CN108640839B - Intermolecular 1, 2-dialkylation reaction method of olefin compound under photo-oxidation-reduction/iron (II) catalytic system - Google Patents
Intermolecular 1, 2-dialkylation reaction method of olefin compound under photo-oxidation-reduction/iron (II) catalytic system Download PDFInfo
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Abstract
The invention discloses an intermolecular 1, 2-dialkylation reaction method of an olefin compound under a photo-oxidation-reduction/iron (II) catalytic system. According to the method, an olefin compound shown as a formula I, a compound shown as a formula II and a 1, 3-dicarbonyl compound shown as a formula III are subjected to intermolecular 1, 2-dialkylation reaction of olefin under a photo-oxidation-reduction catalysis/ferrous iron concerted catalysis system to obtain a series of compounds shown as a formula IV. Has the advantages of simple process, mild reaction conditions, environmental protection, wide application range of reaction substrates and high yield.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an intermolecular 1, 2-dialkylation reaction method of an olefin compound under a photo-oxidation-reduction/iron (II) catalysis system.
Background
The rapid increase in molecular complexity from readily available chemicals (especially feedstocks derived from the petroleum industry, such as olefins, alkanes and aromatics) through a mild, economical and practical selective catalytic pathway is one of the main goals of academia and industry. In this field, the functionalization of molecules by conversion of olefins and/or C-H bonds is an attractive and challenging goal, which has attracted great interest to researchers. Typical strategies include two-carbon functionalization of olefins by introducing two ortho carbon-based functional groups to extend the carbon chain, resulting in compounds with complex structures. However, most olefin two-carbon functionalization processes are often limited to classical cross-coupling reactions, which in turn often require the use of expensive nucleophilic and/or electrophilic reagents (e.g., organometallic compounds and organic halides) and catalytic systems. Furthermore, the addition of alkyl groups to olefins to achieve difunctionalization is rare, in part because of the high propensity to undergo competing side reactions (e.g., Heck-type β -hydrogen elimination, homocoupling, isomerization, etc.).
In addition, olefin dicarbofunctionalization reactions functionalized by oxidative radicals of one or two C-H bonds have attracted increasing interest over the past few years, which do not require the use of expensive functional reagents and noble metals, and offer excellent selectivity, high atom economy and cost advantages. However, the existing processes are still quite limited and limited to two modes, including alkylarylation and acylation, by an intramolecular intrinsic aryl group C (Sp)2) -H cyclization process and is achieved at rather high reaction temperatures. To the best of the inventors' knowledge, different C (sp) s are used3) Examples of-H bonds to achieve intermolecular dialkylation of olefins have never been reported.
The photo-oxidation-reduction/transition metal catalytic system has become a novel and effective synthesis strategy for constructing new chemical bonds in the field of organic synthesis due to the characteristics of high catalytic activity, mild conditions and the like. The inventors have made extensive studies and, in the present invention, have proposed a novel method for intermolecular 1, 2-dialkyl reaction of olefins in a photo-redox/iron (II) catalyst system.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel intermolecular 1, 2-dialkylation reaction method of olefin compounds in a photo-oxidation-reduction/iron (II) catalytic system, which has the advantages of simple process, mild reaction conditions, environmental friendliness, wide application range of reaction substrates and high yield.
The invention provides a method for intermolecular 1, 2-dialkylation reaction of olefin compounds under a photo-oxidation-reduction/iron (II) catalytic system, which comprises the following preparation steps:
into a Schlenk reactor, an olefinic compound of formula I, a compound of formula II, a 1, 3-dicarbonyl compound of formula III, a divalent iron catalyst, a photo-redox catalyst, and a free radical initiator are charged. And then protecting the reactor with inert atmosphere, stirring and reacting for 48 hours under the conditions of 30-120 ℃ and 5W LED blue light lamp irradiation, detecting the complete reaction of the raw materials through TLC and/or GC-MS analysis, and carrying out post-treatment after the reaction is finished to obtain the target product shown in the formula IV.
Wherein R is1Represents hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
R2represents substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20Heteroaryl, substituted or unsubstituted C1-20alkyl-O-CO-;
R3represents hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
R4、R5independently of one another, from hydrogen, substituted or unsubstituted C1-20Or R is4、R5Together with the carbon atom to which they are attached form C3-20Or R is cycloalkyl, or4、R5Together with the carbon atom to which they are attached form C3-20Wherein said cycloalkyl and heterocyclyl may be further substituted by a substituent. Wherein R is4、R5Not hydrogen at the same time.
R6、R7Independently of one another, from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C1-20Alkoxy, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20The heteroaryl group of (a);
R8selected from hydrogen, substituted or unsubstituted C1-20Alkyl group of (1).
Wherein the ferrous catalyst is selected from Fe (OTf)2、FeCl2、Fe(acac)2Any one of them.
The photo-redox catalyst is selected from Eosin Y.
The free radical initiator is selected from any one of DTBP, TBHP and TBPB.
In any part of the present invention, the substituent in the expression "substituted or unsubstituted" may be selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、 C6-C20Aryl of (C)3-C6A cycloalkyl group of (a). It will be appreciated by those skilled in the art that the number of substituents for said "substituted" may be one or more, for example two, three, four, five; when two or more substituents are present, the substituents can then be selected independently of one another from the substituent definitions given above. Further, it is understood by those skilled in the art that adjacent two substituents may also be connected to each other to form a cyclic structure, if necessary.
Preferably, R1Represents hydrogen, C1-20Alkyl group of (1).
R2Is represented by C1-20Alkyl, substituted or unsubstituted C6-20Aryl of (C)1-20alkyl-O-CO-; wherein the substituents of said "substituted" are as defined above.
R3Represents hydrogen.
R4、R5Independently of one another, from hydrogen, C1-20Or R is4、R5Together with the carbon atom to which they are attached form C3-20Or R is cycloalkyl, or4、R5Together with the carbon atom to which they are attached form C3-20The heterocyclic group of (1). Wherein R is4、R5Not hydrogen at the same time.
R6、R7Independently of one another, from C1-20Alkyl of (C)1-20Alkoxy group of (C)6-20Aryl group of (1).
R8Selected from hydrogen, C1-20Alkyl group of (1).
In the present invention, as C1-20Examples of the alkyl group of (a) may be selected from, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, and the like.
In the present invention, as C1-20Examples of the alkoxy group of (1), wherein the alkyl moiety may be specifically selected from the above-mentioned "C1-20Alkyl groups of (1) alkyl groups of the definition of alkyl.
In the present invention, as C6-20Examples 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-C20The 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-C6Examples of cycloalkyl groups of (a) may be selected from, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
According to the preceding radical definitions of the invention, the said "or R4、R5Together with the carbon atom to which they are attached form C3-20In the definition of "cycloalkyl group", as C3-20Examples of the cyclic hydrocarbon group of (2) may be selected from, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl and the like.
According to the preceding radical definitions of the invention, the said "or R4、R5Together with the carbon atom to which they are attached form C3-20The heterocyclic group of (1)' As C in this definition3-20The hetero atom in the heterocyclic group of (2) may be O, S, N, specifically, as C3-20Examples of the heterocyclic group of (3) may be selected from, for example, 1, 4-dioxane, tetrahydrofuranyl, morpholinyl and the like.
Therefore, as a further preferable aspect of the present invention,R1represents hydrogen, methyl, ethyl, propyl.
R2Is represented by C1-6Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, C1-6alkyl-O-CO-; wherein the substituents of said "substituted" are as defined above.
R3Represents hydrogen.
R4、R5Independently of one another, from hydrogen; c1-6Alkyl groups of (a); or R4、R5Together with the carbon atom to which they are attached form cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl; or R4、R5Together with the carbon atom to which they are attached form a 1, 4-dioxane group, a tetrahydrofuranyl group, a morpholinyl group. Wherein R is4、R5Not hydrogen at the same time.
R6、R7Independently of one another, from methyl, ethyl, propyl, methoxy, ethoxy, propoxy, phenyl.
R8Selected from hydrogen, methyl, ethyl, propyl.
Wherein, the ferrous catalyst is preferably selected from Fe (OTf)2。
The photo-redox catalyst is selected from Eosin Y.
The radical initiator is preferably selected from DTBP.
According to the reactions of the present invention described above, the reaction time is determined by TLC or GC-MS monitoring, and generally 48 hours is sufficient for completion.
According to the aforementioned reaction of the present invention, the reaction temperature is 30 to 120 ℃, preferably 30 to 100 ℃.
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 reaction of the invention, the molar ratio of the olefin compound shown in the formula I, the 1, 3-dicarbonyl compound shown in the formula III, the ferrous catalyst, the photo-oxidation-reduction catalyst and the free radical initiator is 1 (1-3): (10-30%): 5-15%): 1-3; preferably, the molar ratio of the olefinic compound of formula I, the 1, 3-dicarbonyl compound of formula III, the ferrous catalyst, the photo-redox catalyst, and the free radical initiator is 1:2: 20% to 10: 2.
In the present invention, the aforementioned reaction does not require the use of an additional organic solvent, and the compounds represented by formula II such as cyclopentane, cyclohexane and the like are used as solvents in the present invention, and the amount thereof is not particularly limited so as to sufficiently disperse the respective materials.
In the invention, the DTBP, TBHP and TBPB have the known definitions in the field, wherein the Chinese name of DTBP is di-tert-butyl peroxide, and the structural formula of DTBP is shown in the specification
TBHP is named as tert-butyl hydroperoxide or tert-butyl hydroperoxide in Chinese and has a structural formula
TBPB is named tert-butyl peroxybenzoate in Chinese and has a structural formula
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 using column chromatography to obtain the target product shown in the formula IV, wherein the eluent separated by using the column chromatography is the mixed solution of normal hexane and ethyl acetate.
The invention has the following beneficial effects:
1. the invention reports a series of synthetic strategies of the compounds shown in the formula IV by using the olefin compounds shown in the formula I, the compounds shown in the formula II and the 1, 3-dicarbonyl compounds shown in the formula III under a photo-oxidation-reduction catalysis/ferrous iron concerted catalysis system for the first time, and the method is not reported in the prior art.
2. The method has mild reaction conditions, can carry out reaction of most raw materials at 30 ℃, obviously reduces the reaction temperature by using the photocatalyst Eosin Y, and saves energy consumption.
3. The method has the advantages of simple operation, wide application range of reaction substrates, low cost of the generation process, environmental friendliness and high yield of target products.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1-16 optimization of reaction conditions
P-methoxystyrene shown as a formula I-1, cyclohexane shown as a formula II-1 and 1, 3-dicarbonyl compound 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 studied, and representative examples 1-16 are selected. The results are shown in table one.
A typical experimental procedure for example 1 is as follows:
to a Schlenk reactor was added p-methoxystyrene of formula I-1 (0.2mmol), cyclohexane of formula II-1 (2mL), 1, 3-dicarbonyl compound of formula III-1 (0.3mmol), Fe (OTf)2(20 mol%; i.e., 0.04 mmol), Eosin Y (10 mol%; i.e., 0.02mmol), and DTBP (2 equiv; i.e., 0.4 mmol). And then, the reactor is protected by argon, the mixture is stirred and reacted for 48 hours under the irradiation condition of a 5W LED blue light lamp at the temperature of 30 ℃, the TLC and/or GC-MS analysis detects that the raw materials are completely reacted, the vacuum concentration is carried out after the reaction is finished, and the residue is separated by silica gel column chromatography (ethyl acetate/normal hexane is used as eluent) to obtain the target product IV-1 with the yield of 82 percent. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.09(d,J＝7.2 Hz,0.67H),7.79(d,J＝7.6Hz,1.36H),7.58(t,J＝7.2Hz,0.38H),7.47(m,1.44H), 7.34(t,J＝7.6Hz,1.0H),7.21(d,J＝8.0Hz,0.74H),7.09(d,J＝8.0Hz,1.36H), 6.84(d,J＝8.0Hz,0.73H),6.68(d,J＝8.0Hz,1.33H),4.64-4.56(m,1.0H), 4.21-4.16(m,1.0H),3.89-3.58(m,5.0H),1.93-1.87(m,1.0H),1.66-1.34(m,6.0H), 1.26-1.21(m,2.0H),1.07-1.01(m,3.0H),0.94-0.84(m,4.0H)；13C NMR(100MHz, CDCl3):194.1,193.8,168.7,168.0,158.3,157.9,136.9,133.6,133.4,133.1,129.5, 129.2,128.7,128.4,113.6,61.9,61.6,61.4,61.1,55.1,55.0,42.2,42.11,41.9,41.5, 34.6,34.5,34.4,34.2,31.7,31.5,26.5,26.5,26.1,25.9,14.1,13.7；LRMS(EI,70eV) m/z(％):408(M+,1),390(14),217(12),121(100)；HRMS m/z(ESI)calcd for C26H33O4([M+H]+)409.2373,found 409.2381。
table one:
| examples | Reaction conditions (variables) | Separation yield [% ]] |
| 1 | ---- | 82 |
| 2 | No addition of Fe (OTf)2 | Trace amount ofa |
| 3 | Fe(OTf)2(10 mol%) reaction temperature is 60 DEG C | 40 |
| 4 | Fe(OTf)2(30mol％) | 53 |
| 5 | FeCl2In place of Fe (OTf)2 | 71 |
| 6 | Fe(acac)2In place of Fe (OTf)2 | 62 |
| 7 | Fe(OTf)3In place of Fe (OTf)2 | 8 |
| 8 | FeCl3In place of Fe (OTf)2 | 21 |
| 9 | No addition of Eosin Y | Trace amount ofb/36c/80d |
| 10 | Ru(bpy)3Cl2In place of Eosin Y | <5 |
| 11 | Ir(ppy)3In place of Eosin Y | <5/51e |
| 12 | Without addition of DTBP | Trace amount ofa |
| 13 | TBHP substituted for DTBP | 22 |
| 14 | TBPB instead of DTBP | 57 |
| 15 | Without illumination | Trace/78d |
| 16 | The feed amount is amplified by 5 times | 80 |
Wherein a represents a reaction temperature of 30 ℃ or 120 ℃; b represents a reaction temperature of 30 ℃ or 100 ℃; c represents a reaction temperature of 110 ℃; d represents a reaction temperature of 120 ℃; e denotes a reaction temperature of 80 ℃.
The specific operations and parameters of examples 2-16 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 to 16, no Fe (OTf) was added2In the case of (1), even if the reaction temperature is raised to 120 ℃, the intended target product IV-1 (example 2) cannot be obtained; fe (OTf)2The amount of the iron (III) catalyst, e.g. Fe (OTf), and the type of the iron (II) catalyst are influenced to different extents3And FeCl3The reaction was not promoted to proceed smoothly well (examples 3 to 8). In the absence of the photocatalyst Eosin Y, even if the reaction temperature is raised to 100 ℃, the reaction can detect only a trace amount of the target product by GC, but interestingly, Eosin was not added to the photocatalystWhen the reaction temperature was further increased to 110 ℃ and 120 ℃ in the case of Y, the desired product was able to be obtained in yields of 36% or 80%, respectively (example 9), indicating that the use of the photocatalyst Eosin Y is necessary for reactions below 100 ℃. Other photocatalysts, e.g. Ru (bpy)3Cl2And Ir (ppy)3All are much less effective than Eosin Y, but when the photocatalyst is selected from Ir (ppy)3And a yield of 51% of the desired product was still obtained at a reaction temperature of 80 ℃ (examples 10-11). Only traces of the target product were detected by GC without adding DTBP, but the different radical reagents such as TBHP, TBPB were not as effective as DTBP (examples 13-14). The formation of traces of the target product was detected by GC in the absence of light, but a yield of 78% of the target product was also obtained at elevated temperature up to 120 ℃ (example 15), consistent with the absence of photocatalyst Eosin Y (example 9). The charge of each material in the reaction is enlarged by 5 times, and the equivalent yield of the target product under the standard condition can still be obtained (example 16), which shows that the process of the invention is easy to be scaled up.
Based on the representative conditions optimization test results described above, examples 1-16, the reaction conditions of example 1 were selected as the optimal reaction conditions. On this basis, the inventors further selected reaction starting materials of different substituents to prepare various target compounds of formula IV.
Example 17
The p-methylstyrene of formula I-2 is used as the starting material, and the remaining reaction materials, operations and parameters are the same as those of example 1, to obtain the target product IV-2 with a yield of 70%. dr is 1.3: 1; a light yellow oily liquid;1H NMR(400MHz, CDCl3):8.09(d,J＝7.2Hz,1.0H),7.80(d,J＝7.6Hz,1.0H),7.58(t,J＝7.0Hz, 0.50H),7.50-7.44(m,1.66H),7.33(t,J＝6.8Hz,1.0H),7.17(d,J＝7.6Hz,1.0H), 7.11-7.05(m,2.0H),6.94(d,J＝7.6Hz,1H),4.67-4.58(m,1.0H),4.23-4.15(m, 1.0H),3.83-3.73(m,2.0H),2.32-2.20(m,4.0H),1.96-1.93(m,1.0H),1.70-1.65(m, 1.0H),1.54-1.43(m,4.0H),1.38-1.32(m,1.0H),1.26-1.20(m,2.0H),1.07-1.05(m, 2.0H),0.94-0.84(m,4H)；13C NMR(100MHz,CDCl3):193.9,193.8,168.7,167.9, 138.4,138.1,137.0,136.9,136.1,135.8,133.5,133.0,128.89,128.7,128.4,128.3, 128.1,61.8,61.5,61.4,61.1,42.5,42.1(2C),41.5,34.6,34.4(2C),34.2,31.7,31.5, 26.5,26.5,26.1,25.8,21.1,20.9,14.1,13.6；LRMS(EI,70eV)m/z(％):392(M+,1), 374(10),278(28),105(100)；HRMS m/z(ESI)calcd for C26H33O3([M+H]+) 393.2424,found 393.2432。
example 18
The p-bromostyrene of the formula I-4 is used as a raw material, and the rest of the reaction raw materials, operations and parameters are the same as those of the example 1, so that the target product IV-4 is obtained with the yield of 75%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz, CDCl3):8.08(d,J＝7.6Hz,2H),7.61(t,J＝7.2Hz,1H),7.50(t,J＝7.6Hz,2H), 7.43(d,J＝8.0Hz,2H),7.18(d,J＝8.0Hz,2H),4.56(d,J＝10.4Hz,1H), 3.82-3.76(m,3H),1.95-1.85(m,1H),1.72-1.61(m,2H),1.54-1.34(m,7H), 1.07-1.02(s,2H),0.91-0.86(m,4H)；13C NMR(100MHz,CDCl3):193.4,167.7, 140.4,136.7,133.7,131.4,130.3,128.8,128.7,120.5,61.4,61.3,42.3,42.0,34.5, 34.4,31.5,26.4,26.1,25.8,13.7；LRMS(EI,70eV)m/z(％):458(M++2,1),456 (M+,1),440(5),342(16),105(100)；HRMS m/z(ESI)calcd for C25H30 79BrO3([M+H]+)457.1373,found 457.1381.。
example 19
The reaction temperature was 100 ℃ using p-cyanostyrene of the formula I-5 as a starting material, and the other reaction materials, operations and parameters were the same as those of example 1 to obtain the objectiveThe product IV-5 was obtained in 46% yield. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.08(d,J＝8.0Hz,1.0H),7.80(d,J＝7.6Hz,1.0H), 7.63-7.60(m,1.6H),7.52-7.42(m,3.54H),7.41-7.32(m,2.0H),4.66(d,J＝10.8Hz, 0.48H),4.62(d,J＝10.8Hz,0.50H),4.22-4.15(m,1H),3.95-3.85(m,1H), 3.80-3.75(m,1H),1.91-1.88(m,1.0H),1.71-1.34(m,6.0H),1.26-1.20(m,3H), 1.09-1.04(m,2H),0.88-0.84(m,4H)；13C NMR(100MHz,CDCl3):193.1,192.8, 168.0,167.4,147.5,147.3,136.5,136.3,133.8,133.5,132.0,129.4,129.1,128.8, 128.6,128.5,128.3,118.7,118.7,110.6,110.3,61.7,61.3,60.9,60.8,42.8,42.51, 41.72,41.1,34.6,34.4,34.3,34.2,31.6,31.4,26.3,26.3,25.9,25.9,25.7,14.0,13.6； (EI,70eV)m/z(％):403(M+,1),298(11),192(8),105(100)；HRMS m/z(ESI) calcd for C26H30NO3([M+H]+)404.2220,found 404.2228.。
example 20
The o-methoxystyrene of the formula I-9 is used as a raw material, and the rest of the reaction raw materials, operations and parameters are the same as those of example 1, so that the target product IV-9 is obtained with the yield of 74%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz, CDCl3):8.09(d,J＝7.2Hz,1.0H),7.80(d,J＝7.6Hz,1.0H),7.59-7.42(m,2.0H), 7.34(t,J＝7.6Hz,1.0H),7.19(t,J＝8.0Hz,1H),7.12(d,J＝7.2Hz,0.43H),7.05(t, J＝7.6Hz,0.44H),6.87(t,J＝7.2Hz,1.0H),6.77(t,J＝7.2Hz,0.46H),6.63(d,J＝ 8.0Hz,0.43H),5.05-4.99(m,1H),4.18-3.96(m,2H),3.88(s,1.55H),3.98-3.87(m, 1H),3.68(s,1.35H),2.05-1.91(m,1.0H),1.71-1.28(m,6.0H),1.22-1.13(m,2.0H), 1.12-1.05(m,3.0H),0.90-0.82(m,4.0H)；13C NMR(100MHz,CDCl3):195.2, 194.2,169.1,168.3,158.2,157.5,137.1,137.1,133.3,132.8,129.7,128.7,128.6, 128.3,128.3,128.2,127.7,127.5,120.3,110.9,110.5,61.7,61.1,60.8,59.0,55.4, 54.9,40.4,39.5,35.0,34.8,34.5,34.4,32.0,31.8,27.8,26.5,26.2,25.9,14.0,13.6； LRMS(EI,70eV)m/z(％):408(M+,1),390(11),217(10),121(100)；HRMS m/z (ESI)calcd for C26H33O4([M+H]+)409.2373,found 409.2378.。
example 21
The target product IV-10 is obtained by using the 3-methoxy-5-methyl styrene of the formula I-10 as a raw material, the reaction temperature is 80 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, and the yield is 64 percent. dr is 1.5: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.09(d,J＝7.6Hz,1.0H),7.77(d,J＝ 7.6Hz,1.0H),7.59(t,J＝7.2Hz,0.67H),7.47(m,1.59H),7.34(t,J＝7.6Hz,1.0H), 7.07-7.03(m,1.0H),6.95-6.89(m,1.0H),6.74(d,J＝8.4Hz,0.65H),6.58(d,J＝8.4 Hz,0.41H),4.63-4.54(m,1.0H),4.25-4.10(m,1.0H),3.81-3.65(m,5.0H),2.21(s, 1.63H),2.07(s,1.30H),1.98-1.90(m,1.0H),1.69-1.62(m,2.0H),1.47-1.32(m,3H), 1.23-1.21(m,2.0H),1.11-1.03(s,3H),0.900.86(m,5.0H)；13C NMR(100MHz, CDCl3):194.3,194.0,168.8,168.0,156.4,156.1,137.1,137.0,133.5,132.9,132.7, 130.6,130.3,128.7,128.4,128.3,126.9,126.7,126.0,109.6,109.5,62.0,61.6,61.4, 61.2,55.2,55.1,42.2,41.9,41.6,34.6,34.5,34.4,34.2,31.7,31.6,26.6,26.5,26.1, 25.9,16.3,16.2,14.1,13.7；LRMS(EI,70eV)m/z(％):422(M+,3),404(29),308 (13),135(100)；HRMS m/z(ESI)calcd for C27H35O4([M+H]+)423.2530,found 423.2537.。
example 22
The target product IV-11 is obtained with the compound of the formula I-11 as the raw material and the reaction temperature of 80 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, and the yield is 46 percent. dr is 1.2: 1; a light yellow oily liquid;1H NMR (400MHz,CDCl3):8.04(d,J＝7.6Hz,1H),7.86(d,J＝7.6Hz,1H),7.58(t,J＝ 6.8Hz,0.60H),7.53-7.45(m,1.54H),7.39(t,J＝7.6Hz,1H),6.96(s,0.49H),6.93 (s,0.42H),6.80(s,0.52H),6.67(s,0.42H),6.67(s,0.42H),5.97(d,J＝7.6Hz, 1.0H),5.82(s,0.42H),4.54-4.42(m,1.41H),4.22-4.12(m,1.54H),3.90-3.85(m, 1.0H),2.17-2.02(m,1.0H),1.67-1.57(m,3.0H),1.46-1.34(m,2.0H),1.21-1.18(m, 2.0H),1.10-1.09(m,3.0H),1.00-0.97(m,2.0H),0.88-0.80(m,3.0H)；13C NMR(100 MHz,CDCl3):193.8,193.2,168.5,167.7,147.6,147.4,146.9,146.7,136.8, 136.7,133.6,133.1,128.7,128.7,128.5,128.4,116.3,116.2,112.7,112.6,108.1, 107.6,101.7,101.6,61.5,61.4,61.1,60.5,43.1,41.5,40.6,40.4,34.7,34.6,34.5, 32.5,29.7,26.5,26.3,25.9,14.0,13.7；LRMS(EI,70eV)m/z(％):500(M+,1),421 (94),245(86),105(100)；HRMS m/z(ESI)calcd for C26H30BrO5([M+H]+)501.1271, found 501.1277.。
example 23
The target product IV-12 is obtained by using the 2-naphthylethylene of the formula I-11 as a raw material, controlling the reaction temperature to be 100 ℃, and controlling the rest of the reaction raw materials, the operation and the parameters to be the same as those of the example 1, wherein the yield is 55 percent. dr is 1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.12(d,J＝7.6Hz,1.0H),7.82-7.58(m,5.0H), 7.52-7.34(m,5.0H),7.26(d,J＝8.8Hz,1.0H),4.79(d,J＝10.8Hz,0.50H),4.73(d, J＝10.8Hz,0.51H),4.26-4.16(m,1.0H),4.05-3.95(m,1.0H),3.74-3.61(m,1.0H), 2.02(m,1.0H),1.82(t,J＝12.4Hz,0.62H),1.66-1.60(m,1.47H),1.54-1.43(m, 4.0H),1.37-1.32(m,1.0H),1.26-1.22(m,2.0H),1.10-0.83(m,4.6H),0.71(t,J＝7.0 Hz,1.5H)；13C NMR(100MHz,CDCl3):193.7,168.6,167.9,139.2,138.8,136.9, 136.8,133.6,133.4,133.3,133.1,132.5,132.2,128.8,128.3,127.9,127.7,127.6, 127.6,127.4,126.4,126.2,125.9,125.7,125.5,125.3,61.7,61.6,61.5,61.1,43.0, 42.6,42.0,41.4,34.6,34.5,34.5,34.2,31.7,31.6,26.5,26.5,26.0,25.8,14.1,13.5； LRMS(EI,70eV)m/z(％):428(M+,2),314(13),141(86),105(100)；HRMS m/z (ESI)calcd for C29H33O3([M+H]+)429.2424,found 429.2432.。
example 24
The target product IV-14 is obtained with the yield of 55% by using 1-methyl-1-phenylethene of the formula I-14 as a raw material, the reaction temperature of 80 ℃ and the rest of the reaction raw materials, operation and parameters as in example 1. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.92(d,J＝7.6Hz,1.0H),7.62(d,J＝7.7 Hz,1.0H),7.55-7.39(m,3.0H),7.31-7.24(m,3.0H),7.20-7.10(m,2H),7.02-6.99(m, 0.52H),4.81(s,1.0H),4.17-4.12(m,1.0H),3.84-3.79(m,1.0H),1.95-1.78(m,4.0H), 1.59-1.32(m,4.0H),1.19-0.84(m,11.0H)；13C NMR(100MHz,CDCl3):195.0, 194.4,168.3,167.5,145.3,144.8,138.7,138.2,133.1,132.5,128.6,128.3,128.2, 127.9,127.8,127.8,126.9,126.8,126.2,126.0,63.5,63.4,61.1,60.7,48.3,47.2, 45.4,44.7,35.8,35.6,35.0,34.9,33.9,33.7,26.3,26.3,26.2,26.1,19.8,19.8,14.0, 13.7；(EI,70eV)m/z(％):392(M+,1),347(1),200(40),105(100)；HRMS m/z(ESI) calcd for C26H33O3([M+H]+)393.2424,found 393.2429.。
example 25
1-octene of formula I-15 was used as the starting material at a reaction temperature of 80 ℃ and the remaining reaction materials, operations and parameters were the same as in example 1 to give the desired product of formula IV-15 in a yield of 45%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.02-7.97(m,2.0H),7.57-7.45(m,3.0H),4.38-4.35 (m,0.48H),4.16-4.11(m,1H),4.02(d,J＝9.6Hz,0.42H),2.48-2.32(m,1H), 1.83-1.66(m,5.0H),1.40-1.09(m,19.0H),0.95-0.81(m,4.0H)；13C NMR(100MHz, CDCl3):195.4,195.2,195.0,169.5,169.4,168.2,137.4,137.3,137.1,133.3,133.2, 128.7,128.6,128.4,128.4,81.7,61.8,61.1,57.9,57.9,39.5,39.0,37.8,35.4,35.2, 35.1,35.0,34.4,34.0,32.9,32.6,31.8,31.6,31.5,31.5,31.0,30.7,29.7,29.7,29.5, 27.8,26.6,26.4,26.4,26.2,26.0,26.0,25.9,22.6,22.5,14.1,14.0；LRMS(EI,70eV) m/z(％):386(M+,1),281(3),192(98),105(100)；HRMS m/z(ESI)calcd for C25H39O3([M+H]+)387.2894,found 387.2901.。
example 26
The target product IV-16 is obtained by using the methyl acrylate shown in the formula I-16 as a raw material and the reaction temperature is 100 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, and the yield is 36 percent. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.06-8.02(m,2.0H),7.62-7.56(m,1.0H),7.52-7.44 (m,2.0H),4.74(d,J＝10.6Hz,0.46H),4.67(d,J＝10.6Hz,0.49H),4.14-4.08(m, 2.0H),3.73(s,1.28H),3.64(s,1.66H),3.56-3.47(m,1.0H),1.98-1.90(m,1.0H), 1.67-1.58(m,5.0H),1.51-1.31(m,3.0H),1.19-1.07(m,6.0H),0.97-0.74(m,3.0H)；13C NMR(100MHz,CDCl3):194.0,193.6,175.2,175.0,168.2,168.1,136.8, 135.9,133.8,133.6,128.9,128.8(2C),128.6,61.7,57.8,56.0,51.8,42.7,42.2,38.4, 38.1,35.4,35.2,34.2,34.0,32.2,31.9,26.4,26.4,26.2,26.1,26.0(2C),13.9,13.8； LRMS(EI,70eV)m/z(％):360(M+,1),255(2),192(17),105(100)；HRMS m/z (ESI)calcd for C22H31O5([M+H]+)375.2166,found 375.2180.。
example 27
The cyclopentane of the formula II-2 is used as a raw material, and the rest of the reaction raw materials, operations and parameters are the same as those of the example1 to obtain the target product IV-17 with the yield of 91 percent. dr is 1.6: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3) :7.34(d,J＝7.6Hz,2H),7.23-7.28(m,2H),7.09(t,J＝7.2Hz,1H),6.97(d,J＝ 8.4Hz,2H),6.68(d,J＝8.4Hz,2H),6.03(s,2H),4.87(t,J＝7.6,1H),3.73(s,3H), 3.71(s,3H),3.61(s,6H),3.45-3.37(m,2H)；13C NMR(100MHz,CDCl3):159.4, 159.1,157.4,145.3,134.1,129.8,128.0,127.5,125.1,113.8,113.1,91.4,55.7,55.1, 41.2,37.2；(EI,70eV)m/z(％):394(M+,6),298(21),138(38),105(100)；HRMS m/z(ESI)calcd for C25H31O4([M+H]+)395.2217,found 395.2223.。
example 28
The target product IV-18 is obtained with the cycloheptane of the formula II-3 as a raw material and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, and the yield is 96 percent. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3) :8.01(d,J＝7.6Hz,1.0H),7.71(d,J＝7.6Hz,1.0H),7.51(t,J＝7.2Hz,0.61H), 7.42-7.36(m,1.55H),7.26(t,J＝7.6Hz,1.0H),7.13(d,J＝8.0Hz,1.0H),7.01(d,J ＝8.0Hz,1.0H),6.77(d,J＝8.0Hz,1.0H),6.60(d,J＝8.0Hz,1.0H),4.58-4.49(m, 1H),4.13-4.08(m,1.0H),3.76-3.61(m,5.0H),1.78-1.73(m,1.0H),1.55-1.50(m, 2.0H),1.37-1.26(m,6.0H),1.18-0.99(m,7H),0.80(t,J＝7.4Hz,2H)；13C NMR (100MHz,CDCl3):194.0,193.8,168.6,167.9,158.2,157.9,136.9,133.5,133.3, 133.1,133.0,129.5,129.2,128.7(2C),128.3(2C),113.7(2C),61.8,61.5,61.4, 61.1,55.1,55.0,42.7(2C),42.5,41.9,36.2,36.1,35.7,35.5,32.0(2C),28.8,28.7, 28.3,28.3,26.3(2C),25.9,25.8,14.0,13.7；LRMS(EI,70eV)m/z(％):422(M+,2), 404(15),308(15),121(100)；HRMS m/z(ESI)calcd for C27H35O4([M+H]+) 423.2530,found 423.2541.。
example 29
The cyclooctane of the formula II-4 is used as a raw material, and the rest of the reaction raw materials, operation and parameters are the same as those of the example 1, so that the target product IV-19 is obtained with the yield of 93 percent. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3) :8.09(d,J＝7.6Hz,1.0H),7.79(d,J＝7.6Hz,1.0H),7.59(t,J＝7.2Hz,0.59H), 7.47(m,1.64H),7.34(t,J＝7.2Hz,1.0H),7.21(d,J＝8.0Hz,1.0H),7.09(d,J＝8.0 Hz,1.0H),6.84(d,J＝8.0Hz,1.0H),6.68(d,J＝8.0Hz,1.0H),4.65-4.57(m,1.0H), 4.23-4.17(m,1.0H),3.80-3.69(m,5.0H),1.79-1.73(m,1.0H),1.66-1.54(m,1.0H), 1.48-1.08(m,18H),0.88(t,J＝7.0Hz,2H)；13C NMR(100MHz,CDCl3):194.0, 193.8,168.7,168.0,158.3,157.9,137.0,133.6,133.4,133.1,133.0,129.5,129.3, 128.7,128.4,113.6,61.8,61.6,61.5,61.1,55.1,55.0,42.7,42.6,42.5,41.7,34.4, 34.4,33.9,33.6,29.1,27.6,27.6,26.9,26.9,26.2,25.5,25.4,24.8,24.8,14.1,13.7； (EI,70eV)m/z(％):422(M+,2),418(11),308(21),121(100)；HRMS m/z(ESI) calcd for C28H37O4([M+H]+)437.2686,found 437.2675.。
example 30
Adamantane of the formula II-5 is used as a raw material, the reaction temperature is 80 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, so that the target product IV-20 is obtained, and the yield is 71%. dr is 1.1: 1; a light yellow oily liquid;1H NMR (400MHz,CDCl3):8.11-8.06(m,1.42H),7.84(d,J＝8.0Hz,0.64H),7.62-7.57(m, 0.78H),7.49(t,J＝7.2Hz,1.51H),7.37(t,J＝7.2Hz,0.79H),7.27-7.12(m,2.0H), 6.86-6.81(m,1.53H),6.71(d,J＝7.6Hz,0.63H),4.66-4.50(m,1.0H),4.21-4.16(m, 0.67H),3.89-3.68(m,5.63H),2.01-1.43(m,6.0H),1.36-1.13(m,8.0H),0.93-0.68 (m,4H)；13C NMR(100MHz,CDCl3):193.9,193.8,168.7,168.1,158.3,158.0, 136.9,136.7,135.8,135.5,133.6,133.2,129.9,129.5,128.7,128.6,128.5,128.4, 113.7,113.6,63.0,62.0,61.6,61.5,55.2,55.1,48.8,46.7,42.9,39.5,39.0,36.9,28.6, 20.8,20.3,14.0,13.7；(EI,70eV)m/z(％):460(M+,3),442(34),268(33),135(100)； HRMS m/z(ESI)calcd for C30H37O4([M+H]+)461.2686,found 461.2673.。
example 31
The target product IV-21 is obtained by using normal hexane of the formula II-6 as a raw material and the reaction temperature of 80 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, and the yield is 81%. dr is 1.1: 1; a brown oily liquid;1H NMR (400MHz,CDCl3):8.09(d,J＝7.6Hz,1.0H),7.79(d,J＝7.6Hz,1.0H),7.59(t,J ＝7.2Hz,0.59H),7.50-7.44(m,1.47H),7.34(t,J＝7.2Hz,1.0H),7.21(d,J＝8.0Hz, 1.0H),7.10(d,J＝8.0Hz,1.0H),6.84(d,J＝8.0Hz,1.0H),6.68(d,J＝8.0Hz, 1.0H),4.64(d,J＝10.7Hz,0.49H),4.58(d,J＝10.6Hz,0.48H),4.25-4.10(m, 1.0H),3.82-3.67(m,5.0H),1.80-1.60(m,1.0H),1.55-1.40(m,2.0H),1.27-1.20(m, 3.0H),1.17-1.04(m,3.0H),0.90-0.65(m,9.0H)；13C NMR(100MHz,CDCl3): 194.1,194.0,193.8(2C),168.7,168.6,168.0,167.9,158.3,157.9,136.9,133.5, 133.0,129.5,129.2,128.7,128.7,128.3,113.5,113.5,62.0(2C),61.9,61.8,61.7, 61.7(2C),61.6,61.4(2C),61.1,55.1,55.0,42.8,42.7,42.7,42.5,42.4(3C),42.2, 41.4,41.4,40.7,38.3,38.0,37.8,37.7,37.5,37.3,37.2,35.9,35.8,35.5,35.2,34.8, 34.3,34.3,34.1,34.0,29.9(2C)29.6(2C),29.6,29.0(2C),28.6,28.5,26.7,26.6, 24.1,22.9(2C),22.8(2C),20.8,20.7,19.7,19.7,18.8,18.8,18.6,18.5,14.6,14.6, 14.2(2C),14.1(2C),14.0,13.7,10.9,9.5,9.4；(EI,70eV)m/z(％):410(M+,2),392 (14),219(11),105(100).。
example 32
The mesitylene of the formula II-7 is used as a raw material, the reaction temperature is 80 ℃, and the rest of the reaction raw materials, the operation and the parameters are the same as those of the example 1, so that the target product IV-22 is obtained, and the yield is 72 percent. dr is 1.1: 1; a light yellow oily liquid; 1H NMR (400MHz, CDCl3):8.07(d, J ═ 7.6Hz,143H),7.80(d, J ═ 7.6Hz,0.62H), 7.58(t, J ═ 7.2Hz,0.74H),7.47(t, J ═ 7.2Hz,1.73H),7.35(t, J ═ 7.6Hz,0.70H), 7.25(d, J ═ 7.6Hz,1.56H),7.13(d, J ═ 8.4Hz,0.63H),6.88(d, J ═ 8.4Hz,1.63H), 6.79-72(m,1.48H),6.68(s,0.621H),6.62(s,1.30H),4.7-4.63(m, 1.4H), 4.81-14.7H, 3.7-3H, 1.7H, 3.7-8H, 1.7H, 3H, 1.3H, 3H, 1.3.7-3H, 1.7.7-3H, 1.3H, 1.7.7-3H, 1.7H, 1.7.7.7.7.7.7H, 1.7H, 1.7.7H, 3H, 1.7H, 3H, 1.7H, 1.3H, 1.7H, 1.;13C NMR(100MHz, CDCl3):193.8,193.8,168.6,167.9,158.5,158.2,141.8,137.7,137.6,136.9,136.8, 133.6,133.1,133.0,132.8,129.6,129.3,128.7,128.4,128.4,127.4,127.3,126.14, 126.0,113.7,61.5,61.4,61.2,61.1,55.2,55.1,45.0,44.5,36.6,35.8,33.5,33.2,21.2, 21.1,14.0,13.7；LRMS(EI,70eV)m/z(％):444(M+,2),426(3),105(100)；HRMS m/z(ESI)calcd for C29H33O4([M+H]+)445.2373,found 445.2381.。
example 33
The target product IV-23 is obtained with the reaction temperature of 80 ℃ and the rest of the reaction raw materials, operation and parameters the same as those of example 1 by using the 1, 4-dioxane of the formula II-8 as a raw material, and the yield is 62%. dr is 1.2: 1; a light yellow oily liquid; 1H NMR (400MHz, CDCl3):8.09(t, J ═ 8.0Hz,2.0H),7.61-7.55(m,1.0H), 7.50-7.46(m,2.0H),7.23(d, J ═ 8.0Hz,2.0H),6.87-6.83(m,2.0H),4.74(d, J ═ 10.8Hz, 0.51H),4.68(d, J ═ 10.8Hz,0.45H),3.85-3.72(m,6.0H),3.68-3.10(m,7.0H), 1.81-1.60(m,2.0H),0.87(t, J ═ 6.8Hz, 3.0H);13C NMR(100MHz,CDCl3): 193.6,192.9,167.9,167.7,158.7,158.5,136.7,136.7,133.7,133.5,132.8,132.1, 129.5,129.4,128.8(2C),128.7,128.7,128.5,113.9,113.8,72.9,72.9,71.0,70.7, 66.6,66.3,66.0,61.3,61.2,60.8,60.7,55.2,40.9,40.7,36.7,36.5,13.7；LRMS(EI, 70eV)m/z(％):412(M+,3),348(18),261(30),105(100)；HRMS m/z(ESI)calcd for C24H29O6([M+H]+)413.1959,found 413.1973.。
example 34
The 1, 3-dicarbonyl compound of formula III-2 was used as the starting material, and the remaining reaction materials, operations and parameters were the same as in example 1 to obtain the target product IV-24 with a yield of 92%. dr is 1.2: 1; a light yellow oily liquid;1H NMR(400 MHz,CDCl3):8.08(d,J＝8.4Hz,1.0H),7.82(d,J＝8.4Hz,1.0H),7.21(d,J＝7.6Hz,1.0H),7.10(d,J＝8.0Hz,1.0H),6.95(d,J＝8.4Hz,1.0H),6.83(t,J＝8.4 Hz,2.0H),6.69(d,J＝7.6Hz,1.0H),4.60-4.51(m,1.0H),4.22-4.15(m,1.0H),3.87 (s,1.61H),3.81-3.75(m,5H),3.70(s,1.53H),1.98-1.89(m,1H),1.73-1.34(m, 7.0H),1.27-1.21(m,2H),1.09-1.03(m,2H),0.90-0.87(m,4.0H)；13C NMR(100 MHz,CDCl3):192.1,192.1,168.9,168.2,163.9,163.5,158.2,157.8,133.6,133.3, 131.1,130.8,130.0,129.9,129.4,129.2,113.9,113.5,61.5,61.3,61.2,61.0,55.5, 55.4,55.1,55.0,42.1,42.0,41.7,41.5,34.6,34.4(2C),34.2,31.6,31.5,26.5(2C), 26.1,25.8,14.1,13.7；(EI,70eV)m/z(％):438(M+,6),420(13),216(46),121(100)； HRMS m/z(ESI)calcd for C27H35O5([M+H]+)439.2479,found 439.2491.。
example 35
The 1, 3-dicarbonyl compound of formula III-3 was used as the starting material, the reaction temperature was 60 ℃, and the remaining reaction materials, operations and parameters were the same as those of example 1, to obtain the target product IV-25 with a yield of 42%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.11-7.07(m,2.0H),6.82(d,J＝8.0Hz, 2.0H),3.78(s,3.0H),3.75(s,1.67H),3.73-3.66(m,1.0H),3.50-3.46(m,1.0H),3.40 (s,1.34H),2.28(s,1.57H),1.88-1.86(m,2.56H),1.66-1.62(m,1.0H),1.56-1.47(m, 3.0H),1.42-1.32(m,2.0H),1.26-1.3(m,1.0H),1.06-1.01(m,3.0H),0.90-0.88(s, 2.0H)；13C NMR(100MHz,CDCl3):202.7(2C),169.1,168.6,158.3,158.2,132.8, 132.6,129.1,129.0,114.0,113.7,67.9,67.0,55.1(2C),52.4,52.1,42.2,42.0,41.9, 41.5,34.5(2C),34.2,34.1,31.6,30.2,26.5,26.1(2C),25.8；LRMS(EI,70eV)m/z (％):332(M+,3),314(7),161(25),121(100)；HRMS m/z(ESI)calcd for C20H29O4 ([M+H]+)333.2060,found 333.2069.。
example 36
The 1, 3-dicarbonyl compound of formula III-4 was used as the starting material, the reaction temperature was 60 ℃, and the remaining reaction materials, operations and parameters were the same as those of example 1, to obtain the target product IV-26 with a yield of 52%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.11-7.07(m,2.0H),6.81(d,J＝8.0Hz, 2.0H),5.11-5.05(m,0.50H),4.72-4.66(m,0.45H),3.78(s,3.0H),3.70-3.62(m, 1.0H),3.46(t,J＝11.2Hz,1H),2.28(s,1.53H),1.94-1.88(s,2.53H),1.70-1.66(m, 1.11H),1.54(s,2.02H),1.47-1.36(m,2.04H),1.29-1.25(m,5.0H),1.10-0.98(m, 4.0H),0.95-0.76(m,5.0H)；13C NMR(100MHz,CDCl3):202.8,202.7,168.1, 167.7,158.3,158.2,133.0,132.9,129.3,129.1,113.9,113.6,68.9,68.5,68.2,67.5, 55.2,55.1,42.0,41.8,34.5,34.5,34.2,34.1,31.7,31.6,30.0,29.1,26.5(2C),26.1, 25.8,21.7,21.6,21.3,21.2；LRMS(EI,70eV)m/z(％):360(M+,3),342(8),217 (11),121(100)；HRMS m/z(ESI)calcd for C22H33O4([M+H]+)361.2373,found 361.2381.。
example 37
The 1, 3-dicarbonyl compound of formula III-5 was used as the starting material, and the remaining reaction materials, operations and parameters were the same as in example 1 to obtain the target product IV-27 with a yield of 50%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400 MHz,CDCl3):7.05-7.00(m,2.0H),6.75(d,J＝8.0Hz,2.0H),4.27-4.23(m,1.0H), 3.96-3.84(m,1.0H),3.78-3.67(m,4.0H),3.57-3.51(m,1.0H),3.45-3.36(m,1H), 3.31-3.11(m,4.0H),2.21(s,1.52H),1.84-1.76(s,2.55H),1.61-1.18(m,9.0H), 1.05-0.92(m,2.0H),0.85-0.74(m,4.0H)；13C NMR(100MHz,CDCl3):202.6, 202.5,168.6,168.2,158.3,158.2,132.8,132.6,129.2,129.1,113.9,113.6,70.2,70.0, 67.7,66.9,64.1,63.8,60.9,58.9,58.7,55.1,42.2,41.9,41.8,41.6,34.5,34.4,34.2, 34.1,32.4,31.6,31.5,30.2,29.4,26.5,26.5,26.1,26.1,25.8；(EI,70eV)m/z(％): 376(M+,3),354(7),217(15),121(100)；HRMS m/z(ESI)calcd for C22H33O5 ([M+H]+)377.2323,found 377.2330.。
example 38
The target product IV-28 is obtained with 80% yield by using the 1, 3-dicarbonyl compound of formula III-6 as the raw material and the reaction temperature of 80 deg.C and the rest of the reaction raw materials, operation and parameters as in example 1. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.11-7.06(m,2.0H),6.81(d,J＝8.0Hz,2H), 3.78(s,3H),3.75-3.70(m,2.79H),3.54-3.45(m,1.0H),3.39(s,1.26H),2.67-2.48 (m,1.0H),2.34-2.24(m,1.0H),2.00-1.80(m,2.0H),1.65-1.62(m,2.0H),1.54-1.35 (m,3.0H),1.12-1.02(m,4.0H),0.87(m,3.48H),0.72(t,J＝7.2Hz,1.66H)；13C NMR(100MHz,CDCl3):205.1(2C),169.1,168.6,158.2(2C),133.0,132.7,129.1, 129.1,113.9,113.6,66.8,66.1,55.1(2C),52.3,52.0,42.3,41.8,41.7,41.5,37.0, 36.2,34.5(2C),34.3,34.12,31.6,26.5,26.1,25.8,7.5,7.2；LRMS(EI,70eV)m/z (％):346(M+,2),328(9),217(9),121(100)；HRMS m/z(ESI)calcd for C21H31O4 ([M+H]+)347.2217,found 347.2210.。
example 39
The target product IV-29 is obtained with the yield of 64% by using the 1, 3-dicarbonyl compound of the formula III-7 as a raw material and the reaction temperature of 80 ℃ and the rest of the reaction raw materials, operation and parameters as in example 1. dr is 1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.10(d,J＝8.0Hz,2H),6.81(d,J＝8.0Hz, 2H),4.25-4.19(m,0.50H),3.86-3.81(m,1.52H),3.78(s,3.0H),3.74-3.65(m,1.0H), 3.50(t,J＝10.4Hz,1H),2.60-2.52(m,1.67H),2.29-2.19(m,1.0H),1.90-1.82(m, 1.0H),1.66-1.36(m,6.0H),1.30-1.21(m,4.0H),1.10-1.00(m,3.0H),0.96-0.83(m, 7.0H)；13C NMR(100MHz,CDCl3):204.5,168.1,158.2,133.2,129.2,113.6,67.2, 61.0,55.1,44.6,41.8,41.7,34.5,34.3,31.6,26.5,26.1,25.8,16.8,13.8,13.6；LRMS (EI,70eV)m/z(％):374(M+,1),356(9),217(11),121(100)；HRMS m/z(ESI) calcd for C23H35O4([M+H]+)375.2530,found 375.2539.。
example 40
The 1, 3-dicarbonyl compound of formula III-8 was used as the starting material, and the remaining reaction materials, operations and parameters were the same as in example 1, to obtain the target product IV-30 with a yield of 74%. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400 MHz,CDCl3):1H NMR(400MHz,CDCl3)7.13-7.08(m,2.0H),6.83-6.79(m, 2.0H),4.24-4.21(m,1.0H),3.90-3.72(m,5.0H),3.55(t,J＝11.2Hz,1H),2.31-2.22 (m,0.64H),1.90-1.85(m,1.59H),1.69-1.52(m,4.0H),1.48-1.39(m,2.0H), 1.34-1.26(m,2.0H),1.14-1.07(m,4.0H),0.97-0.90(m,5.0H),0.75-0.56(m,2.0H)；13C NMR(100MHz,CDCl3):204.9,204.4,168.9,168.3,158.2(2C),133.2,133.0, 129.3,129.2,113.7,113.6,68.1,67.6,61.3,60.9,55.1(2C),42.1,42.0,41.8,41.7, 34.5(2C),34.3,34.2,31.6,26.5,26.1(2C),25.8,20.6,19.7,14.1,13.8,12.4,11.7, 11.6,11.5；(EI,70eV)m/z(％):372(M+,3),354(7),217(15),121(100)；HRMS m/z (ESI)calcd for C23H33O4([M+H]+)373.2373,found 373.2381.。
EXAMPLE 41
The 1, 3-dicarbonyl compound of formula III-9 was used as the starting material, the reaction temperature was 60 ℃ and the remaining reaction materials, operations and parameters were the same as those of example 1 to obtain the target product IV-31 with a yield of 53%. dr is 1.2: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):7.12-7.05(m,2.0H),6.80(d,J＝8.4Hz, 2.0H),4.28-4.16(m,1.0H),3.98-3.92(m,1.0H),3.79(s,3.0H),3.70(d,J＝12.0Hz, 0.49H),3.58(d,J＝12.0Hz,0.55H),2.20(s,1.35H),1.96(s,1.65H),1.89-1.87(m, 1.0H),1.78-1.70(m,2.0H),1.59-1.53(m,2.0H),1.44-1.26(m,6.0H),1.14-1.01(m, 4.0H),0.95-0.85(s,3.0H)；13C NMR(100MHz,CDCl3):206.1,205.3,172.2, 171.5,158.4,131.6,131.5(2C),130.4,113.5,113.3,64.9,64.6,61.20,61.1,55.1, 45.9,45.0,38.9(2C),34.9,34.8,34.7,31.6,27.2,27.1,26.6,26.5,26.2,25.9,17.1, 14.8,14.0,13.8；LRMS(EI,70eV)m/z(％):360(M+,1),217(26),121(100)；HRMS m/z(ESI)calcd for C22H33O4([M+H]+)361.2373,found 361.2386.。
example 42
The target product IV-32 is obtained with the reaction temperature of 80 ℃ and the rest of the reaction raw materials, operation and parameters the same as those of example 1 by using the 1, 3-dicarbonyl compound shown in the formula III-10 as a raw material, and the yield is 55%. A light yellow oily liquid;1H NMR(400MHz,CDCl3):7.07(d,J＝8.0Hz,2H),6.82(d,J＝8.0Hz,2H),3.97(d, J＝11.6Hz,1H),3.78(s,3H),3.52(t,J＝11.2Hz,1H),2.25(s,3H),1.91-1.89(m, 1H),1.79(s,3H),1.66-1.64(s,1H),1.57-1.37(m,3H),1.26-1.17(m,2H),1.10-1.05 (m,3H),0.89-0.80(m,3H)；13C NMR(100MHz,CDCl3):203.8,203.7,158.3, 132.6,129.0,114.0,55.1,42.6,42.2,34.5,34.0,31.6,30.2,29.3,26.4,26.1,25.8；(EI, 70eV)m/z(％):316(M+,3),273(49),177(48),121(100)；HRMS m/z(ESI)calcd for C20H29O3([M+H]+)317.2111,found 317.2120.。
example 43
The target product IV-33 is obtained with a yield of 53% by using the 1, 3-dicarbonyl compound of formula III-11 as a raw material and a reaction temperature of 80 ℃ and the rest of the reaction raw materials, operations and parameters as in example 1. dr is 1.1: 1; a light yellow oily liquid;1H NMR(400MHz,CDCl3):8.07(d,J＝7.6Hz,1.0H),7.75(d,J＝8.0 Hz,1.0H),7.60(t,J＝7.2Hz,0.57H),7.51-7.45(m,1.50H),7.33(t,J＝7.6Hz, 1.0H),7.17(d,J＝8.4Hz,1.0H),7.07(d,J＝8.0Hz,1.0H),6.85(d,J＝8.0Hz, 1.0H),6.68(d,J＝8.4Hz,1.0H),4.86-4.76(m,1.0H),3.87-3.76(m,2.68H),3.69(s, 1.41H),2.23(s,1.56H),1.96-1.93(m,1.0H),1.87(s,1.58H),1.64-1.53(m,3.0H), 1.43-1.28(m,3.0H),1.06-1.01(m,3.0H),0.92-0.80(m,3.0H)；13C NMR(100MHz, CDCl3):204.1,203.3,195.4,195.2,158.3,158.0,137.3,137.2,133.7,133.3,133.0, 132.8,129.3,129.1,128.8,128.8,128.5,128.4,114.0,113.7,71.9,71.3,55.1,55.0, 43.1,42.8,42.5,41.6,34.6,34.4,34.2,34.0,31.7,31.6,27.9,27.3,26.5,26.1,25.9； (EI,70eV)m/z(％):378(M+,2),335(88),239(26),121(100)；HRMS m/z(ESI) calcd for C25H31O3([M+H]+)379.2268,found 379.2281.。
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 method for intermolecular 1, 2-dialkylation of olefin compounds under a photo-redox/iron (II) catalytic system is characterized by comprising the following preparation steps:
charging an olefinic compound of formula I, a compound of formula II, a 1, 3-dicarbonyl compound of formula III, a ferrous iron catalyst, a photo-redox catalyst, and a free radical initiator into a Schlenk reactor; then protecting the reactor with inert atmosphere, stirring and reacting for 48 hours under the irradiation condition of a 5W LED blue light lamp at the temperature of 30-120 ℃, detecting that the raw materials completely react through TLC and/or GC-MS analysis, and carrying out post-treatment after the reaction is finished to obtain a target product shown in a formula IV;
wherein R is1Selected from hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
R2selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20Heteroaryl, substituted or unsubstituted C1-20alkyl-O-CO-;
R3selected from hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
R4、R5independently of one another, from hydrogen, substituted or unsubstituted C1-20Or R is4、R5Together with the carbon atom to which they are attached form C3-20Or R is cycloalkyl, or4、R5Together with the carbon atom to which they are attached form C3-20Wherein said cycloalkyl and heterocyclyl are optionally substituted with a substituent; wherein R is4、R5Not hydrogen at the same time;
R6、R7independently of one another, from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C1-20Alkoxy, substituted or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20The heteroaryl group of (a);
R8selected from hydrogen, substituted or unsubstituted C1-20Alkyl groups of (a);
all substituents in the expression "substituted or unsubstituted" as mentioned above are selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a);
wherein the ferrous catalyst is selected from Fe (OTf)2、FeCl2、Fe(acac)2Any one of the above;
the photo-redox catalyst is selected from the group consisting of EosinY;
the free radical initiator is selected from any one of DTBP, TBHP and TBPB.
2. The method of claim 1, wherein R is1Selected from hydrogen, C1-20Alkyl groups of (a);
R2is selected from C1-20Alkyl, substituted or unsubstituted C6-20Aryl of (C)1-20alkyl-O-CO-; wherein the "substituted or unsubstituted" substituents are as defined in claim 1;
R3represents hydrogen;
R4、R5independently of one another, from hydrogen; c1-20Alkyl groups of (a); or R4、R5Together with the carbon atom to which they are attached form C3-20A cyclic hydrocarbon group of (a); or
R4、R5Together with the carbon atom to which they are attached form C3-20A heterocyclic group of (a); wherein R is4、R5Not hydrogen at the same time;
R6、R7independently of one another, from C1-20Alkyl of (C)1-20Alkoxy group of (C)6-20Aryl of (a);
R8selected from hydrogen, C1-20Alkyl group of (1).
3. The method of claim 2, wherein R is1Selected from hydrogen, methyl, ethyl, propyl;
R2is selected from C1-6Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, C1-6alkyl-O-CO-; wherein the "substituted or unsubstituted" substituents are as defined in claim 1;
R3selected from hydrogen;
R4、R5independently of one another, from hydrogen; c1-6Alkyl groups of (a); or R4、R5Together with the carbon atom to which they are attached form cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl; or R4、R5Together with the carbon atom to which they are attached form a 1, 4-dioxane group, a tetrahydrofuranyl group, a morpholinyl group;
wherein R is4、R5Not hydrogen at the same time;
R6、R7independently of one another, from methyl, ethyl, propyl, methoxy, ethoxy, propoxy, phenyl;
R8selected from hydrogen, methyl, ethyl, propyl.
4. The method according to any one of claims 1 to 3, wherein the ferrous catalyst is Fe (OTf)2(ii) a The photooxidation-reduction catalyst is EosinY; the free radical initiator is DTBP.
5. A process according to any one of claims 1 to 3, characterized in that the reaction temperature is 30 to 100 ℃.
6. The method according to any one of claims 1 to 3, wherein the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
7. The method of any one of claims 1 to 3, wherein the molar ratio of the olefinic compound of formula I, the 1, 3-dicarbonyl compound of formula III, the ferrous catalyst, the photo-redox catalyst, and the radical initiator is 1 (1-3): (10-30%) (5-15%): 1-3).
8. The method of claim 7, wherein the olefinic compound of formula I, the 1, 3-dicarbonyl compound of formula III, the divalent iron catalyst, the photo-redox catalyst, and the free radical initiator are present in a molar ratio of 1:2: 20% to 10% to 2.
9. A method according to any one of claims 1-3, 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 using column chromatography to obtain the target product shown in the formula IV, wherein the eluent separated by using the column chromatography is the mixed solution of normal hexane and ethyl acetate.
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