CN108707081B - Alkene 1, 2-bifunctional reaction method - Google Patents

Alkene 1, 2-bifunctional reaction method Download PDF

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CN108707081B
CN108707081B CN201810742506.8A CN201810742506A CN108707081B CN 108707081 B CN108707081 B CN 108707081B CN 201810742506 A CN201810742506 A CN 201810742506A CN 108707081 B CN108707081 B CN 108707081B
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宋仁杰
李金恒
欧阳旋慧
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Nanchang Hangkong University
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Abstract

The invention discloses an alkene 1, 2-bifunctional reaction method, which takes an ethylene compound shown in a formula I, an N-substituted phthalimide compound shown in a formula II and amine shown in a formula III as raw materials, and the raw materials are stirred and reacted at room temperature in the presence of a photocatalyst, a reaction auxiliary agent and an organic solvent under the condition of illumination and inert atmosphere to obtain a target product shown in a formula IV. The method has mild reaction conditions, can be carried out at room temperature, and has the photocatalyst Ru (bpy)3Cl2Can be recycled by a filtration method. The method of the invention also has the advantages of simple operation, wide application range of reaction substrates, low cost of the production process and environmental protection.

Description

Alkene 1, 2-bifunctional reaction method
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to an alkene 1, 2-bifunctional reaction method.
Background
Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of the petrochemical industry, and the ethylene product accounts for more than 75 percent of petrochemical products and occupies an important position in national economy. The reactions in which olefinic compounds participate are of great importance in organic synthesis, and because they are relatively inexpensive and readily available and can undergo numerous functional group transformations, it is necessary to develop efficient ways to achieve olefin functionalization.
Since the bifunctional synthesis of olefins into various useful compounds has a remarkable high efficiency, and enables the synthesis of multi-site reaction products in one step, which is economical and efficient, the field has been a research direction favored by chemists in recent years. The research on the catalytic system in the olefin bifunctional reaction is also a research hotspot concerned by chemists. From the literature reports, the catalytic system mainly focuses on the action of transition metal catalysis and some oxidants such as peroxide; although Pd is the main metal catalyst, some catalytic systems using other transition metals such as Rh, Fe, etc. have also been reported in recent years. Meanwhile, the development of asymmetric olefin bifunctional, the application of various new reaction substrates, the proposal of different reaction strategies and the explanation and verification of various different reaction mechanisms are also continuously developing and perfecting. Although transition metal-catalyzed olefin bifunctional reaction has been widely used in pharmaceutical synthesis, the olefin bifunctional reaction is usually limited to the synthesis of common functionalized products, and the problems of harsh reaction conditions and the like also limit the popularization and application of the olefin bifunctional reaction in industrial production. Therefore, it is very important to develop an efficient olefin bifunctional reaction. Therefore, the inventors have made extensive studies and, in the present invention, have proposed a novel method for the 1, 2-bifunctional reaction of olefins.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the alkene 1, 2-bifunctional reaction method which has simple process, mild condition and wide application range of reaction substrates.
The invention provides an alkene 1, 2-bifunctional reaction method, which comprises the following steps:
adding an ethylene compound shown as a formula I, an N-substituted phthalimide compound shown as a formula II, an amine shown as a formula III, a photocatalyst, a reaction auxiliary agent and an organic solvent into a Schlenk tube-sealed reactor, stirring at room temperature under the conditions of illumination and inert atmosphere for reaction, detecting by TLC that the reaction is complete, and carrying out post-treatment to obtain a target product shown as a formula IV.
Figure BDA0001723518000000021
In the above formula I-formula IV, R1Selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20Heteroaryl, substituted or unsubstituted C1-20alkyl-O-CO-;
R2、R3independently of one another, from hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
R4selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C3-C20The heterocycloalkyl group of (a);
R5、R6selected from hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20Or R is5、R6Are linked to each other and together with the nitrogen atom to which they are attached to form a substituted or unsubstituted C with or without other hetero atoms3-C20A cyclic group of (a); provided that R is5、R6Not hydrogen at the same time.
In any part of the present invention, any substituent in the expression "substituted or unsubstituted" is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)6-C20Aryl ethynyl group of3-C8Cycloalkyl of, C1-6alkyl-O-CO-. It will be appreciated by those skilled in the art that the number of substituents in the expression "substituted or unsubstituted" as referred to herein may be one or more, for example where a substituted phenyl group may have one, two, three, four or five substituents, the upper limit of the number of substituents being dependent on the position at which the group may be substituted.
As a further preference of the technical means of the present invention, wherein R1Selected from substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C6-14Aryl, substituted or unsubstituted C4-12Heteroaryl, substituted or unsubstituted C1-6alkyl-O-CO-;
R2、R3independently of one another, from hydrogen, substituted or unsubstituted C1-6Alkyl groups of (a);
R4selected from substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C3-C12The heterocycloalkyl group of (a);
R5、R6selected from hydrogen, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C3-C8Cycloalkyl, substituted or unsubstituted C6-14Aryl, substituted or unsubstituted C4-12Or R is5、R6Are linked to each other and together with the nitrogen atom to which they are attached to form a substituted or unsubstituted C with or without other hetero atoms3-C12A cyclic group of (a); provided that R is5、R6Not hydrogen at the same time.
Wherein the substituted or unsubstituted substituents are as defined herein before.
In the present invention, for said C1-20Alkyl of (C)1-12Examples of the alkyl group of (2) include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and neopentyl,N-hexyl, n-heptyl, undecyl, and the like.
In the present invention, as C1-6Alkoxy group of (C)1-6Examples of the alkyl group of (1), wherein the alkyl moiety may be specifically selected from the above-mentioned "C1-20Alkyl of (2)' C1-6The kind of alkyl group of (1).
In the present invention, as C6-20Aryl of (C)6-14Examples of the aryl group of (a) may be selected from, for example, phenyl, naphthyl, anthryl, phenanthryl and the like.
In the present invention, said C4-C20Heteroaryl of (A), C4-12The heteroatom in the heteroaryl group of (a) may be selected from O, S, N, and specific heteroaryl groups may be selected from, for example, thienyl, furyl, pyridyl, and the like.
In the present invention, as C3-C20Cycloalkyl of, C3-C12Examples of cycloalkyl groups of (a) may be selected, for example, from monocyclic cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; bicyclic, e.g. bicyclo [2.2.2]Octyl, bicyclo [2,2,1 ]]Heptadecyl, decalinyl; polycyclic such as adamantyl and the like.
In the present invention, as C3-C20Heterocycloalkyl of (A), C3-C12Examples of the heterocycloalkyl group of (3) may be selected from, for example, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, morpholinyl, piperazinyl, piperidinyl and the like.
According to the preceding radical definitions of the invention, wherein "or R5、R6Are linked to each other and together with the nitrogen atom to which they are attached to form a substituted or unsubstituted C with or without other hetero atoms3-C20And or R5、R6Are linked to each other and together with the nitrogen atom to which they are attached to form a substituted or unsubstituted C with or without other hetero atoms3-C12In the cyclic group "as C3-C20Cyclic group of (A), C3-C12Examples of cyclic groups which may be chosen from, for example, indolinyl
Figure BDA0001723518000000041
Tetrahydroquinolinyl
Figure BDA0001723518000000042
Benzomorpholinyl
Figure BDA0001723518000000043
And the like.
As a further preferred mode of the present invention, wherein R is1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl;
R2selected from hydrogen; r3Selected from hydrogen or C1-6Alkyl of (2)
R4Is selected from C1-12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl of, C3-C12The heterocycloalkyl group of (a);
R5、R6selected from hydrogen, substituted or unsubstituted C1-6Substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or R5、R6Are linked to each other and together with the linking nitrogen atom to form an indolinyl group
Figure BDA0001723518000000051
Tetrahydroquinolinyl
Figure BDA0001723518000000052
Benzomorpholinyl
Figure BDA0001723518000000053
Provided that R is5、R6Not hydrogen at the same time.
Wherein the substituted or unsubstituted substituents are as defined herein before.
According to the aforementioned method of the present invention, the photocatalyst is selected from Ir (ppy)3、Ru(bpy)3Cl2、Ru(bpy)3Cl2·6H2O、[Ir(dtbbpy)(ppy)2](PF6)2Most preferably any of the aboveRu(bpy)3Cl2。
The reaction auxiliary agent is tris (pentafluorophenyl) boron B (C)6F5)3。
The organic solvent is any one of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), acetonitrile (MeCN) and N-methylpyrrolidone (NMP), and the DMSO is the most preferable. The amount of the solvent to be used is not particularly limited so that the materials can be sufficiently dispersed.
The light source for illumination is provided by, for example, a 9-36W energy-saving lamp, or by a 1-5W blue LED light source.
According to the aforementioned reaction of the present invention, the inert atmosphere is an atmosphere inert to the reaction and is not mechanically considered to be an inert gas. It will be appreciated by those skilled in the art that the inert atmosphere commonly used for organic reactions may be selected from an argon atmosphere or a nitrogen atmosphere.
According to the reactions of the present invention described above, the reaction time is determined by TLC or GC-MS monitoring, and generally, the reaction is completed in 24 hours.
According to the reaction of the invention, the feeding molar ratio of the vinyl compound shown in the formula I, the N-substituted phthalimide compound shown in the formula II, the amine shown in the formula III, the photocatalyst and the reaction auxiliary agent is 1 (1-3), 1-3, 0.1-2%, and 5-20%. Preferably, the feeding molar ratio of the ethylene compound shown in the formula I, the N-substituted phthalimide compound shown in the formula II, the amine shown in the formula III, the photocatalyst and the reaction auxiliary agent is 1:1.5:1.5: 1: 10%.
The aforementioned reaction according to the present invention, wherein the post-treatment operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by silica gel column chromatography to obtain the target product shown in the formula IV, wherein the eluent separated by the silica gel column chromatography is the mixed solution of normal hexane and ethyl acetate.
The invention has the following beneficial effects:
1. the invention reports a synthesis strategy for obtaining a target product shown in a formula IV by taking an ethylene compound shown in a formula I, an N-substituted phthalimide compound shown in a formula II and amine shown in a formula III as raw materials and stirring and reacting at room temperature in the presence of a photocatalyst, a reaction auxiliary agent and an organic solvent under the condition of illumination and an inert atmosphere, wherein the synthesis process is not reported in the prior art.
2. The process has mild reaction condition, can be carried out at room temperature, and has the photocatalyst Ru (bpy)3Cl2Can be recycled by a filtration method.
3. The method has the advantages of simple operation, wide application range of reaction substrates, low cost of the production process and environmental friendliness.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1-12 optimization of reaction conditions
P-methoxystyrene shown as a formula I-1, an N-substituted phthalimide compound shown as a formula II-1 and 2, 3-dimethylaniline shown as a formula III-1 are used as reaction raw materials, the influence of different reaction conditions on the optimization result of the synthesis process is discussed, and representative examples 1-12 are selected. The results are shown in table one.
Figure BDA0001723518000000061
A typical experimental procedure for example 1 is as follows:
to a Schlenk closed-tube reactor were added p-methoxystyrene of the formula I-1 (0.2mmol), an N-substituted phthalimide compound of the formula II-1 (0.3mmol), 2, 3-dimethylaniline of the formula III-1 (0.3mmol), a photocatalyst Ir (ppy)3(1 mol%) and DMSO (2mL) under 5W blue LED illumination and argon atmosphere, stirring at room temperature for 24 hours, detecting by TLC that the reaction is complete, concentrating the mixed solution after the reaction under reduced pressure to obtain residue, and separating the residue by column chromatography to obtain the target product shown in formula IV-1, wherein the eluent separated by the column chromatography is a mixture of n-hexane and ethyl acetateAnd (4) mixing the liquid. The yield was 21%.1H NMR(400MHz,CDCl3):7.23(d,J＝9.2Hz,2H),6.846.82(m,3H),6.50(d,J＝7.6Hz,1H),6.27(d,J＝8.0Hz,1H),4.38(t,J＝7.2Hz,1H),3.77(s,3H),2.27(s,3H),2.12(s,3H),1.81-1.57(m,7H),1.26-1.13(m,3H),1.00-0.93(m,3H)；13C NMR(100MHz,CDCl3):158.3,145.3,137.1,136.2,127.1,126.0,119.7,118.9,113.9,109.1,55.2,54.8,47.5,34.7,33.9,33.0,26.5,26.2,26.1,20.7,12.6；LRMS(EI,70eV)m/z(％):337(M+,7),240(52),121(100)；HRMS m/z(ESI)calcd for C23H32NO([M+H]+)338.2478,found 338.24740.。
Table one:
Figure BDA0001723518000000071
Figure BDA0001723518000000081
the specific operations and parameters of examples 2-12 were the same as in example 1, except that the variables listed in Table one above were different from those of example 1.
As can be seen from examples 1-12, the results of the screening for the reaction solvent show that DMSO is the best reaction solvent, while MeCN and NMP can also achieve a certain yield of the desired product, but none of them is as DMSO (examples 1-3). The screening results for the photocatalyst showed that Ru (bpy)3Cl2Is the best photocatalyst, where the reaction did not proceed well when the photocatalyst was replaced with Eosin Y (examples 4-6). On the basis, in order to further improve the yield of the target product, the inventors explored the influence of various auxiliary agents on the optimization of the reaction result (examples 7-11), and the results show that tris (pentafluorophenyl) boron has a very significant promoting effect on the reaction of the invention when used as a reaction auxiliary agent. Increasing the temperature had an adverse effect on the reaction (example 12). In addition, the inventor also carries out a comparative test of no light and no light catalyst respectively, and the result shows that the catalyst is not usedThe reaction of the present invention is not possible under light conditions and/or without the use of a photocatalyst.
As can be seen from representative examples 1-12 in Table I, the best process conditions for the present invention are the process conditions of example 11. On the basis of obtaining the optimal process conditions, the inventors further selected the reaction raw materials of formula I, formula II and formula III with different substituents, and reacted under the optimal process conditions (example 11) to prepare various target compounds of formula IV.
Example 13
Figure BDA0001723518000000091
The compound of formula II-2 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-2 in 73% yield.1H NMR(400MHz,CDCl3):7.22(d,J＝7.6Hz,2H),6.83-6.81(m,3H),6.48(d,J＝7.2Hz,1H),6.23(d,J＝7.9Hz,1H),4.47-4.40(m,1H),3.75(s,3H),2.26(s,3H),2.11(s,3H),1.72(s,2H),1.50-1.40(m,6H),1.36-1.29(m,4H),1.03(s,3H)；13C NMR(100MHz,CDCl3):158.1,144.9,138.4,136.2,126.9,126.0,119.5,118.7,113.9,108.9,55.2,53.9,38.6,38.3,33.4,26.3,22.1,22.0,20.8,12.6；LRMS(EI,70eV)m/z(％):351(M+,7),240(42),97(100)；HRMS m/z(ESI)calcd for C24H34NO([M+H]+)352.2635,found 352.2630.。
Example 14
Figure BDA0001723518000000092
The compound of formula II-3 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-3 in 76% yield.1H NMR(400MHz,CDCl3):7.20(d,J＝8.4Hz,2H),6.85-6.80(m,3H),6.49(d,J＝7.2Hz,1H),6.22(d,J＝8.0Hz,1H),4.44(d,J＝7.2Hz,1H),3.84(s,1H),3.75(s,3H),2.27(s,3H),2.11(s,3H),1.98-1.90(m,3H),1.70-1.56(m,14H)；13C NMR(100MHz,CDCl3):158.1,144.9,138.4,136.1,126.9,126.0,119.5,118.7,113.9,109.0,55.5,55.2,53.0,43.1,36.9,32.9,28.6,20.8,12.6；LRMS(EI,70eV)m/z(％):389(M+,10),240(100)；HRMS m/z(ESI)calcd for C27H36NO([M+H]+)390.2791,found 390.2798.。
Example 15
Figure BDA0001723518000000101
The compound of formula II-4 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-4 in 47% yield.1H NMR(400MHz,CDCl3):7.18(d,J＝8.0Hz,2H),6.84-6.80(m,3H),6.50(d,J＝7.6Hz,1H),6.23(d,J＝8.0Hz,1H),4.45-4.36(m,1H),3.75(s,3H),3.62(s,3H),2.26(s,3H),2.10(s,3H),1.79-1.71(m,6H),1.66-1.61(m,2H),1.57-1.49(m,6H)；13C NMR(100MHz,CDCl3):178.3,158.2,144.6,137.8,136.2,126.9,126.0,119.5,118.9,113.9,108.9,55.2,53.7,51.8,51.6,38.7,31.1,31.0,28.5,20.7,12.6；(EI,70eV)m/z(％):421(M+,7),301(56),240(100),107(77)；HRMS m/z(ESI)calcd for C27H36NO3([M+H]+)422.2690,found 422.2697.。
Example 16
Figure BDA0001723518000000111
The compound of formula II-5 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-5 in 44% yield.1H NMR(400MHz,CDCl3):7.24(d,J＝8.4Hz,2H),6.86-6.82(m,3H),6.50(d,J＝7.6Hz,1H),6.28(d,J＝8.0Hz,1H),4.31(t,J＝6.4Hz,1H),3.76(s,3H),2.26(s,3H),2.11(s,3H),1.91-1.35(m,12H),1.26-1.14(m,3H)；13C NMR(100MHz,CDCl3):158.3,145.3,136.8,136.2,127.2,126.0,119.7,118.9,113.9,109.1,57.0,55.2,46.0,37.2,32.9,25.1,25.0,20.7,12.6；(EI,70eV)m/z(％):351(M+,7),240(100),121(7)；HRMS m/z(ESI)calcd for C24H34NO([M+H]+)352.2635,found 352.2642.。
Example 17
Figure BDA0001723518000000112
The compound of formula II-6 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-6 in 50% yield.1H NMR(400MHz,CDCl3):7.24(d,J＝8.4Hz,2H),6.84-6.82(m,3H),6.50(d,J＝7.6Hz,1H),6.28(d,J＝8.0Hz,1H),4.30(t,J＝6.4Hz,1H),3.76(s,3H),2.26(s,3H),2.11(s,3H),1.84-1.48(m,12H),1.26-1.14(m,3H)；13C NMR(100MHz,CDCl3):158.3,145.3,136.8,136.2,127.2,126.0,119.7,118.9,113.9,109.1,57.0,55.2,46.0,37.2,32.9,25.1,25.0,20.7,12.6；LRMS(EI,70eV)m/z(％):323(M+,5),240(37),121(100)；HRMS m/z(ESI)calcd for C22H30NO([M+H]+)324.2322,found 324.2329.。
Example 18
Figure BDA0001723518000000121
The compound of formula II-6 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-6 in 46% yield.1H NMR(400MHz,CDCl3):7.31(d,J＝8.0Hz,1H),7.23(d,J＝6.4Hz,1H),6.85-6.78(m,3H),6.50-6.45(m,1H),6.20-6.14(m,1H),4.65-4.58(m,0.55H),4.37-4.34(m,0.48H),3.97-3.86(m,2H),3.79-3.76(m,4H),2.27(s,3H),2.14-2.10(m,3H),2.00-1.78(m,5H),1.54-1.45(m,1H)；13C NMR(100MHz,CDCl3):158.4,158.2,146.0,145.3,137.0,136.1,136.1,135.5,127.4,127.1,125.9,125.7,120.7,119.7,118.9,118.3,113.9,113.8,109.4,108.6,78.5,76.2,67.9,67.8,58.2,55.3,55.2,55.1,45.2,43.0,38.4,36.2,32.3,31.6,25.5,25.2,20.7,12.6,12.6；(EI,70eV)m/z(％):325(M+,8),240(28),71(100)；HRMS m/z(ESI)calcd for C21H28NO2([M+H]+)326.2115,found 326.2119.。
Example 19
Figure BDA0001723518000000122
The compound of formula II-8 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-8 in 53% yield.1H NMR(400MHz,CDCl3):7.33-7.12(m,7H),6.79(d,J＝8.0Hz,2H),6.72(t,J＝7.2Hz,1H),6.46(d,J＝6.8Hz,1H),6.00(d,J＝7.6Hz,1H),4.20-4.09(m,2H),3.74(s,3H),2.24(s,3H),2.14-1.99(m,2H),1.91(s,3H),0.89-0.78(m,3H),0.59-0.56(m,1H)；13C NMR(100MHz,CDCl3):158.3,145.0,144.2,136.7,135.9,129.0,128.5,127.1,126.4,125.7,119.9,118.9,113.8,109.3,56.7,55.2,50.1,24.0,20.7,14.3,12.3,11.4；(EI,70eV)m/z(％):371(M+,6),240(100),207(12)；HRMS m/z(ESI)calcd for C26H30NO([M+H]+)372.2322,found 372.2329.。
Example 20
Figure BDA0001723518000000131
The compound of formula II-9 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-9 in 51% yield.1H NMR(400MHz,CDCl3):77.24(d,J＝8.0Hz,2H),6.84-6.82(m,3H),6.50(d,J＝7.2Hz,1H),6.27(d,J＝8.0Hz,1H),4.34(t,J＝7.2Hz,1H),3.76(s,3H),2.26(s,3H),2.11(s,3H),1.76-1.61(m,2H),1.41-1.26(m,5H),0.90-0.80(m,6H)；13C NMR(100MHz,CDCl3):158.3,145.3,137.1,136.2,127.1,126.0,119.7,118.9,113.9,109.1,55.5,55.2,43.5,37.3,25.6,25.2,20.7,12.6,10.9,10.4；LRMS(EI,70eV)m/z(％):325(M+,7),240(37),121(100)；HRMS m/z(ESI)calcd for C22H32NO([M+H]+)326.2478,found 326.2488.。
Example 21
Figure BDA0001723518000000132
The compound of formula II-10 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-10 in 50% yield.1H NMR(400MHz,CDCl3):7.22(d,J＝8.8Hz,2H),6.86-6.81(m,3H),6.49(d,J＝7.6Hz,1H),6.25(d,J＝8.0Hz,1H),4.41(t,J＝6.0Hz,1H),3.86(s,1H),3.76(s,3H),2.26(s,3H),2.11(s,3H),1.71(d,J＝6.0Hz,2H),1.01(s,9H)；13C NMR(100MHz,CDCl3):158.3,145.0,138.2,136.2,127.0,126.0,119.6,118.8,114.0,109.0,55.3,54.9,54.2,31.1,30.3,20.8,12.6；LRMS(EI,70eV)m/z(％):311(M+,12),240(36),121(42),57(100)；HRMS m/z(ESI)calcd for C21H30NO([M+H]+)312.2322,found 312.2330.。
Example 22
Figure BDA0001723518000000141
The compound of formula II-11 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, giving the desired product IV-11 in 52% yield.1H NMR(400MHz,CDCl3):7.24(d,J＝8.8Hz,2H),6.86-6.82(m,3H),6.50(d,J＝7.2Hz,1H),6.26(d,J＝8.0Hz,1H),4.26(t,J＝6.8Hz,1H),3.88(s,1H),2.27(s,3H),2.12(s,3H),1.82-1.77(m,2H),1.35-1.25(m,10H),0.87(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):158.4,145.3,136.7,136.3,127.3,126.0,119.8,119.0,113.9,109.2,57.7,55.2,39.3,31.8,29.5,29.2,26.5,22.7,20.8,14.1,12.6；LRMS(EI,70eV)m/z(％):339(M+,9),240(52),121(100)；HRMS m/z(ESI)calcd for C23H34NO([M+H]+)340.2635,found 340.2641.。
Example 23
Figure BDA0001723518000000142
The compound of formula II-12 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-12 in 44% yield.1H NMR(400MHz,CDCl3):7.23(d,J＝8.0Hz,2H),6.83(d,J＝7.6Hz,3H),6.50(d,J＝7.2Hz,1H),6.26(d,J＝7.6Hz,1H),4.26(t,J＝6.4Hz,1H),3.76(s,3H),2.26(s,3H),2.11(s,3H),1.90-1.70(m,2H),1.41-1.19(m,20H),0.91-0.86(m,3H)；13C NMR(100MHz,CDCl3):158.3,145.3,136.6,136.2,127.2,126.0,119.8,118.9,113.8,109.1,57.7,55.2,39.3,31.9,29.6,29.6,29.6,29.5,29.5,29.3,26.4,22.7,20.7,14.1,12.6；LRMS(EI,70eV)m/z(％):409(M+,14),240(100)；HRMS m/z(ESI)calcd for C28H44NO([M+H]+)410.3417,found 410.3423.。
Example 24
Figure BDA0001723518000000151
The compound of formula II-13 was used as the starting material, and the remaining starting materials, operations and parameters were the same as in example 11, to give the desired product IV-13 in 50% yield. 1H NMR (400MHz, CDCl3):7.23(d, J ═ 8.0Hz,2H),6.86-6.82(m,3H),6.50(d, J ═ 7.2Hz,1H),6.27(d, J ═ 8.0Hz,1H),4.26(t, J ═ 6.8Hz,1H),4.13-4.08(m,2H),3.76(s,3H),2.30-2.24(m,5H),2.11(s,3H),1.82-1.75(m,2H),1.62-1.59(m,2H),1.44-1.35(m,4H),1.24(t, J ═ 7.2Hz, 3H);13C NMR(100MHz,CDCl3):173.7,158.4,145.2,136.3,136.2,127.2,125.9,119.8,119.0,113.9,109.1,60.2,57.5,55.2,39.0,34.2,29.0,26.1,24.8,20.7,14.2,12.6；LRMS(EI,70eV)m/z(％):383(M+,9),240(85),121(100)；HRMS m/z(ESI)calcd for C24H34NO3([M+H]+)384.2533,found 384.2539.。
example 25
Figure BDA0001723518000000161
The target product IV-14 is obtained with the compounds of the formulas II-3 and III-2 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11, and the yield is 57%.1H NMR(400MHz,CDCl3):7.22(d,J＝7.2Hz,2H),7.07(t,J＝7.2Hz,2H),6.83(d,J＝7.2Hz,2H),6.61(t,J＝7.2Hz,1H),6.47(d,J＝7.6Hz,2H),4.44-4.37(m,1H),3.93(s,1H),3.75(s,3H),1.94(s,3H),1.71-1.52(m,14H)；13C NMR(100MHz,CDCl3):158.2,147.1,138.2,129.0,127.0,116.8,113.9,113.1,55.2,55.0,53.1,43.0,36.9,32.9,28.6；(EI,70eV)m/z(％):361(M+,7),269(9),212(73),135(100)；HRMS m/z(ESI)calcd for C25H32NO([M+H]+)362.2478,found 362.2470.。
Example 26
Figure BDA0001723518000000162
The target product IV-15 is obtained with the compound of the formula II-3 and III-3 as the reaction raw material and the rest of the reaction raw materials, operation and parameters as in example 11, with the yield of 35%.1H NMR(400MHz,CDCl3):7.23(d,J＝8.0Hz,2H),6.83(d,J＝7.6Hz,2H),6.68(d,J＝8.0Hz,2H),6.43(d,J＝7.6Hz,2H),4.37-4.28(m,1H),3.77(s,3H),3.68(s,3H),1.99-1.90(m,3H),1.70-1.51(m,14H)；13C NMR(100MHz,CDCl3):158.1,151.6,141.6,138.5,127.1,114.7,114.2,113.9,55.7,55.2,55.0,54.0,43.0,36.9,33.0,28.6；LRMS(EI,70eV)m/z(％):391(M+,3),242(18),135(100)；HRMS m/z(ESI)calcd for C26H34NO2([M+H]+)392.2584,found 392.2594.。
Example 27
Figure BDA0001723518000000171
The target product IV-16 is obtained by using the compounds of the formulas II-3 and III-4 as reaction raw materials and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 11, and the yield is 47 percent.1H NMR(400MHz,CDCl3):7.20(d,J＝7.6Hz,2H),6.97(t,J＝7.6Hz,1H),6.84(d,J＝7.6Hz,2H),6.57(d,J＝8.0Hz,1H),6.46(s,1H),6.33(d,J＝8.4Hz,1H),4.37(t,J＝5.6Hz,1H),4.00(s,1H),3.77(s,3H),1.99-1.92(m,3H),1.72-1.48(m,14H)；13C NMR(100MHz,CDCl3):158.3,148.2,137.4,134.7,130.0,127.0,116.8,114.0,112.8,111.3,55.2,54.9,53.1,43.0,36.9,33.0,28.6；LRMS(EI,70eV)m/z(％):397(M++2,1),395(M+,3),246(39),135(100)；HRMS m/z(ESI)calcd for C25H31ClNO([M+H]+)396.2089,found 396.2085.。
Example 28
Figure BDA0001723518000000172
The target product IV-17 is obtained with 48% yield by using the compounds of the formulas II-3 and III-5 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.23-7.19(m,3H),6.95(t,J＝8.0Hz,1H),6.83(d,J＝7.6Hz,2H),6.53(t,J＝7.6Hz,1H),6.37(d,J＝8.4Hz,1H),4.65(s,1H),4.42-4.38(m,1H),3.76(s,3H),2.02-1.90(m,3H),1.71-1.52(m,14H)；13C NMR(100MHz,CDCl3):158.3,142.8,137.5,128.8,127.6,126.9,118.8,116.7,114.0,112.2,55.2,53.0,43.0,36.9,32.9,28.6；LRMS(EI,70eV)m/z(％):397(M++2,1),395(M+,3),246(38),135(100)；HRMS m/z(ESI)calcd for C25H31ClNO([M+H]+)396.2089,found 396.2083.。
Example 29
Figure BDA0001723518000000181
The target product IV-18 is obtained by using the compounds of the formulas II-3 and III-6 as reaction raw materials and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 11, and the yield is 31 percent.1H NMR(400MHz,CDCl3):7.63(d,J＝8.0Hz,1H),7.19(d,J＝7.6Hz,2H),7.01(t,J＝7.6Hz,1H),6.83(d,J＝7.6Hz,2H),6.35(t,J＝7.2Hz,1H),6.27(d,J＝8.0Hz,1H),4.56(s,1H),4.45-4.43(m,1H),3.77(s,3H),2.00-1.92(s,3H),1.71-1.53(m,14H)；13C NMR(100MHz,CDCl3):158.3,146.0,138.8,137.3,129.2,126.9,118.1,114.0,111.7,85.2,55.3,55.2,53.3,43.1,36.9,32.9,28.6；LRMS(EI,70eV)m/z(％):487(M+,4),338(35),135(100)；HRMS m/z(ESI)calcd for C25H31INO([M+H]+)488.1445,found 488.1455.。
Example 30
Figure BDA0001723518000000182
The target product IV-19 is obtained with the compound of the formula II-3 and III-7 as the reaction raw material and the rest of the reaction raw materials, operation and parameters as in example 11, with the yield of 35%.1H NMR(400MHz,CDCl3):7.36(d,J＝7.6Hz,1H),7.23-7.19(m,3H),6.85(d,J＝7.6Hz,2H),6.60(t,J＝7.6Hz,1H),6.42(d,J＝8.4Hz,1H),4.85-4.84(m,1H),4.48(s,1H),3.77(s,3H),2.00-1.93(s,3H),1.71-1.54(m,14H)；13C NMR(100MHz,CDCl3):158.5,149.1,136.5,134.1,132.5,126.8,118.0,116.3,114.1,111.8,95.6,55.2,54.9,52.9,42.9,36.8,32.9,28.5；LRMS(EI,70eV)m/z(％):386(M+,2),269(13),237(57),135(100)；HRMS m/z(ESI)calcd for C26H31N2O([M+H]+)387.2431,found 387.2437.。
Example 31
Figure BDA0001723518000000191
The target product IV-20 is obtained with 50% yield by using the compounds of the formulas II-3 and III-8 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.53(d,J＝7.2Hz,2H),7.38-7.32(m,4H),7.23(d,J＝8.4Hz,2H),7.02(t,J＝7.6Hz,1H),6.84(d,J＝7.6Hz,2H),6.57(t,J＝7.2Hz,1H),6.32(d,J＝8.0Hz,1H),5.08(s,1H),4.51-4.43(m,1H),3.75(s,3H),1.97-1.90(m,3H),1.69-1.54(m,14H)；13C NMR(100MHz,CDCl3):158.2,147.8,137.7,131.8,131.3,129.8,128.4,128.1,126.9,123.4,116.0,114.0,110.7,107.3,94.9,86.4,55.3,55.2,53.2,43.1,36.9,32.9,28.6；HRMS m/z(ESI)calcd for C33H36NO([M+H]+)462.2791,found 462.2795.。
Example 31
Figure BDA0001723518000000201
The target product IV-21 is obtained with 48% yield by using the compounds of the formulas II-3 and III-9 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.86(d,J＝8.0Hz,1H),7.76(d,J＝6.8Hz,1H),7.45-7.43(m,2H),7.26(d,J＝7.6Hz,2H),7.20-7.12(m,2H),6.81(d,J＝7.6Hz,2H),6.33(d,J＝7.2Hz,1H),4.70(s,1H),4.63-4.59(m,1H),3.73(m,3H),1.97-1.88(s,3H),1.75-1.61(m,14H)；13C NMR(100MHz,CDCl3):158.2,141.9,137.7,134.2,128.7,126.9,126.7,125.5,124.6,123.1,119.6,116.6,114.0,105.5,55.4,55.2,53.2,43.1,36.9,33.0,28.6；(EI,70eV)m/z(％):411(M+,20),262(100),230(12)；HRMS m/z(ESI)calcd for C29H34NO([M+H]+)412.2635,found 412.2632.。
Example 33
Figure BDA0001723518000000202
The target product IV-22 is obtained with the compound of the formula II-3 and III-10 as the reaction raw material and the rest of the reaction raw materials, operation and parameters as in example 11, and the yield is 52%.1H NMR(400MHz,CDCl3):7.22(t,J＝7.2Hz,2H),7.15(d,J＝8.0Hz,2H),6.80(t,J＝7.2Hz,4H),6.69(t,J＝7.2Hz,1H),5.10(t,J＝6.0Hz,1H),3.76(s,3H),2.65(s,3H),1.90(s,3H),1.85-1.75(m,2H),1.67-1.49(m,12H)；13C NMR(100MHz,CDCl3):158.2,149.9,134.5,129.1,128.3,116.3,113.4,113.3,56.2,55.1,46.0,42.9,37.0,32.6,32.1,28.7；(EI,70eV)m/z(％):375(M+,7),226(100)；HRMS m/z(ESI)calcd for C26H34NO([M+H]+)376.2635,found 376.2638.。
Example 34
Figure BDA0001723518000000211
The target product IV-23 is obtained with 61% yield by using the compounds of the formulas II-3 and III-11 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.23(d,J＝8.0Hz,2H),7.05(t,J＝7.6Hz,1H),6.97(d,J＝6.8Hz,1H),6.80(d,J＝7.6Hz,2H),6.61(d,J＝7.6Hz,1H),6.53(t,J＝7.2Hz,1H),4.82(t,J＝6.0Hz,1H),3.75(s,3H),3.49-3.42(m,1H),3.14-3.07(m,1H),2.89-2.77(m,2H),1.94-1.86(m,3H),1.78(d,J＝6.4Hz,2H),1.67-1.48(m,12H)；13C NMR(100MHz,CDCl3):158.4,150.8,133.4,129.8,129.1,127.1,124.4,116.2,113.4,106.4,55.1,53.2,46.3,44.7,43.0,37.0,32.6,28.7,27.9；(EI,70eV)m/z(％):387(M+,4),238(12),135(100)；HRMS m/z(ESI)calcd for C27H34NO([M+H]+)388.2635,found 388.2644.。
Example 35
Figure BDA0001723518000000212
The target product IV-24 is obtained with the compound of the formula II-3 and III-12 as the reaction raw material and the rest of the reaction raw materials, operation and parameters as in example 11, and the yield is 63%.1H NMR(400MHz,CDCl3):7.21(d,J＝8.0Hz,2H),7.05(t,J＝7.6Hz,1H),6.92(d,J＝7.2Hz,1H),6.86(d,J＝8.4Hz,1H),6.80(d,J＝8.0Hz,2H),6.53(t,J＝7.2Hz,1H),5.13(t,J＝6.0Hz,1H),3.75(s,3H),3.27-3.22(m,1H),3.00-2.96(m,1H),2.70-2.60(m,2H),1.91-1.80(m,6H),1.68-1.52(m,13H)；13C NMR(100MHz,CDCl3):158.2,145.1,134.4,129.3,128.5,127.0,122.9,115.0,113.4,111.2,55.1,54.2,45.1,43.0,37.0,32.8,28.7,21.9；LRMS(EI,70eV)m/z(％):401(M+,9),252(100)；HRMS m/z(ESI)calcd for C28H36NO([M+H]+)402.2791,found 402.2799.。
Example 36
Figure BDA0001723518000000221
The target product IV-25 is obtained with 59% yield by using the compounds of the formulas II-3 and III-13 as reaction raw materials and the rest of the reaction raw materials, operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.22(d,J＝7.2Hz,2H),7.04(d,J＝8.0Hz,1H),6.89-6.70(m,4H),6.59(d,J＝7.6Hz,1H),5.13(t,J＝6.0Hz,1H),4.11-4.08(m,1H),3.84-3.76(m,1H),3.76(s,3H),3.26-3.24(m,1H),3.05-3.04(m,1H),1.95-1.89(s,3H),1.78(d,J＝6.0Hz,2H),1.69-1.50(m,12H)；13C NMR(100MHz,CDCl3):158.5,144.1,134.7,133.2,128.8,121.5,116.7,116.6,113.4,112.6,64.2,55.1,54.2,44.1,43.0,40.5,36.9,32.7,28.6；LRMS(EI,70eV)m/z(％):403(M+,15),254(100)；HRMS m/z(ESI)calcd for C27H34NO2([M+H]+)404.2584,found 404.2580.。
Example 37
Figure BDA0001723518000000222
The target product IV-26 is obtained with 83% yield by using the compounds of the formulas I-2, II-3 and III-2 as reaction raw materials and the rest of the operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.20(d,J＝7.6Hz,2H),7.11-7.06(m,4H),6.61(t,J＝7.2Hz,1H),6.47(d,J＝7.6Hz,2H),4.42(t,J＝5.2Hz,1H),3.97(s,1H),2.30(s,3H),1.98-1.91(s,3H),1.71-1.53(m,14H)；13C NMR(100MHz,CDCl3):147.1,143.2,136.0,129.3,129.0,125.9,116.8,113.1,55.1,53.5,43.0,36.9,33.0,28.7,21.0；LRMS(EI,70eV)m/z(％):345(M+,3),196(100),135(30)；HRMS m/z(ESI)calcd for C25H32N([M+H]+)346.2529,found 346.2519.。
Example 38
Figure BDA0001723518000000231
The target product IV-27 is obtained with 71% yield by using the compounds of the formulae I-3, II-3, III-2 as reaction raw materials and the rest of the operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.15-7.07(m,2H),6.97-6.92(m,2H),6.69-6.61(m,1H),6.48-6.40(m,2H),5.88(d,J＝11.2Hz,2H),4.81-4.73(m,1H),2.00-1.92(m,3H),1.76-1.40(s,14H)；13C NMR(100MHz,CDCl3):147.8,147.1,146.4,138.0,129.2,117.2,112.9,112.6,112.0,107.3,101.5,53.3,52.9,43.2,36.9,33.3,28.7；LRMS(EI,70eV)m/z(％):455(M++2,3),453(M+,3),306(49),135(100)；HRMS m/z(ESI)calcd for C25H29BrNO2([M+H]+)454.1376,found 454.1371.。
Example 39
Figure BDA0001723518000000232
The target product IV-28 is obtained with 53% yield by using the compounds of the formulae I-4, II-3, III-2 as reaction raw materials and the rest of the operation and parameters as in example 11.1H NMR(400MHz,CDCl3):7.11(t,J＝6.8Hz,2H),7.03-6.98(m,1H),6.80-6.74(s,1H),6.67(t,J＝7.6Hz,1H),6.51(d,J＝7.6Hz,2H),4.74-4.67(m,1H),3.93(s,1H),2.27(s,3H),2.00-1.91(s,3H),1.71-1.57(m,14H)；13C NMR(100MHz,CDCl3):146.9,145.6,130.4,130.2,129.1,121.8,117.5,113.1,54.1,48.6,43.0,36.8,32.9,28.6,13.9；LRMS(EI,70eV)m/z(％):351(M+,4),202(31),135(100)；HRMS m/z(ESI)calcd for C23H30NS([M+H]+)352.2093found 352.2099.。
Example 40
Figure BDA0001723518000000241
The compounds of the formulas I-5, II-3 and III-2 are used as transThe starting materials, the remaining operations and parameters were the same as in example 11, giving the desired product IV-29 in 33% yield.1H NMR(400MHz,CDCl3):7.18(d,J＝7.6Hz,2H),7.07(t,J＝7.2Hz,2H),6.83(d,J＝7.6Hz,2H),6.61(t,J＝7.2Hz,1H),6.42(d,J＝7.6Hz,2H),4.66(s,1H),4.06(s,1H),3.77(s,3H),2.04-1.94(m,3H),1.67-1.56(m,13H),0.83(d,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3):158.0,147.0,136.8,129.0,127.5,116.6,113.6,113.1,55.4,55.2,51.4,40.6,37.1,35.3,28.8,6.1；LRMS(EI,70eV)m/z(％):375(M+,3),212(100),135(10)；HRMS m/z(ESI)calcd for C26H34NO([M+H]+)376.2635,found 376.2646.。
The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.

Claims (9)

1. A process for the 1, 2-difunctionalization of olefins, characterized in that it comprises the following steps:
adding an ethylene compound shown as a formula I, an N-substituted phthalimide compound shown as a formula II, an amine shown as a formula III, a photocatalyst, a reaction auxiliary agent and an organic solvent into a Schlenk tube-sealed reactor, stirring at room temperature under the conditions of illumination and inert atmosphere for reaction, detecting by TLC that the reaction is complete, and carrying out aftertreatment to obtain a target product shown as a formula IV;
Figure FDA0002561107630000011
wherein R is1Selected from substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20The heteroaryl group of (a);
R2selected from hydrogen;
R3selected from hydrogen, C1-20Alkyl groups of (a);
R4selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C3-C20The heterocycloalkyl group of (a);
R5selected from hydrogen, C1-20Alkyl groups of (a);
R6selected from substituted or unsubstituted C6-20Aryl of (a);
or R5、R6Are linked to each other and together with the nitrogen atom to which they are linked to form C with or without other hetero atoms3-C20A cyclic group of (a);
in all the radical definitions mentioned above, the substituents in the expression "substituted or unsubstituted" are selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -CN, C6-C20Aryl of (C)6-C20Aryl ethynyl group of3-C8Cycloalkyl of, C1-6alkyl-O-CO-;
and wherein the photocatalyst is selected from Ir (ppy)3、Ru(bpy)3Cl2、Ru(bpy)3Cl2·6H2O、[Ir(dtbbpy)(ppy)2](PF6)2Any one of the above;
the reaction auxiliary agent is tris (pentafluorophenyl) boron B (C)6F5)3。
2. The method of claim 1, wherein R is1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl;
R2selected from hydrogen; r3Selected from hydrogen or C1-6Alkyl groups of (a);
R4is selected from C1-12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl of, C3-C12The heterocycloalkyl group of (a);
R5selected from hydrogen, C1-6Alkyl groups of (a);
R6selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or R5、R6Are linked to each other and together with the linking nitrogen atom to form an indolinyl group
Figure FDA0002561107630000021
Tetrahydroquinolinyl
Figure FDA0002561107630000022
Benzomorpholinyl
Figure FDA0002561107630000023
Wherein the substituents in said "substituted or unsubstituted" are as defined in claim 1.
3. The method according to any one of claims 1 to 2, wherein the organic solvent is any one of dimethylsulfoxide, N-dimethylformamide, acetonitrile, N-methylpyrrolidone.
4. The method of any one of claims 1-2, wherein the source of illumination is provided by a 9-36W energy saving lamp or by a 1-5W blue LED source.
5. The method according to any one of claims 1-2, wherein the photocatalyst is Ru (bpy)3Cl2And the organic solvent is selected from DMSO.
6. The method according to any one of claims 1-2, wherein the inert atmosphere is selected from an argon atmosphere or a nitrogen atmosphere.
7. The method according to any one of claims 1 to 2, wherein the ethylene compound of formula I, the N-substituted phthalimide compound of formula II, the amine of formula III, the photocatalyst and the reaction assistant are added in a molar ratio of 1 (1-3) to 1-3 (0.1-2%) to 5-20%.
8. The method as claimed in claim 7, wherein the feeding molar ratio of the vinyl compound of formula I, the N-substituted phthalimide compound of formula II, the amine of formula III, the photocatalyst and the reaction assistant is 1:1.5:1.5: 1: 10%.
9. A method according to any of claims 1-2, characterized in that the post-processing operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by silica gel column chromatography to obtain the target product shown in the formula IV, wherein the eluent separated by the silica gel column chromatography is the mixed solution of normal hexane and ethyl acetate.
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