CN112778068B - Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method - Google Patents

Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method Download PDF

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CN112778068B
CN112778068B CN202110002366.2A CN202110002366A CN112778068B CN 112778068 B CN112778068 B CN 112778068B CN 202110002366 A CN202110002366 A CN 202110002366A CN 112778068 B CN112778068 B CN 112778068B
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欧阳旋慧
江慧敏
宋仁杰
李金恒
梁云燕
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Abstract

The invention discloses a novel method for catalyzing alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction by copper. The method takes olefin, polyhalogenated alkane and alcohol as raw materials, and leads C (sp) of the polyhalogenated alkane to be reacted by using 4-methoxybenzene diazo tetrafluoroborate as a free radical initiator under the catalysis of copper 3 ) the-H bond is broken to form a polyhalogenated alkyl free radical intermediate, the intermediate is applied to the preparation of various 1-alkoxy-2-polyhalogenated alkyl hydrocarbon compounds, has excellent functional group tolerance and wide substrate application range, and can also be applied to the realization of post-synthesis modification of natural products.

Description

Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method
Technical Field
The application belongs to the technical field of organic synthesis methodology, and particularly relates to a copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method.
Background
Polychlorinated alkyl compounds, particularly di-or trichloromethyl-containing compounds, are widely found in natural products, pesticides, and a variety of biologically active molecules. Since Kharasch reported an atom transfer radical addition reaction (ATRA) with a terminal alkene using monobromo trichloromethane as the trichloromethyl donor unit (see science, 1945,102,128-128 j.am. Chem.soc.,1945,67, 1626-1626.), radical addition reactions of alkenes, including bifunctional reactions of alkenes, have become one of the powerful strategies for rapidly constructing a variety of complex molecules containing polyhaloalkyl groups from simple, readily available starting materials. However, traditional olefin difunctionalization methods for the synthesis of polyhaloalkyl-containing compounds generally focus on one-component Atom Transfer Radical Cyclization (ATRC) and two-component Atom Transfer Radical Addition (ATRA) strategies, generating radicals by photo-catalysis (e.g. uv, daylight), thermo-catalysis and/or highly toxic organic initiators (e.g. azobisisobutyronitrile, organotin) with simultaneous formation of C-halogen bonds (see chem. Soc. Rev.,2002,31,1-11, angelw. Chem., int.ed.,2016,55,58-102, chem.rev.,2009,109,3817-3858, eur.j.org.chem.,2016,13, 1-2243, org.org.m., 2012,77,6778-6788, angelw.chem, 201ed., chem., 2017,56,8780-8784, am.10827, 20120, 201em., 141, 20120, 201em., 26, 6405, 22, 18, 22. As an extension of this alkene bifunctional reaction, recent studies have reported that two-or three-component polyhalogenated alkanes and nucleophilic reagents (e.g., aryl C (sp) compounds) 2 ) -H bond, O - ,N 3 - Etc.) olefin difunctionalization, by manipulating the enthalpy and the stereoelectronic effect, the C-H bond of the polyhalogenated alkane is preferentially cleaved to form a polyhalogenated alkyl radical (see org. Chem. Front.,2014,1,1289-1294; org, lett.,2014,16,4698-4701; RSC adv.,2014,4,64855-64859; chem.,2016,36,325-329; j.org.chem.,2015,80,2621-2626; org, biomol, chem, 2018,16,5752-5755; chem. Commun.,2018,54,11013-11016; org. Chem. Front.,2019,6, 512-516.).
In the present invention, the inventors reportedA copper-catalyzed process for the dual-functionalization of 1, 2-alkoxy/polyhalogenated alkyl olefin with high universality features that the olefin, polyhalogenated alkane and alcohol are used as raw materials and the C (sp) of polyhalogenated alkane is passed through 3 ) the-H bond is broken to prepare various 1-alkoxy-2-polyhalogenated alkyl alkane compounds, and the compound has excellent functional group tolerance and wide substrate application range. 4-methoxybenzene diazo tetrafluoroborate is used as a free radical initiator to promote the formation of a polyhaloalkyl free radical intermediate, and the method can be applied to the realization of post-synthesis modification of natural products.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel method for copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction. The method takes olefin, polyhalogenated alkane and alcohol as raw materials, and leads C (sp) of the polyhalogenated alkane to be reacted by using 4-methoxybenzene diazo tetrafluoroborate as a free radical initiator under the catalysis of copper 3 ) the-H bond is broken to form a polyhalogenated alkyl free radical intermediate, and the intermediate is applied to the preparation of various 1-alkoxy-2-polyhalogenated alkyl alkane compounds, has excellent functional group tolerance and wide substrate application range, and can also be applied to the realization of post-synthesis modification of natural products.
The invention provides a method for copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction, which comprises the following steps:
sequentially adding a copper catalyst, 4-methoxybenzene diazo tetrafluoroborate, alkali, an olefin compound shown as a formula 1, an alcohol compound shown as a formula 3 and a polyhalogenated alkane compound shown as a formula 2 into a reactor, heating and stirring for reaction under the protection of inert atmosphere, and carrying out post-treatment after the reaction is completed to obtain an olefin bifunctional target product shown as a formula 4. The reaction formula is as follows:
Figure BDA0002881802940000031
in the above reaction formula, R 1 Selected from substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 6-20 An aryl vinyl group; wherein the substituted or unsubstituted substituents are selected from halogen, C 1-6 Alkyl radical, C 1-6 Haloalkyl, C 1-6 Alkoxy radical,
Figure BDA0002881802940000032
C 1-6 Alkylthio, benzyloxy, C 6-20 An aryl group; or R 1 Is selected from
Figure BDA0002881802940000033
Figure BDA0002881802940000034
R 2 Selected from hydrogen, C 1-20 Alkyl, substituted or unsubstituted C 6-20 An aryl group; wherein the substituted or unsubstituted substituents are selected from halogen, C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 1-6 Alkylthio, benzyloxy, C 6-20 And (3) an aryl group.
R 3 Selected from hydrogen, C 1-20 An alkyl group.
R 4 ,R 5 Independently of one another, from hydrogen, halogen, C 1-6 Alkyl radical, C 1-6 A haloalkyl group.
R 6 Selected from hydrogen, chlorine or bromine.
X is selected from fluorine, chlorine or bromine.
R 7 Selected from substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 A cycloalkyl group; wherein the substituents in the substituted or unsubstituted group are selected from halogen, C 1-6 Alkyl radical, C 2-6 Alkenyl radical, C 6-20 And (3) an aryl group.
Preferably, in the above reaction formula, R 1 Selected from substituted or unsubstituted phenyl or naphthyl, substituted or unsubstituted thienyl or pyridyl, substituted or unsubstituted phenylvinyl; wherein said substituted or unsubstituted substituents are selected from the group consisting of fluorine, chlorine, bromine methyl, ethyl, tert-butyl, trifluoromethyl, methoxy, ethoxy,
Figure BDA0002881802940000041
Methylthio, benzyloxy, phenyl; or R 1 Is selected from
Figure BDA0002881802940000042
R 2 Selected from hydrogen, methyl, substituted or unsubstituted phenyl; wherein the substituted or unsubstituted substituent is selected from fluorine, chlorine, bromine, methyl, methoxy, methylthio.
R 3 Selected from hydrogen and methyl.
R 4 ,R 5 Independently of one another, from hydrogen, chlorine, bromine, monochloromethyl, monobromomethyl, dichloromethyl, dibromomethyl, trichloromethyl, tribromomethyl.
R 6 Selected from hydrogen, chlorine or bromine.
X is selected from chlorine or bromine.
R 7 Selected from substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 3-10 A cycloalkyl group; wherein the substituted or unsubstituted substituents are selected from the group consisting of fluorine, chlorine, bromine, methyl, isopropyl, vinyl, phenyl.
Most preferably, the olefinic compound of formula 1 is selected from compounds having the following structural formula:
Figure BDA0002881802940000043
the polyhaloalkane compounds of formula 2 are selected from compounds having the following structural formula:
Figure BDA0002881802940000051
the alcohol compound of formula 3 is selected from compounds having the following structural formula:
Figure BDA0002881802940000052
the aforementioned method according to the present invention, wherein the copper catalyst is selected from Cu (MeCN) 4 BF 4 。
The method according to the present invention, wherein the base is an organic base or an inorganic base; the organic base is selected from triethylamine, 2, 6-dimethylpyridine and pyridine; the inorganic base is selected from sodium carbonate, sodium bicarbonate, dipotassium hydrogen phosphate and potassium carbonate. Preferably, the base is sodium carbonate.
According to the foregoing method of the present invention, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere, preferably an argon atmosphere.
The aforementioned method according to the present invention, wherein the reaction temperature of the heating and stirring reaction is 50 to 100 ℃, preferably 70 to 90 ℃, and most preferably 80 ℃. The reaction time is 3 to 12 hours, preferably 6 hours.
According to the method of the invention, the feeding molar ratio of the copper catalyst, the 4-methoxybenzene diazo tetrafluoroborate, the base, the olefin compound of formula 1 and the alcohol compound of formula 3 is (0.01-0.2), (1-3), (1.0), (1-10); preferably, the feeding molar ratio of the copper catalyst, the 4-methoxybenzene diazo tetrafluoroborate, the alkali, the olefin compound of formula 1 and the alcohol compound of formula 3 is 0.1. The compound of formula 2 serves as a reaction solvent in the reaction at the same time, and the amount thereof can be routinely determined by those skilled in the art according to the actual circumstances of the reaction.
According to the method of the invention, the post-treatment operation is as follows: filtering after the reaction is completed, concentrating the filtrate, and separating the residue by silica gel column chromatography to obtain the target product of the alkene dual-functionalization shown in the formula 4, wherein the elution solvent separated by the silica gel column chromatography is a mixed solvent of petroleum ether and ethyl acetate.
The method of the invention achieves the following beneficial effects:
the invention reports a novel method for the copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction for the first time. The method uses olefin, polyhalogenated alkane and alcohol as raw materials, cu (MeCN) 4 BF 4 Under catalysis by using4-methoxybenzene diazo tetrafluoroborate as a free radical initiator to react C (sp) of polyhalogenated alkanes 3 ) the-H bond is broken to form a polyhalogenated alkyl free radical intermediate, and the intermediate is applied to the preparation of various 1-alkoxy-2-polyhalogenated alkyl alkane compounds, has excellent functional group tolerance and wide substrate application range, and can also be applied to the realization of post-synthesis modification of natural products. In Cu (MeCN) 4 BF 4 4-methoxybenzene diazo tetrafluoroborate/Na 2 CO 3 The optimal synergistic catalytic effect can be obtained under the catalytic system, at the reaction temperature of 80 ℃ and in 6 hours, and good reaction condition mildness and high efficiency are reflected.
In the reaction of the invention, meOC 6 H 4 N 2 BF 4 The method comprises the steps of forming free radicals under heating and alkaline conditions, reacting with a polyhalogenated alkane substrate to form a free radical intermediate A, oxidizing monovalent copper into divalent copper, adding the polyhalogenated alkane free radical intermediate A and double bonds to obtain a free radical intermediate B, oxidizing the free radical intermediate B by the divalent copper to obtain a carbocation intermediate C, and capturing the carbocation intermediate C by an alcohol substrate to obtain a target product.
Detailed Description
The present invention will be described in further detail with reference to specific examples. In the following, unless otherwise specified, the methods employed in the present invention are all conventional in the art, and the reagents and starting materials used are either commercially available from conventional sources and/or prepared by synthetic routes known in the art.
Examples 1-19 optimization of reaction conditions
The influence of p-methoxystyrene of formula 1a, chloroform (formula 2 a) and ethanol (formula 3 a) on the yield of the target product of 4aaa under different catalytic conditions was investigated, wherein the representative test results are shown in table 1, and the reaction formula is as follows:
Figure BDA0002881802940000071
table 1:
examples Reaction operating condition variables Isolated yield/%)
1 Is composed of 91
2 No addition of 4-MeOC 6 H 4 N 2 BF 4 0
3 No addition of Cu (MeCN) 4 BF 4 63
4 CuCl instead of Cu (MeCN) 4 BF 4 83
5 CuCl 2 Instead of Cu (MeCN) 4 BF 4 68
6 Cu(OTf) 2 Instead of Cu (MeCN) 4 BF 4 67
7 FeCl 2 Instead of Cu (MeCN) 4 BF 4 75
8 Ni(acac) 2 Instead of Cu (MeCN) 4 BF 4 71
9 No Na addition was made 2 CO 3 58
10 K 2 HPO 4 Substitute for Na 2 CO 3 81
11 2,6-lutidine in place of Na 2 CO 3 63
12 NaHCO 3 Substitute for Na 2 CO 3 85
13 KOH instead of Na 2 CO 3 33
14 K 2 CO 3 In place of Na 2 CO 3 73
15 The reaction temperature is 70 DEG C 69
16 The reaction temperature is 90 DEG C 86
17 4-MeOC 6 H 4 N 2 BF 4 (1.5equiv) 77
18 4-MeOC 6 H 4 N 2 BF 4 (2.5equiv) 88
19 DTBP instead of 4-MeOC 6 H 4 N 2 BF 4 56
Wherein example 1 operates as follows:
to a Schlenk closed tube reactor, cu (MeCN) was added in sequence 4 BF 4 (0.02mmol,10mol％),4-MeOC 6 H 4 N 2 BF 4 (0.4mmol,2equiv),Na 2 CO 3 (0.4 mmol, 2equiv), p-methoxystyrene of formula 1a (0.2 mmol), ethanol of formula 3a (0.6 mmol) and chloroform of formula 2a (2 mL), followed by argon blanketing of the reactor, placing the reactor at 80 ℃ and stirring for reaction for 6 hours, monitoring by TLC or GC-MS to show complete consumption of the starting material, filtering the reaction solution, concentrating the filtrate in vacuo to give a residue, separating the residue by silica gel column chromatography (eluting solvent petroleum ether/ethyl acetate) to give the desired product of formula 4aaa at a yield of 91%, as a yellow oily liquid; 1 H NMR(500MHz,CDCl 3 )δ7.28(d,J＝9.0Hz,2H),6.90(d,J＝9.0Hz,2H),4.68-4.66(m,1H),3.81(s,3H),3.40-3.38(m,2H),3.29-3.25(m,1H),2.97-2.93(m,1H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,133.4,127.7,114.0,97.6,78.7,64.3,62.1,55.3,15.2；LRMS(EI,70eV)m/z(％):298(M + +2,4),296(M + ,4),165(100),137(61),109(24)；HRMS m/z(ESI)calcd for C 12 H 16 O 2 Cl 3 ([M+H] + )297.0210,found 297.0217。
the reaction conditions for examples 2-19 were the same as in example 1 except that the variables listed in Table 1 were different from those in example 1.
Examples 20-30 reaction substrate extension test
On the basis of obtaining the optimal reaction conditions (example 1), the adaptability of different alcoholic substrates to the optimal reaction conditions was explored, i.e. only the species of alcoholic substrate was replaced, and the remaining reaction conditions were the same as in example 1, and the isolated yields were calculated, the reaction formula is as follows:
Figure BDA0002881802940000081
the results were as follows:
Figure BDA0002881802940000091
and (3) product structure characterization:
compound 4aab: 1 H NMR(500MHz,CDCl 3 )δ7.28-7.26(m,2H),6.92-6.90(m,2H),4.56-4.54(m,1H),3.82(s,3H),3.29-3.25(m,1H),3.23(s,3H),2.99-2.96(m,1H)； 13 C NMR(125MHz,CDCl 3 )δ159.5,132.6,127.9,127.8,114.1,114.0,97.4,80.6,62.1,56.4,55.3；LRMS(EI,70eV)m/z(％):284(M + +2,3),282(3),151(100),135(16),108(6)；HRMS m/z(ESI)calcd for C 11 H 14 O 2 Cl 3 ([M+H] + )283.0054,found 283.0058。
compound 4aac: 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝9.0Hz,2H),6.90(d,J＝8.5Hz,2H),4.66-4.64(m,1H),3.81(s,3H),3.32-3.29(m,2H),3.28-3.23(m,1H),2.96-2.92(m,1H),1.55-1.51(m,2H),1.40-1.32(m,2H),0.87(t,J＝7.5Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.3,133.4,127.8,114.0,97.6,78.9,68.6,62.2,55.3,31.8,19.4,13.8；LRMS(EI,70eV)m/z(％):326(M + +2,2),324(2),193(52),137(100),109(17)；HRMS m/z(ESI)calcd for C 14 H 20 O 2 Cl 3 ([M+H] + )325.0523,found 325.0522。
compound 4aad: 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝8.0Hz,2H),6.90(d,J＝8.5Hz,2H),4.65-4.63(m,1H),3.82(s,3H),3.31-3.29(m,2H),3.28-3.25(m,1H),2.96-2.92(m,1H),1.55-1.52(m,2H),1.30-1.24(m,18H),0.88(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.3,133.4,127.8,114.0,97.6,79.0,69.0,62.2,55.3,31.9,29.7,29.6(3H),29.4,29.3,29.2,26.2,22.7,14.1；LRMS(EI,70eV)m/z(％):438(M + +2,2),436(2),305(56),137(100),109(7)；HRMS m/z(ESI)calcd for C 22 H 36 O 2 Cl 3 ([M+H] + )437.1775,found 437.1779。
compound 4aae: 1 H NMR(500MHz,CDCl 3 )δ7.26(d,J＝8.5Hz,2H),6.90(d,J＝8.5Hz,2H),4.63-4.61(m,1H),3.81(s,3H),3.30-3.25(m,1H),2.94(s,2H),2.93-2.90(m,1H),0.89(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ159.3,133.5,127.7,114.0,97.6,79.2,79.1,62.4,55.2,31.9,26.8；LRMS(EI,70eV)m/z(％):340(M + +2,3),338(3),207(38),155(28),137(100)；HRMS m/z(ESI)calcd for C 15 H 22 O 2 Cl 3 ([M+H] + )339.0680,found 339.0685。
compound 4aaf: 1 H NMR(500MHz,CDCl 3 )δ7.28-7.26(m,2H),6.91-6.89(m,2H),5.82-5.77(m,1H),5.06-4.99(m,2H),4.68-4.66(m,1H),3.82(s,3H),3.38-3.35(m,2H),3.30-3.26(m,1H),2.97-2.93(m,1H),2.32-2.30(m,2H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,135.3,133.2,127.8,116.2,114.1,97.5,79.1,68.3,62.1,55.3,34.2；LRMS(EI,70eV)m/z(％):324(M + +2,5),322(5),191(100),161(30),137(49)；HRMS m/z(ESI)calcd for C 14 H 18 O 2 Cl 3 ([M+H] + )323.0367,found 323.0371。
compound 4aag: 1 H NMR(500MHz,CDCl 3 )δ7.26(d,J＝7.0Hz,2H),6.91(d,J＝8.5Hz,2H),4.68-4.67(m,1H),3.82(s,3H),3.55-3.50(m,2H),3.43(t,J＝6.0Hz,2H),3.28-3.24(m,1H),2.96-2.93(m,1H),2.09-2.04(m,2H)； 13 C NMR(125MHz,CDCl 3 )δ159.5,132.8,127.8,114.2,97.4,79.2,66.1,62.0,55.3,32.9,30.7；LRMS(EI,70eV)m/z(％):392(M + +4,2),390(M + +2,4),388(2),257(68),137(100),109(30)；HRMS m/z(ESI)calcd for C 13 H 17 O 2 Cl 3 Br([M+H] + )388.9472,found 388.9473。
compound 4aah: 1 H NMR(500MHz,CDCl 3 )δ7.25-7.21(m,4H),7.16(d,J＝7.5Hz,1H),7.13(d,J＝7.5Hz,2H),6.89(d,J＝8.5Hz,2H),4.65-4.63(m,1H),3.79(s,3H),3.32(t,J＝6.5Hz,2H),3.29-3.24(m,1H),2.96-2.92(m,1H),2.57(t,J＝7.5Hz,2H),1.69-1.64(m,2H),1.61-1.56(m,2H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,142.4,133.3,128.4,128.2,127.8,125.6,114.0,97.6,79.0,68.6,62.1,55.2,35.6,29.3,28.0；LRMS(EI,70eV)m/z(％):402(M + +2,1),400(1),253(17),137(82),91(100)；HRMS m/z(ESI)calcd for C 20 H 24 O 2 Cl 3 ([M+H] + )401.0836,found 401.0840。
compound 4aai: 1 H NMR(500MHz,CDCl3)δ7.28-7.25(m,2H),6.91-6.88(m,2H),4.64-4.62(m,1H),3.81(s,3H),3.30–3.25(m,1H),3.08-3.06(m,2H),2.96-2.92(m,1H),1.86-1.80(m,1H),0.91-0.86(m,6H)； 13 C NMR(125MHz,CDCl 3 )δ159.3,133.4,127.8,114.0,97.6,79.1,75.7,62.3,55.3,28.6,19.5(2H)；LRMS(EI,70eV)m/z(％):326(M + +2,4),324(4),253(5),193(37),137(100)；HRMS m/z(ESI)calcd for C 14 H 20 O 2 Cl 3 ([M+H] + )325.0523,found 325.0521。
compound 4aaj: 1 H NMR(500MHz,CDCl 3 )δ7.28-7.26(m,2H),6.88(d,J＝8.5Hz,2H),4.88-4.86(m,1H),3.81(s,3H),3.33-3.29(m,1H),3.04-3.00(m,1H),2.92-2.87(m,1H),2.24-2.21(m,2H),1.55-1.52(m,1H),1.21-1.17(m,2H),0.92(d,J＝6.5Hz,3H),0.88(s,1H),0.84(d,J＝7.0Hz,3H),0.81-0.76(m,2H),0.26(d,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,133.3,128.9,113.8,97.6,74.3,74.2,61.9,55.3,48.4,39.4,34.5,31.4,24.8,22.8,22.5,21.3,15.5；LRMS(EI,70eV)m/z(％):408(M + +2,2),406(2),275(17),253(10),137(100)；HRMS m/z(ESI)calcd for C 20 H 30 O 2 Cl 3 ([M+H] + )407.1306,found 407.1302。
compound 4aak: 1 H NMR(500MHz,CDCl 3 )δ7.28(d,J＝8.5Hz,2H),6.88(d,J＝8.0Hz,2H),4.88-4.87(m,1H),3.81(s,3H),3.35(s,1H),3.33-3.29(m,1H),2.97-2.93(m,1H),2.23(d,J＝12.0Hz,1H),2.11-2.08(m,2H),1.77-1.66(m,9H),1.40(d,J＝12.0Hz,2H)； 13 C NMR(125MHz,CDCl 3 )δ159.2,134.1,128.0,113.9,97.6,79.5,76.0,62.5,55.2,37.6,36.7,36.4,33.3,31.6,31.5,30.4,27.4(2C)；LRMS(EI,70eV)m/z(％):404(M + +2,3),402(3),271(63),155(32),135(100)；HRMS m/z(ESI)calcd for C 20 H 26 O 2 Cl 3 ([M+H] + )403.0993,found 403.0997。
compound 4aal: 1 H NMR(500MHz,CDCl 3 )δ7.29(d,J＝8.5Hz,2H),6.86(d,J＝8.5Hz,2H),5.00-4.98(m,1H),3.80(s,3H),3.22-3.17(m,1H),2.88-2.84(m,1H),1.13(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ159.0,137.0,127.6,113.8,97.5,75.2,72.1,63.1,55.3,28.9；LRMS(EI,70eV)m/z(％):326(M + +2,6),324(6),193(24),137(100),109(35)；HRMS m/z(ESI)calcd for C 14 H 20 O 2 Cl 3 ([M+H] + )325.0523,found 325.0524。
examples 31-39 reaction substrate extension test
On the basis of obtaining the optimal reaction conditions (example 1), the adaptability of different polyhalogenated alkane substrates to the optimal reaction conditions was explored, i.e. only the species of the polyhalogenated alkane substrates were replaced, and the rest of the reaction conditions were the same as in example 1, and the separation yield was calculated, and the reaction formula is as follows:
Figure BDA0002881802940000121
the results were as follows:
Figure BDA0002881802940000131
wherein, the first and the second end of the pipe are connected with each other, c representing polyhaloalkanes as CBrCl 3 (2mL). d Denotes a polyhaloalkane as CCl 4 (2mL). e Denotes a polyhaloalkane as CHBrCl 2 (2mL). f Represents a polyhaloalkane as CH 2 Cl 2 (2mL). g Denotes a polyhaloalkane as CBr 4 (2mL)。
And (3) product structure characterization:
compound 4aba: 1 H NMR(500MHz,CDCl 3 )δ7.23(d,J＝8.5Hz,2H),6.90(d,J＝8.5Hz,2H),5.91-5.88(m,1H),4.44-4.42(m,1H),3.81(s,3H),3.39-3.27(m,2H),2.66-2.61(m,1H),2.39-2.33(m,1H),1.15(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,132.6,127.7,114.0,77.9,70.9,64.0,55.3,52.0,15.2；LRMS(EI,70eV)m/z(％):264(M + +2,6),262(6),165(100),137(48),109(21)；HRMS m/z(ESI)calcd for C 12 H 17 O 2 Cl 2 ([M+H] + )263.0600,found 263.0599。
compound 4afa: 1 H NMR(500MHz,CDCl 3 )δ7.31(d,J＝8.5Hz,2H),6.91(d,J＝8.5Hz,2H),4.59-4.57(m,1H),3.81(s,3H),3.64-3.60(m,1H),3.43-3.40(m,2H),3.35-3.31(m,1H),1.20(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.3,133.3 127.8,114.0,81.0,66.3,64.3,55.3,37.2,15.3；LRMS(EI,70eV)m/z(％):432(M + +4,3),430(M + +2,3),428(1),165(100),137(48),109(22)；HRMS m/z(ESI)calcd for C 12 H 16 O 2 Br 3 ([M+H] + )428.8695,found 428.8691。
compound 4afa': 1 H NMR(500MHz,CDCl 3 )δ7.24(d,J＝8.5Hz,2H),6.89(d,J＝8.5Hz,2H),5.81-5.79(m,1H),4.42-4.39(m,1H),3.81(s,3H),3.40–3.28(m,2H),2.85-2.79(m,1H),2.58-2.53(m,1H),1.16(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,132.5,127.7,114.0,79.2,64.1,55.3,53.7,43.0,15.2；LRMS(EI,70eV)m/z(％):352(M + +2,1),350(1),165(100),137(49),109(23)；HRMS m/z(ESI)calcd for C 12 H 17 O 2 Br 2 ([M+H] + )350.9590,found 350.9595。
compound 4aga': 1 H NMR(500MHz,CDCl 3 )δ7.23(d,J＝8.5Hz,2H),6.88(d,J＝9,0Hz,2H),4.42-4.39(m,1H),3.81(s,3H),3.42-3.39(m,1H),3.37-3.30(m,1H),3.36–3.28(m,2H),2.34-2.27(m,1H),2.08-2.04(m,1H),1.17(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.2,133.7,127.7,127.3,113.9,78.9,64.0,55.2,41.1,30.5,15.3；LRMS(EI,70eV)m/z(％):274(M + +2,3),272(3),165(100),137(62),109(28)；HRMS m/z(ESI)calcd for C 12 H 18 O 2 Br([M+H] + )273.0485,found 273.0489。
compound 4aia: 1 H NMR(500MHz,CDCl 3 )δ7.26-7.23(m,2H),6.89(d,J＝8.0Hz,2H),4.58(d,J＝8.5Hz,1H),3.81(s,3H),3.36-3.33(m,2H),2.91-2.86(m,1H),2.79-2.76(m,1H),2.62(s,3H),1.16(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.2,133.8,127.6,114.0,80.5,66.9,64.0,60.5,55.3,41.7,15.3；LRMS(EI,70eV)m/z(％):368(M + +4,1),366(M + +2,3),364(1),165(100),137(48),109(18)；HRMS m/z(ESI)calcd for C 13 H 18 O 2 Br 2 ([M+H] + )364.9746,found 364.9749。
compound 4aja: 1 H NMR(500MHz,CDCl 3 )δ7.24(d,J＝8.5Hz,2H),6.89(d,J＝8.5Hz,2H),4.52-4.50(m,1H),3.81(s,3H),3.78-3.70(m,2H),3.44-3.41(m,1H),3.34-3.30(m,2H),2.31-2.27(m,1H),1.84-1.81(m,1H),1.17(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.2,134.0,128.0,127.5,127.3,114.0,113.9,113.7,77.5,64.2,63.8,58.5,58.1,55.3,55.2,49.1,48.6,44.6,43.1,15.3,15.2；LRMS(EI,70eV)m/z(％):278(M + +2,3),276(5),165(100),137(55),109(24)；HRMS m/z(ESI)calcd for C 13 H 19 O 2 Cl 2 ([M+H] + )277.0757,found 277.00761。
compound 4aka: 1 H NMR(500MHz,CDCl 3 )δ7.26-7.23(m,2H),6.89(d,J＝8.5Hz,2H),4.63-4.60(m,1H),4.29(d,J＝12.0Hz,1H),4.11(d,J＝12.0Hz,1H),3.81(s,3H),3.37-3.26(m,2H),2.95-2.91(m,1H),2.52-2.49(m,1H),1.16(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.4,133.1,127.7,114.0,89.8,78.6,63.9,55.3,54.8,52.1,15.1；LRMS(EI,70eV)m/z(％):312(M + +2,3),310(3),165(100),137(51),109(32)；HRMS m/z(ESI)calcd for C 13 H 18 O 2 Cl 3 ([M+H] + )311.0367,found 311.0363。
compound 4ala: 1 H NMR(500MHz,CDCl 3 )δ7.24(d,J＝6.0Hz,2H),6.89(d,J＝8.5Hz,2H),6.47(s,1H),4.70-4.67(m,1H),3.81(s,3H),3.37-3.26(m,2H),3.11-3.08(m,1H),2.58-2.55(m,1H),1.17(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.5,132.5,127.8,114.1,93.1,78.5,78.3,64.0,55.3,52.0,15.1；LRMS(EI,70eV)m/z(％):346(M + +2,3),344(2),165(100),137(51),109(22)；HRMS m/z(ESI)calcd for C 13 H 17 O 2 Cl 4 ([M+H] + )344.9977,found 344.9982。
examples 40-65 reaction substrate extension test
On the basis of obtaining the optimum reaction conditions (example 1), the adaptability of the different olefinic compounds to the optimum reaction conditions was investigated, i.e. only the type of olefinic compound was replaced, the remaining reaction conditions were the same as in example 1, and the isolated yields were calculated as follows:
Figure BDA0002881802940000161
the results are as follows:
Figure BDA0002881802940000162
wherein, the first and the second end of the pipe are connected with each other, b the reaction temperature was 60 ℃.
Structural characterization data:
compound 4baa: 1 H NMR(500MHz,CDCl 3 )δ7.27-7.25(m,2H),6.90-6.88(m,2H),4.67-4.65(m,1H),4.05-4.01(m,2H),3.40-3.37(m,2H),3.29-3.25(m,1H),2.97-2.93(m,1H),1.42(t,J＝7.0Hz,3H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ158.8,133.2,127.7,114.5,97.6,78.8,64.2,63.4,62.1,15.2,14.8；LRMS(EI,70eV)m/z(％):312(M + +2,20),310(20),179(100),151(80),123(74)；HRMS m/z(ESI)calcd for C 13 H 18 O 2 Cl 3 ([M+H] + )311.0367,found 311.0371。
compound 4caa: 1 H NMR(500MHz,CDCl 3 )δ7.43(d,J＝7.0Hz,2H),7.39(t,J＝7.5Hz,2H),7.33(d,J＝7.5Hz,1H),7.27(d,J＝8.5Hz,2H),6.97(d,J＝9.0Hz,2H),5.06(s,2H),4.68-4.66(m,1H),3.40-3.38(m,2H),3.29-3.24(m,1H),2.96-2.93(m,1H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ158.6,136.8,133.6,128.6,128.0,127.8,127.5,114.9,97.5,78.7,70.0,64.3,62.1,15.2；LRMS(EI,70eV)m/z(％):374(M + +2,3),372(3),285(17),241(73),91(100)；HRMS m/z(ESI)calcd for C 18 H 20 O 2 Cl 3 ([M+H] + )373.0523,found 373.0524。
compound 4 daa; 13C NMR (125MHz, CDCl3) delta 138.3,138.1,127.0,126.6,97.4,78.8,64.5,62.0,15.7,15.2; LRMS (EI, 70 eV) M/z (%): 314 (M + +2, 5), 312 (5), 181 (100), 153 (50), 109 (21); HRMS M/z (ESI) calcd for C12H16OSCl3 ([ M + H ] +) 312.9982, found 312.9979.
Compound 4eaa: 1 H NMR(500MHz,CDCl 3 )δ7.61-7.58(m,4H),7.46-7.43(m,4H),7.35(t,J＝7.5Hz,1H),4.79-4.77(m,1H),3.48-3.44(m,2H),3.34-3.29(m,1H),3.02-2.99(m,1H),1.22(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ141.0,140.6,140.4,128.8,127.4(2H),127.1,127.0,97.5,79.0,64.6,62.2,15.2；LRMS(EI,70eV)m/z(％):344(M + +2,4),342(4),211(100),183(42),155(29)；HRMS m/z(ESI)calcd for C 17 H 18 OCl 3 ([M+H] + )343.0418,found 348.0414。
compound 4gaa: 1 H NMR(500MHz,CDCl 3 )δ7.44(d,J＝7.5Hz,1H),7.28(t,J＝7.5Hz,1H),6.99(t,J＝7.5Hz,1H),6.88(d,J＝8.0Hz,1H),5.14(d,J＝7.0Hz,1H),3.85(s,3H),3.47-3.44(m,2H),3.12-3.08(m,1H),2.98-2.95(m,1H),1.22(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ156.5,129.3,128.8,126.7,120.7,110.4,98.0,73.8,64.8,60.3,55.2,15.3；LRMS(EI,70eV)m/z(％):298(M + +2,12),296(12),166(35),137(88),107(100)；HRMS m/z(ESI)calcd for C 12 H 17 O 2 Cl 3 ([M+H] + )297.0210,found 297.0209。
compound 4haa: 1 H NMR(500MHz,CDCl 3 )δ7.15–7.12(m,2H),6.81(d,J＝8.5Hz,1H),4.65-4.63(m,1H),3.83(s,3H),3.42-3.36(m,2H),3.29-3.24(m,1H),2.97-2.93(m,1H),2.23(s,3H),1.19(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ157.5,132.8,128.8,127.0,125.0,109.7,97.6,78.8,64.2,62.2,55.3,16.3,15.2；LRMS(EI,70eV)m/z(％):312(M + +2,9),310(9),197(100),151(97),123(90)；HRMS m/z(ESI)calcd for C 13 H 18 OCl 3 ([M+H] + )311.0367,found 311.0370。
compound 4iaa: 1 H NMR(500MHz,CDCl 3 )δ7.09(t,J＝8.0Hz,1H),7.03-7.01(m,1H),6.89-6.87(m,1H),5.12-5.10(m,1H),3.89(s,3H),3.88(s,3H),3.44(m,2H),3.22(m,1H),3.00(m,1H),1.20(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ152.6,146.4,134.8,124.2,118.8,111.8,97.8,73.9,64.7,60.8,60.7,55.7,15.2；LRMS(EI,70eV)m/z(％):328(M + +2,30),326(30),196(68),167(100),139(97)；HRMS m/z(ESI)calcd for C 13 H 18 O 3 Cl 3 ([M+H] + )327.0316,found 327.0311。
compound 4jaa: 1 H NMR(500MHz,CDCl 3 )δ6.86(s,1H),6.81(s,1H),5.16-5.14(m,1H),3.55-3.51(m,1H),3.39-3.31(m,2H),3.00-2.97(m,1H),2.46(s,3H),2.41(s,3H),2.26(s,3H),1.16(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ137.2(2H),136.2,133.7,131.2,129.0,98.4,75.3,63.9,60.1,20.8(2H),20.4,15.3；LRMS(EI,70eV)m/z(％):310(M + +2,9),308(9),177(100),149(69),121(74)；HRMS m/z(ESI)calcd for C 14 H 20 OCl 3 ([M+H] + )309.0574,found 309.0570。
compound 4 kaa; 13C NMR (125MHz, CDCl3). Delta.148.1 (2H), 133.6,112.9,112.6,107.5,101.9,97.1,77.7,64.7,60.1,15.2; LRMS (EI, 70 eV) M/z (%): 392 (M + +4, 9), 390 (M + +2, 18), 388 (9), 257 (100), 229 (86), 122 (90); HRMS M/z (ESI) calcd for C12H13O3BrCl3 ([ M + H ] +) 388.9108, found 388.9105.
Compound 4laa: 1 H NMR(500MHz,CDCl3)δ7.19(d,J＝5.0Hz,1H),6.79(d,J＝5.0Hz,1H),5.05-5.03(m,1H),3.52-3.41(m,2H),3.36-3.32(m,1H),3.04-3.01(m,1H),2.26(s,3H),1.19(d,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ138.7,134.4,130.0,124.0,97.1,73.1,64.4,61.8,15.1,13.9；LRMS(EI,70eV)m/z(％):288(M + +2,6),286(6),155(70),127(100),99(35)；HRMS m/z(ESI)calcd for C 10 H 14 SOCl 3 ([M+H] + )286.9825,found 286.9828。
compound 4naa: 1 H NMR(500MHz,CDCl 3 )δ7.34(d,J＝9.0Hz,2H),6.87(d,J＝9.0Hz,,2H),6.57(d,J＝16.0Hz,1H),5.99-5.95(m,1H),4.21-4.28(m,1H),3.82(s,3H),3.65-3.62(m,1H),3.46-3.42(m,1H),3.18-3.14(m,1H),2.98-2.95(m,1H),1.22(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.5,132.2,128.9,127.8,126.2,114.0,97.3,78.2,64.0,60.1,55.3,15.2；LRMS(EI,70eV)m/z(％):324(M + +2,4),322(4),191(100),163(23),145(15)；HRMS m/z(ESI)calcd for C 14 H 18 O 2 Cl 3 ([M+H] + )323.0367,found 323.0371。
compound 4oaa: 1 H NMR(500MHz,CDCl 3 )δ7.35(d,J＝8.0Hz,2H),7.23(d,J＝8.5Hz,2H),3.39-3.36(M,1H),3.30-3.17(m,2H),3.11-3.08(m,1H),2.49(s,3H),1.86(s,3H),1.16(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ140.8,137.7,127.0,126.1,96.2,78.4,64.9,57.2,22.1,15.5,15.5；LRMS(EI,70eV)m/z(％):328(M + +2,3),326(3),195(100),167(34),151(27)；HRMS m/z(ESI)calcd for C 13 H 18 OSCl 3 ([M+H] + )327.0138,found 327.0841。
compound 4paa: 1 H NMR(500MHz,CDCl 3 )δ7.99(s,1H),7.88(d,J＝7.5Hz,1H),7.77(d,J＝7.5Hz,1H),7.68(d,J＝8.5Hz,1H),7.51-7.45(m,2H),7.40(d,J＝7.5Hz,2H),7.29-7.21(m,4H),4.03-3.93(m,2H),3.38-3.33(m,1H),3.28-3.22(m,1H),1.22(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ143.6,141.6,132.7,132.5,128.4,127.9(2C),127.5(2C),127.3,126.2,126.2(2C),125.1,96.6,81.6,58.2,55.4,15.0；LRMS(EI,70eV)m/z(％):394(M + +2,4),392(4),261(100),233(18),105(81)；HRMS m/z(ESI)calcd for C 21 H 20 OCl 3 ([M+H] + )393.0574,found 393.0571。
compound 4qaa: 1 H NMR(500MHz,CDCl 3 )δ8.51-8.50(m,1H),7.63(t,J＝8.0Hz,1H),7.56(d,J＝8.0Hz,1H),7.38(d,J＝7.5Hz,2H),7.27(t,J＝7.5Hz,2H),7.21(d,J＝7.5Hz,1H),7.13(t,J＝6.5Hz,1H),4.22-4.10(m,2H),3.50–3.44(m,1H),3.29-3.23(m,1H),1.24(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ163.3,147.8,142.9,136.6,128.0,127.2,127.0,122.2,122.1,96.9,82.9,58.5,54.2,15.0；LRMS(EI,70eV)m/z(％):345(M + +2,2),343(2),227(100),182(50),105(75)；HRMS m/z(ESI)calcd for C 16 H 17 ONCl 3 ([M+H] + )344.0370,found 344.0373。
compound 4raa: 1 H NMR(500MHz,CDCl 3 )δ7.69(s,1H),7.27-7.19(m,7H),7.03(d,J＝7.5Hz,1H),3.97(d,J＝15.0Hz,1H),3.75(d,J＝15.0Hz,1H),3.31(s,1H),3.11(s,1H),1.88(s,3H),1.20(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ142.8,141.2,132.6,128.1,127.8,127.6,127.1,126.7,125.3,96.8,81.5,57.6,21.2,15.1；LRMS(EI,70eV)m/z(％):358(M + +2,4),356(4),225(100),197(28),105(78)；HRMS m/z(ESI)calcd for C 18 H 20 OCl 3 ([M+H] + )357.0574,found 357.0577。
compound 4saa:1H NMR (500mhz, cdcl3) δ 7.38-7.36 (m, 2H), 7.28 (t, J =7.5hz, 2h), 7.23-7.13 (m, 4H), 7.04 (d, J =7.0hz, 1h), 3.88-3.80 (m, 2H), 3.28-3.21 (m, 2H), 2.31 (s, 3H), 1.19 (t, J =7.0hz, 3h); 13C NMR (125MHz, CDCl3) delta 144.0,137.5,128.0,127.9,127.8,127.4,127.1,124.5,96.6,81.5,58.0,55.7,21.6,15.0; LRMS (EI, 70 eV) M/z (%): 358 (M + +2, 4), 356 (4), 225 (100), 197 (29), 105 (67); HRMS M/z (ESI) calcd for C18H20OCl3 ([ M + H ] +) 357.0574, found 357.0578.
Compound 4taa: 1 H NMR(500MHz,CDCl 3 )δ7.37–7.36(m,2H),7.29-7.21(m,5H),7.09(d,J＝8.0Hz,2H),3.87-3.79(m,2H),3.29-3.26(m,1H),3.23-3.20(m,1H),2.31(s,3H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ144.1,141.1,136.9,128.6,127.8,127.4,127.3,127.1,96.6,81.5,58.0,55.7,21.0,15.0；LRMS(EI,70eV)m/z(％):358(M + +2,4),356(4),225(100),197(29),105(67)；HRMS m/z(ESI)calcd for C 18 H 20 OCl 3 ([M+H] + )357.0574,found 357.0571。
compound 4uaa: 1 H NMR(500MHz,CDCl 3 )δ7.35-7.29(m,5H),7.26-7.25(m,2H),6.97(t,J＝8.5Hz,2H),3.89-3.77(m,2H),3.34-3.28(m,1H),3.21-3.16(m,1H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ162.9,160.9,143.9,139.7(2H),129.2,128.1,127.5,127.3,114.8,114.6,96.3,81.2,58.1,55.6,15.0； 19 F NMR(471MHz,CDCl 3 )δ-115.45(s)；LRMS(EI,70eV)m/z(％):362(M + +2,3),360(3),229(100),201(45),123(83)；HRMS m/z(ESI)calcd for C 17 H 17 NOFCl 3 ([M+H] + )361.0324,found 361.0319。
compound 4vaa:1H NMR (500mhz, cdcl3) δ 7.36 (d, J =8.0hz, 4h), 7.29 (t, J =7.5hz, 4h), 7.22 (t, J =7.0hz, 2h), 3.86 (s, 2H), 3.28-3.24 (m, 2H), 1.19 (t, J =7.0hz, 3h); 13C NMR (125MHz, CDCl3) delta 144.0,127.9,127.4,127.2,96.5,81.5,58.1,55.6,15.0; LRMS (EI, 70 eV) M/z (%): 344 (M + +2, 4), 342 (4), 211 (93), 183 (36), 105 (100); HRMS M/z (ESI) calcd for C17H18OCl3 ([ M + H ] +) 343.0418, found 342.0414.
Compound 4waa: 1 H NMR(500MHz,CDCl 3 )δ7.32-7.29(m,4H),6.99(t,J＝8.5Hz,4H),3.79(s,2H),3.26-3.21(m,2H),1.18(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ163.0,161.0,139.6(2H),129.2,129.1,114.95(s),114.8,96.1,80.9,58.1,55.5,14.9； 19 F NMR(471MHz,CDCl 3 )δ-114.93(s)；LRMS(EI,70eV)m/z(％):380(M + ,3),378(3),247(87),219(51),123(100)；HRMS m/z(ESI)calcd for C 17 H 16 OF 2 Cl 3 ([M+H] + )379.0229,found 379.0233。
compound 4xaa: 1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝8.5Hz,2H),6.91(d,J＝8.5Hz,2H),5.06(s,1H),3.81(s,3H),3.50-3.38(m,2H),2.63-2.59(m,1H),1.28(d,J＝6.5Hz,3H),1.19(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ158.9,133.6,127.1,113.8,104.6,79.3,65.1,61.4,55.3,15.3,9.9；LRMS(EI,70eV)m/z(％):312(M + +2,4),310(4),165(67),137(100),109(45)；HRMS m/z(ESI)calcd for C 13 H 18 O 2 Cl 3 ([M+H] + )311.0367,found 311.0363。
compound 4yaa: 1 H NMR(500MHz,CDCl 3 )δ7.01(s,1H),6.52(s,1H),5.39(s,1H),3.91(s,3H),3.88(s,3H),3.83(s,3H),3.49-3.43(m,2H),2.74-2.72(m,1H),1.25(d,J＝6.5Hz,3H),1.21(t,J＝7.0Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ150.3,148.7,142.8,120.4,111.0,104.8,96.9,74.9,65.2,57.6,56.6,56.1,55.8,15.3,10.2；LRMS(EI,70eV)m/z(％):372(M + +2,3),370(3),225(100),197(17),169(14)；HRMS m/z(ESI)calcd for C 15 H 22 O 4 Cl 3 ([M+H] + )371.0578,found 371.0581。
compound 4zaa:1H NMR (500MHz, CDCl3). Delta.5.29-5.25 (m, 1H), 3.57-3.52 (m, 1H), 3.39-3.32 (m, 2H), 3.04-3.01 (m, 1H), 2.62-2.59 (m, 2H), 2.37-2.34 (m, 3H), 2.32-2.28 (m, 3H), 2.13-2.10 (m, 3H), 1.85-1.75 (m, 2H), 1.58-1.50 (m, 4H), 1.40-1.34 (m, 4H), 1.28-1.23 (m, 11H), 1.16-1.13 (m, 6H), 0.87-0.84 (m, 14H); 13C NMR (125MHz, CDCl3) delta 151.1,134.6,133.5,133.4,132.2,127.8,124.0,121.8,118.6,116.3,98.7,75.6,75.5,75.0,74.8,63.6,61.2,61.0,40.3,39.4,37.5,37.4,37.3,32.8,32.7,31.4,31.3,28.0,24.8,24.4,24.0,23.8,23.7,22.7,22.6,21.4,21.0,20.7,19.8,19.7,16.6,16.2,15.7,15.4,15.3,15.2,12.3, 11.6; HRMS M/z (ESI) calcd for C34H58O2Cl3 ([ M + H ] +) 603.3497, found 603.3497.
Compound 4abaa:1H NMR (500mhz, cdcl3) δ 7.29 (d, J =7.5hz, 1h), 7.14 (s, 1H), 7.08 (s, 1H), 4.67 (d, J =6.0hz, 1h), 3.44-3.40 (m, 2H), 3.28-3.23 (m, 1H), 2.96-2.93 (m, 3H), 2.54-2.49 (m, 1H), 2.44-2.42 (m, 1H), 2.33-2.31 (m, 1H), 2.19-2.13 (m, 1H), 2.10-2.03 (m, 2H), 1.99-1.97 (m, 1H), 1.68-1.62 (m, 2H), 1.56-1.45 (m, 4H), 1.20 (t, J = 6.92, 3h, 0.92H, 3H); 13C NMR (125MHz, CDCl3) delta 220.9,139.5,138.8,136.9 (2C), 126.9 (2C), 125.7 (2C), 123.8 (2C), 97.7,79.0,78.9,64.6,62.2,50.5,47.9,44.4,38.1,35.8,31.6,29.4,26.4,25.7,21.6,15.2,13.8; HRMS M/z (ESI) calcd for C23H30O2Cl3 ([ M + H ] +) 443.1306, found 443.1308.
Compound 4acaa: 1 H NMR(500MHz,CDCl 3 )δ7.43(d,J＝8.0Hz,1H),7.38(d,J＝7.5Hz,2H),7.29-7.27(m,2H),7.22-7.20(m,1H),7.19-7.17(m,1H),7.07-7.04(m,1H),3.88-3.76(m,2H),3.33-3.26(m,2H),3.21-3.17(m,1H),2.87-2.85(m,2H),2.53-2.47(m,1H),2.40-2.47(m,1H),2.29-2.25(m,1H),2.17-2.10(m,1H),2.02-1.99(m,1H),1.96-1.94(m,1H),1.66-1.64(m,2H),1.49-1.46(m,2H),1.27-1.25(m,2H),1.21-1.18(m,3H),0.91(s,3H)； 13 C NMR(125MHz,CDCl 3 )δ220.8,143.8(2C),141.4,141.3,138.7,138.6,135.9,131.7,128.0,127.7,127.6(2C),127.5,127.4,127.1,127.0(2C),127.6(2C),125.0,124.9(2C),124.8(2C),124.2,124.1,96.7,82.4,81.5,81.4,60.4,59.3,58.0,55.8(2C),50.5,47.9,44.3,38.0(2C),35.8,31.6,29.5,29.5,26.5,25.54(s),21.5,21.0,15.4,15.0,14.2,13.9,13.8；HRMS m/z(ESI)calcd for C 29 H 34 O 2 Cl 3 ([M+H] + )519.1619,found 519.1616。
compound 4adaa： 1 H NMR(500MHz,CDCl 3 )δ7.37-7.32(m,4H),5.36-5.35(m,1H),4.72-4.71(m,1H),4.55(s,2H),3.42-3.38(m,2H),3.28-3.24(m,2H),2.95-2.92(m,1H),2.44-2.42(m,1H),2.31-2.26(m,1H),2.02-1.96(m,3H),1.89-1.79(m,2H),1.61-1.44(m,8H),1.35-1.33(m,4H),1.26(d,J＝7.0Hz,2H),1.18(d,J＝6.9Hz,3H),1.12-1.04(m,5H),1.02(s,3H),1.00-0.95(m,2H),0.91(d,J＝6.5Hz,3H),0.87-0.86(m,6H),0.68(s,3H)； 13 C NMR(125MHz,CDCl 3 )δ140.9,140.5,138.9,128.0(2C),126.5,121.6,97.5,79.0,78.8,69.6,64.5,62.2,56.8,56.1,50.2,42.3,39.8,39.5,39.1,37.2,36.9,36.2,35.8,31.9(2C),28.4,28.2,28.0,24.3,23.8,22.8,22.6,21.0,19.4,18.7,15.2,11.8；HRMS m/z(ESI)calcd for C 39 H 60 O 2 Cl 3 ([M+H] + )665.3653,found 665.3650。

Claims (12)

1. A process for copper-catalyzed double functionalization of an olefin 1, 2-alkoxy/polyhaloalkyl comprising the steps of:
sequentially adding a copper catalyst, 4-methoxybenzene diazo tetrafluoroborate, alkali, an olefin compound shown as a formula 1, an alcohol compound shown as a formula 3 and a polyhalogenated alkane compound shown as a formula 2 into a reactor, heating and stirring for reaction under the protection of inert atmosphere, and carrying out post-treatment after complete reaction to obtain an olefin bifunctional target product shown as a formula 4; the reaction formula is as follows:
Figure FDA0003942590970000011
in the above reaction formula, R 1 Selected from substituted or unsubstituted phenyl or naphthyl, substituted or unsubstituted thienyl or pyridyl, substituted or unsubstituted phenylvinyl; wherein the substituted or unsubstituted substituents are selected from halogen, C 1-6 Alkyl radical, C 1-6 Haloalkyl, C 1-6 Alkoxy radical,
Figure FDA0003942590970000012
C 1-6 Alkylthio, benzyloxy, phenyl(ii) a Or R 1 Is selected from
Figure FDA0003942590970000013
R 2 Selected from hydrogen, C 1-20 Alkyl, substituted or unsubstituted phenyl; wherein the substituents in the substituted or unsubstituted group are selected from halogen, C 1-6 An alkyl group;
R 3 selected from hydrogen, C 1-20 An alkyl group;
R 4 ,R 5 independently of one another, from hydrogen, halogen, C 1-6 Alkyl radical, C 1-6 A haloalkyl group;
R 6 selected from hydrogen, chlorine or bromine;
x is selected from fluorine, chlorine or bromine;
R 7 selected from substituted or unsubstituted C 1-20 Alkyl, wherein the substituents in said substituted or unsubstituted are selected from halogen, C 1-6 Alkyl radical, C 2-6 Alkenyl, phenyl; or R 7 Selected from substituted or unsubstituted C 3-20 Cycloalkyl, wherein the substituents in said substituted or unsubstituted are selected from C 1-6 An alkyl group;
wherein the copper catalyst is selected from Cu (MeCN) 4 BF 4 ；
The alkali is organic alkali or inorganic alkali; the organic base is selected from triethylamine, 2, 6-dimethylpyridine and pyridine; the inorganic base is selected from sodium carbonate, sodium bicarbonate, dipotassium hydrogen phosphate, and potassium carbonate.
2. The method of claim 1, wherein R is 1 Selected from substituted or unsubstituted phenyl or naphthyl, substituted or unsubstituted thienyl or pyridyl, substituted or unsubstituted phenylvinyl; wherein said substituted or unsubstituted substituents are selected from the group consisting of fluorine, chlorine, bromine methyl, ethyl, tert-butyl, trifluoromethyl, methoxy, ethoxy,
Figure FDA0003942590970000021
Methylthio, benzyloxy, phenyl(ii) a Or R 1 Is selected from
Figure FDA0003942590970000022
Figure FDA0003942590970000023
R 2 Selected from hydrogen, methyl, substituted or unsubstituted phenyl; wherein said substituted or unsubstituted substituents are selected from the group consisting of fluorine, chlorine, bromine, methyl;
R 3 selected from hydrogen, methyl;
R 4 ,R 5 independently of one another, from hydrogen, chlorine, bromine, monochloromethyl, monobromomethyl, dichloromethyl, dibromomethyl, trichloromethyl, tribromomethyl;
R 6 selected from hydrogen, chlorine or bromine;
x is selected from chlorine or bromine;
R 7 selected from substituted or unsubstituted C 1-12 Alkyl, wherein the substituted or unsubstituted substituents are selected from the group consisting of fluoro, chloro, bromo, methyl, isopropyl, vinyl, phenyl; or R 7 Selected from substituted or unsubstituted C 3-10 Cycloalkyl, wherein the substituted or unsubstituted substituents are selected from methyl, isopropyl.
3. Process according to claim 1 or 2, characterized in that the olefinic compound of formula 1 is selected from the compounds having the following structural formula:
Figure FDA0003942590970000031
the polyhaloalkane compounds of formula 2 are selected from compounds having the following structural formula:
Figure FDA0003942590970000041
the alcohol compound of formula 3 is selected from compounds having the following structural formula:
Figure FDA0003942590970000042
4. the process according to any one of claims 1-2, characterized in that the base is sodium carbonate.
5. The method according to any one of claims 1-2, wherein the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
6. The method of claim 5, wherein the inert atmosphere is an argon atmosphere.
7. The method according to any one of claims 1 to 2, wherein the reaction temperature of the heating and stirring reaction is 50 to 100 ℃; the reaction time is 3 to 12 hours.
8. The method of claim 7, wherein the reaction temperature of the heating and stirring reaction is 70-90 ℃; the reaction time was 6 hours.
9. The method of claim 8, wherein the reaction temperature of the heating and stirring reaction is 80 ℃.
10. The method as claimed in any one of claims 1-2, wherein the molar ratio of the copper catalyst, the 4-methoxybenzene diazo tetrafluoroborate, the base, the olefinic compound of formula 1, and the alcoholic compound of formula 3 is (0.01-0.2) to (1-3) to (1-10).
11. The method as claimed in claim 10, wherein the feeding molar ratio of the copper catalyst, the 4-methoxybenzene diazo tetrafluoroborate, the base, the olefin compound of formula 1, and the alcohol compound of formula 3 is 0.1; the compound of formula 2 serves as a reaction solvent in the reaction at the same time.
12. A method according to any one of claims 1-2, characterized in that the post-processing operation is as follows: filtering after the reaction is completed, concentrating the filtrate, and separating the residue by silica gel column chromatography to obtain the target product of the alkene dual-functionalization shown in the formula 4, wherein the elution solvent separated by the silica gel column chromatography is a mixed solvent of petroleum ether and ethyl acetate.
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