 2H), 7.01 (d, J=8.0Hz, 2H), 6.32 (d, J =16.0Hz, 1H), 5.91 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 2.27 (s, 3H), 2.04-1.97 (m, 1H), 1.46- 1.42 (m, 2H), 1.35-1.24 (m, 6H), 0.87 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ169.56,149.42,135.89,135.84,128.70,126.84, 121.54,45.17,34.86,31.45,30.21,29.65,28.21,22.87,21.11,14.13,11.86。
Embodiment 9
It is added in reaction tube p-methylstyrene 9-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 9-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil baths are reacted 3 hours.It is cooled to room temperature, is diluted with ethyl acetate, diatomite filters, it is dense to be evaporated under reduced pressure after reaction Contracting removes solvent, and for crude product through pillar layer separation, products therefrom sample is denoted as 9-3, total 86.9mg, yield 71%.
The nuclear-magnetism detection data of Product samples 9-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.29 (d, J=8.6Hz, 2H), 6.84 (d, J=8.7Hz, 2H), 6.26 (d, J =15.8Hz, 1H), 5.80 (dd, J1=15.8Hz, J2=9.0Hz, 1H), 3.79 (s, 3H), 1.99-1.96 (m, 1H), 1.51- 1.37 (m, 2H), 1.35-1.23 (m, 6H), 0.87 (t, J=7.2Hz, 6H).
13C NMR(100MHz,CDCl3)δ158.59,133.50,130.88,128.89,127.00,113.90,55.32, 45.13,34.97,29.66,28.31,22.90,14.14,11.88。
Embodiment 10
It is added in reaction tube ortho position styrene 10-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 10-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C of oil baths are reacted 3 hours.It is cooled to room temperature, is diluted with ethyl acetate, diatomite filters, it is dense to be evaporated under reduced pressure after reaction Contracting removes solvent, and for crude product through pillar layer separation, products therefrom sample is denoted as 10-3, total 104mg, yield 98%.
The nuclear-magnetism detection data of Product samples 10-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.52 (d, J=8.0Hz, 1H), 7.33 (d, J=8.0Hz, 1H), 7.24 (t, J =8.0Hz, 1H), 7.12 (t, J=8.0Hz, 1H), 6.72 (d, J=16.0Hz, 1H), 5.96 (dd, J1=8.0Hz, J2= 12.0Hz, 1H), 2.10-2.06 (m, 1H), 1.54-1.46 (m, 2H), 1.38-1.26 (m, 6H), 0.90 (t, J=8.0Hz, 6H)。
13C NMR(100MHz,CDCl3)δ138.55,132.56,129.58,127.75,126.69,125.68,45.21, 34.70,29.59,28.09,22.86,14.12,11.84。
Embodiment 11
It is added in reaction tube styrene compound 11-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 11-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then throw Enter to 100 DEG C of oil baths and reacts 3 hours.It is cooled to room temperature, is steamed with ethyl acetate dilution, diatomite filtering, decompression after reaction It evaporates concentration and removes solvent, for crude product through pillar layer separation, products therefrom sample is denoted as 11-3, total 74.9mg, yield 96%.
The nuclear-magnetism detection data of Product samples 11-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.24 (s, 1H), 7.02 (d, J=8.0Hz, 1H), 6.94 (d, J=8.0Hz, 1H), 6.50 (d, J=16.0Hz, 1H), 5.81 (dd, J1=12.0Hz, J2=16.0Hz, 1H), 2.31 (s, 3H), 2.29 (s, 3H), 2.03-2.00 (m, 1H), 1.53-1.46 (m, 2H), 1.33-1.26 (m, 6H), 0.90 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ137.01,136.75,135.32,131.84,130.07,127.70, 127.48,126.16,45.48,34.94,29.70,28.32,22.88,21.06,19.42,14.17,11.94。
Embodiment 12
It is added in reaction tube thiophenes 12-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 12- 2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into It is reacted 3 hours to 100 DEG C of oil baths.It is cooled to room temperature after reaction, with ethyl acetate dilution, diatomite filtering, vacuum distillation Concentration removes solvent, and for crude product through pillar layer separation, products therefrom sample is denoted as 12-3, total 54.9mg, yield 53%.
The nuclear-magnetism detection data of Product samples 12-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.07 (d, J=4.0Hz, 2H), 6.93 (t, J=4.0Hz, 1H), 6.86 (d, J =2.8Hz, 1H), 6.45 (d, J=16.0Hz, 1H), 5.81 (dd, J1=8.0Hz, J2=12.0Hz, 1H), 1.98-1.94 (m, 1H), 1.52-1.43 (m, 2H), 1.35-1.23 (m, 6H), 0.88 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ143.34,135.65,127.19,124.07,122.90,122.84,45.05, 34.73,29.62,28.09,22.86,14.10,11.84。
Embodiment 13
It is added in reaction tube styrene compound 13-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 13-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then throw Enter to 100 DEG C of oil baths and reacts 3 hours.It is cooled to room temperature, is steamed with ethyl acetate dilution, diatomite filtering, decompression after reaction It evaporates concentration and removes solvent, for crude product through pillar layer separation, products therefrom sample is denoted as 13-3, total 127mg, yield 98%.
The nuclear-magnetism detection data of Product samples 13-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.34-7.29 (m, 4H), 6.32 (d, J=16.0Hz, 1H), 5.94 (dd, J1= 8.0Hz,J2=16.0Hz, 1H), 2.01-1.97 (m, 1H), 1.51-1.43 (m, 2H), 1.35-1.22 (m, 15H), 0.87 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ149.77,135.26,134.87,129.37,125.69,125.43,45.27, 35.02,34.52,31.38,29.71,28.37,22.92,14.18,11.93。
Embodiment 14
It is added in reaction tube styrene compound 14-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 14-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then throw Enter to 100 DEG C of oil baths and reacts 3 hours.It is cooled to room temperature, is steamed with ethyl acetate dilution, diatomite filtering, decompression after reaction It evaporates concentration and removes solvent, for crude product through pillar layer separation, products therefrom sample is denoted as 14-3, total 101.2mg, yield 74%.
The nuclear-magnetism detection data of Product samples 14-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.36 (d, J=8.0Hz, 2H), 7.29 (d, J=8.0Hz, 2H), 6.34 (d, J =16.0Hz, 1H), 5.99 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 5.07 (s, 2H), 2.08 (s, 3H), 2.03-1.99 (m, 1H), 1.53-1.52 (m, 2H), 1.36-1.22 (m, 6H), 0.87 (t, J=8.0Hz, 6H).
13C NMR(100MHz,CDCl3)δ170.84,138.11,136.21,134.33,129.17,128.66, 126.12,66.18,45.22,34.86,29.67,28.21,22.89,21.01,14.14,11.88。
Embodiment 15
It is added in reaction tube styrene compound 15-1 (1 equivalent, 0.5mmol), t-butyl peroxy ester type compound 15-2 (3 equivalents, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then throw Enter to 100 DEG C of oil baths and reacts 3 hours.It is cooled to room temperature, is steamed with ethyl acetate dilution, diatomite filtering, decompression after reaction It evaporates concentration and removes solvent, for crude product through pillar layer separation, products therefrom sample is denoted as 15-3, total 86.9mg, yield 71%.
The nuclear-magnetism detection data of Product samples 15-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.35 (d, J=8.0Hz, 2H), 7.24 (d, J=8.0Hz, 2H), 6.34 (d, J =16.0Hz, 1H), 5.96 (dd, J1=8.0Hz, J2=16.0Hz, 1H), 4.42 (s, 2H), 3.35 (s, 3H), 2.05-1.96 (m, 1H), 1.52-1.42 (m, 2H), 1.36-1.22 (m, 6H), 0.88 (t, J=7.4Hz, 6H).
13C NMR(100MHz,CDCl3)δ137.49,136.66,135.65,129.35,127.99,126.00,74.50, 57.93,45.22,34.91,29.69,28.25,22.92,14.16,11.90。
Embodiment 16
It is added in reaction tube styrene 16-1 (1 equivalent, 0.5mmol), (3 work as t-butyl peroxy ester type compound 16-2 Amount, 1.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 100 DEG C oil bath is reacted 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration after reaction Solvent is removed, for crude product through pillar layer separation, products therefrom sample is denoted as 16-3, total 44mg, yield 56%.
The nuclear-magnetism detection data of Product samples 16-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.35 (d, J=4.0Hz, 2H), 7.28 (t, J=8.0Hz, 2H), 7.18 (t, J =8.0Hz, 1H), 6.36-6.27 (m, 2H), 2.63-2.53 (m, 1H), 3.12-3.07 (m, 1H), 2.19-2.13 (m, 2H), 2.04-1.80(m,4H)。
13C NMR(100MHz,CDCl3)δ137.81,135.30,128.50,127.62,126.84,126.00,38.78, 28.80,18.62。
Embodiment 17
It is added in reaction tube styrene 17-1 (3 equivalents, 1.5mmol), peroxide ester type compound 17-2 (1 equivalent, 0.5mmol), trifluoromethanesulfonic acid iron (1mol%) and tetrahydrofuran (2mL) are added magnetic stir bar, then put into 120 DEG C of oil Bath reaction 3 hours.It is cooled to room temperature, is removed with ethyl acetate dilution, diatomite filtering, vacuum distillation concentration molten after reaction Agent, crude product is through pillar layer separation, and products therefrom sample is denoted as 17-3-1 and 17-3-2, total 88mg, 17-3-1: yield is 47%.17-3-1:17-3-2=1:13.2.
The nuclear-magnetism detection data of Product samples 17-3-1 and 17-3-2 are as follows:
1H NMR(400MHz,CDCl3) δ 7.26 (d, J=4.0Hz, 2H), 2.21 (d, J=8.0Hz, 2H), 7.11 (t, J =8.0Hz, 1H), 6.19 (d, J=16.0Hz, 1H), 6.08 (dd, J1=8.0Hz, J2=12.0Hz, 1H), 5.65 (s, 1H), 2.33-2.18(m,5H),2.07-2.04(m,1H),1.95-1.90(m,1H),1.84-1.81(m,1H),1.73-1.71(m, 1H),1.61-1.53(m,2H),1.46-1.40(m,3H),1.37-1.34(m,1H),1.24-1.15(m,3H),1.09-1.03 (m, 4H), 0.80 (s, 3H), 0.67 (d, J=16.0Hz, 1H).
13C NMR(100MHz,CDCl3)δ199.67,171.52,137.81,133.87,128.89,128.51, 126.84,125.99,123.81,53.70,52.60,50.88,44.66,38.69,36.15,35.71,34.75,33.99, 32.98,32.47,28.49,25.70,20.92,20.27,17.48。
Embodiment 18
It is added in reaction tube end vinyl compound 18-1 (1 equivalent, 0.3mmol), t-butyl peroxy ester type compound 18- 2 (4 equivalents, 1.2mmol), trifluoromethanesulfonic acid iron (5mol%) and tetrahydrofuran (1.5mL) are added magnetic stir bar, then throw Enter to 100 DEG C of oil baths and reacts 3 hours.It is cooled to room temperature, is steamed with ethyl acetate dilution, diatomite filtering, decompression after reaction It evaporates concentration and removes solvent, for crude product through pillar layer separation, products therefrom sample is denoted as 18-3, total 64mg, yield 58%.It is suitable Formula: trans-=3:1.
The nuclear-magnetism detection data of Product samples 18-3 is as follows:
1H NMR(400MHz,CDCl3) δ 7.07 (d, J=8.0Hz, 1H), 6.30 (d, J=8.0Hz, 1H), 6.23 (s, 1H),5.82(s,1H),2.56-2.40(m,3H),2.19-2.09(m,2H),1.97-1.87(m,3H),1.72-1.60(m, 3H), 1.49-1.28 (m, 7H), 1.20 (s, 3H), 1.00 (s, 3H), 0.91 (t, J=8.0Hz, 3H), 0.85 (t, J= 8.0Hz,3H)。
13C NMR(100MHz,CDCl3)δ219.21,186.41,162.11,153.68,135.92,133.09, 127.69,122.04,49.08,49.02,47.77,41.32,38.38,37.35,36.92,35.57,31.29,25.47, 24.55,21.46,31.37,20.04,13.87,10.80,10.28。
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (8)

1. containing the synthetic method of non-end group double bond compound III, which is characterized in that end group is Olefination in the presence of a catalyst It closes object I and t-butyl peroxy ester type compound II and coupling reaction occurs, production contains non-end group double bond compound III；
The end group olefin(e) compound I is selected from least one of compound with chemical structural formula shown in Formulas I -1, has formula In at least one of compound of chemical structural formula shown in I-2, the compound with chemical structural formula shown in Formulas I -3 at least A kind of at least one of or compound with chemical structural formula shown in Formulas I -4:
The t-butyl peroxy ester type compound II is selected from least one of the compound with chemical structural formula shown in Formula II:
It is described containing non-end group double bond compound III be in the compound for have chemical structural formula shown in formula III -1 at least one Kind, at least one of compound with chemical structural formula shown in formula III -2, with chemical structural formula shown in formula III -3 At least one of at least one of compound, compound with chemical structural formula shown in formula III -4:
Wherein, R1, R2Independently selected from hydrogen, alkyl, substituted hydrocarbon radical, heteroaryl or substituted heteroaryl；R3Independently selected from alkyl or Substituted hydrocarbon radical；
M is selected from alkyl or substituted hydrocarbon radical, m=0,1,2,3 or 4；N is selected from alkyl or substituted hydrocarbon radical, n=0,1,2,3,4 or 5；
Substituent group in the substituted hydrocarbon radical, substituted heteroaryl is non-hydrocarbon substituents；
The non-hydrocarbons substituent group is selected from oxygen, halogen, the group with structural formula shown in formula (3), has structural formula shown in formula (4) Group, the group with structural formula shown in formula (5), at least one of the group with structural formula shown in formula (6):
In formula (3), R31Selected from hydrogen, C1~C10Alkyl；
In formula (4), R41Selected from hydrogen, C1~C10Alkyl；
R51- O- formula (5)
In formula (5), R51Selected from hydrogen, C1~C10Alkyl；
R61-O—A62- formula (6)
In formula (6), R61Selected from hydrogen, C1~C10Alkyl；A62Selected from C1~C10Alkylene alkyl；
The catalyst is selected from trifluoromethanesulfonic acid root anionic metallic catalysts.
2. the method according to claim 1, wherein the t-butyl peroxy ester type compound II, which is selected from, has formula In at least one of compound of chemical structural formula shown in II-1, the compound with chemical structural formula shown in Formula II -2 extremely At least one of few a kind of, with chemical structural formula shown in Formula II -3 compound has chemical structural formula shown in Formula II -4 At least one of compound, the compound with chemical structural formula shown in Formula II -5 or there is chemical structure shown in Formula II -6 The compound of formula:
Wherein, R4, R5, R6Independently selected from alkyl or substituted hydrocarbon radical；
X is selected from alkyl or substituted hydrocarbon radical, x=0,1,2,3 or 4；
Y is selected from alkyl or substituted hydrocarbon radical, y=0,1,2,3,4 or 5；
Z is selected from alkyl or substituted hydrocarbon radical, z=0,1,2 or 3；
Substituent group in the substituted hydrocarbon radical is non-hydrocarbon substituents；
The non-hydrocarbons substituent group is selected from oxygen, halogen, the group with structural formula shown in formula (3), has structural formula shown in formula (4) Group, the group with structural formula shown in formula (5), at least one of the group with structural formula shown in formula (6):
In formula (3), R31Selected from hydrogen, C1~C10Alkyl；
In formula (4), R41Selected from hydrogen, C1~C10Alkyl；
R51- O- formula (5)
In formula (5), R51Selected from hydrogen, C1~C10Alkyl；
R61-O-A62Formula (6)
In formula (6), R61Selected from hydrogen, C1~C10Alkyl；A62Selected from C1~C10Alkylene alkyl.
3. the method according to claim 1, wherein R1, R2Independently selected from hydrogen, C1~C10Alkyl, C1~ C10Alkane substitute base, the group with chemical structural formula shown in formula (1) or the group with chemical structural formula shown in formula (2):
In formula (1), l=0,1,2,3,4 or 5；R11It is C selected from carbon atom number1~C10Alkyl, C1~C10Alkane substitute At least one of base, non-hydrocarbons substituent group；
In formula (2), A is selected from N, O or S；P=0,1,2 or 3；R21It is C selected from carbon atom number1~C10Alkyl, C1~C10Take For at least one of alkyl, non-hydrocarbons substituent group；
Substituent group in the alkane substitute base is non-hydrocarbon substituents；
The non-hydrocarbons substituent group is selected from oxygen, halogen, the group with structural formula shown in formula (3), has structural formula shown in formula (4) Group, the group with structural formula shown in formula (5), at least one of the group with structural formula shown in formula (6):
In formula (3), R31Selected from hydrogen, C1~C10Alkyl；
In formula (4), R41Selected from hydrogen, C1~C10Alkyl；
R51- O- formula (5)
In formula (5), R51Selected from hydrogen, C1~C10Alkyl；
R61-O-A62Formula (6)
In formula (6), R61Selected from hydrogen, C1~C10Alkyl；A62Selected from C1~C10Alkylene alkyl.
4. according to the method described in claim 2, it is characterized in that, R4, R5, R6Independently selected from C1~C10Alkyl, C2~ C10Alkyl containing at least one carbon-carbon double bond or carbon-carbon triple bond.
5. the method according to claim 1, wherein the catalyst is selected from trifluoromethanesulfonic acid ferrous iron, fluoroform Sulfonic acid palladium, trifluoromethanesulfonic acid indium, trifluoromethanesulfonic acid neodymium, trifluoromethanesulfonic acid yttrium, trifluoromethanesulfonic acid iron, trifluoromethanesulfonic acid, fluoroform At least one of sulfonic acid copper, silver trifluoromethanesulfonate, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid cerium.
6. the method according to claim 1, wherein the end group olefin(e) compound I and t-butyl peroxy esters The molar ratio of compound II is 1:1.5~3；
The molar ratio of the catalyst and end group olefin(e) compound I are 0.5~10:100；
The reaction temperature of the coupling reaction is not more than 100 DEG C, and the reaction time is no more than 5 hours.
7. method according to any one of claims 1 to 6, which is characterized in that containing organic in the coupling reaction system Solvent；The organic solvent be selected from tetrahydrofuran, 1,4- dioxane, dimethylformamide, methyl pyrrolidone, to toluene sulphur At least one of acid.
8. the method according to the description of claim 7 is characterized in that at least including the following steps:
A) end group olefin(e) compound I, t-butyl peroxy ester type compound II, catalyst and organic solvent are placed in reaction vessel In, it is cooled to room temperature after being stirred 6 minutes~3.5 hours at 20 DEG C~100 DEG C；
B) it is filtered after ethyl acetate dilution is added with diatomite, removes solvent, pillar layer separation through vacuum distillation to get non-end group Double bond compound III.
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