CN114805182A - Method for synthesizing indole spiro cyclopropane compound by visible light catalysis - Google Patents

Method for synthesizing indole spiro cyclopropane compound by visible light catalysis Download PDF

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CN114805182A
CN114805182A CN202210467773.5A CN202210467773A CN114805182A CN 114805182 A CN114805182 A CN 114805182A CN 202210467773 A CN202210467773 A CN 202210467773A CN 114805182 A CN114805182 A CN 114805182A
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visible light
indole spiro
nmr
spiro cyclopropane
cdcl
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赵帅
穆壮壮
保宁
徐丽琴
钱明成
陈新
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Changzhou University
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Changzhou University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/96—Spiro-condensed ring systems

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Abstract

The invention belongs to the technical field of chemical pharmacy and fine chemical preparation, and particularly relates to a method for synthesizing indole spiro cyclopropane compounds by visible light catalysis. The technical points are as follows: under the irradiation of visible light, the 3-diazoindole and olefin or olefin derivative undergo a cycloaddition reaction to generate the indole spiro cyclopropane compound. The invention provides a method for synthesizing indole spiro cyclopropane compounds by photocatalysis, which takes 3-diazoindole and olefin or olefin derivatives as raw materials, and the raw materials undergo a cycloaddition reaction under the irradiation of visible light to generate the indole spiro cyclopropane compounds. The reaction condition is very mild, the operation is simple and convenient, the yield is high, and the product is easy to separate and purify. Provides a green, environment-friendly, economic and safe way for synthesizing the compounds, and the method has wide application prospect in the technical fields of chemical pharmacy and fine chemical preparation.

Description

Method for synthesizing indole spiro cyclopropane compound by visible light catalysis
Technical Field
The invention belongs to the technical field of chemical pharmacy and fine chemical preparation, and particularly relates to a method for synthesizing indole spiro cyclopropane compounds by visible light catalysis.
Background
Indole spiro cyclopropane compounds are important heterocyclic skeletons, which are widely present in a variety of natural products and bioactive molecules. Such as non-nucleoside reverse transcriptase inhibitors, inotropic drugs and anti-tumor drugs.
Currently, indole spiro cyclopropane compounds are mainly obtained by performing cycloaddition reaction on corresponding diazonium and olefin. Transition metal catalyzed cycloaddition of diazo compounds with olefins is the most widely used method for the synthesis of such compounds. The following formula:
Figure BDA0003625151850000011
however, the transition metal catalyzed method has disadvantages such as expensive catalyst, harsh reaction conditions, easy heavy metal residue in the product, etc. With the gradual deepening of the energy-saving and environment-friendly concept of people, the development of metal-free catalytic reaction gradually becomes one of the research hotspots in the field of organic synthesis.
The preparation of indole spiro cyclopropane compounds by metal-free catalyzed cycloaddition of diazo to olefins has been successfully accomplished. The following formula:
Figure BDA0003625151850000021
although the method does not use a metal catalyst, the temperature required by the reaction is higher, and the method does not accord with the production concepts of energy conservation, environmental protection and green safety.
In view of the defects of the synthesis method of the indole spiro cyclopropane compound and the importance of the structure, the inventor develops a method for synthesizing the indole spiro cyclopropane compound by visible light catalysis based on years of abundant experience and professional knowledge of the materials and by matching theoretical analysis and innovation.
Disclosure of Invention
The invention aims to provide a method for synthesizing indole spiro cyclopropane compounds by visible light catalysis, which can generate the indole spiro cyclopropane compounds under the irradiation of visible light without adding extra catalysts, and has the advantages of mild reaction conditions, simple and convenient operation, high yield and easy separation of products.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a method for synthesizing indole spiro cyclopropane compounds by visible light catalysis, which is characterized in that under the irradiation of visible light, 3-diazoindole and olefin or olefin derivatives undergo a cycloaddition reaction to generate the indole spiro cyclopropane compounds.
The reaction equation of the invention is as follows:
Figure BDA0003625151850000022
the reaction mechanism is as follows:
Figure BDA0003625151850000031
firstly, 3-diazoindole 1 jumps to an excited state 1 under the irradiation of visible light, then loses one molecule of nitrogen to generate a singlet carbene intermediate, and then performs cycloaddition reaction with olefin 2 to obtain an indole spiro cyclopropane compound 3.
R in the above reaction equation 1 Is various substituents at each position (specifically 4, 5, 6, 7) on the benzene ring of the 3-diazoindole, including but not limited to alkyl, alkoxy, alkenyl, aryl, halogen, amino, nitro, carbonyl or trifluoromethyl, etc.
R 2 Is a substituent on the nitrogen atom in the 3-diazoindole, and includes but is not limited to alkyl, alkenyl, aryl, alkynyl or acyl, and the like.
R 3 、R 4 、R 5 Is a substituent on the olefin structure, including but not limited to hydrogen, alkyl, aryl, alkoxy, alkenyl, alkynyl, ester, cyano, trifluoromethyl, or the like.
R 6 Is a substituent on the olefin structure, including but not limited to aryl, alkenyl, ester, amido, cyano, trifluoromethyl, and the like。
Further, the structural general formula of the 3-diazoindole is as follows:
Figure BDA0003625151850000032
wherein R is 1 Is any one of alkyl, alkoxy, alkenyl, aryl, halogen, amino, nitro, carbonyl or trifluoromethyl; r 2 Is any one of alkyl, alkenyl, aryl, alkynyl or acyl.
Further, the structural formula of the olefin or the olefin derivative is as follows:
Figure BDA0003625151850000033
wherein R is 3 、R 4 And R 5 Respectively is any one of hydrogen, alkyl, aryl, alkoxy, alkenyl, alkynyl, ester group, cyano or trifluoromethyl; r 6 Is any one of aryl, alkenyl, ester group, amido, cyano or trifluoromethyl.
Further, aryl is any one of phenyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, thiazolyl, or triazolyl.
Further, the ester group is any one of carboxylate, phosphate, carbonate, sulfate, or sulfite.
Furthermore, the visible light is white light or a single-wavelength LED light source with the wavelength range of 400-780 nm.
Further, the method for synthesizing the indole spiro cyclopropane compound by visible light catalysis, which is provided by the invention, comprises the following specific operation steps:
s1, uniformly mixing the 3-diazoindole and the olefin or the olefin derivative;
s2, placing the reaction system in the step S1 under visible light for irradiation;
s3, after the reaction in the step S2 is finished, removing the solvent, and purifying the crude product to obtain the indole spiro cyclopropane compound.
Further, in step S1, the 3-diazoindole is dissolved in the organic solvent and then mixed with the olefin or the olefin derivative.
Further, the organic solvent comprises any one or a mixture of several of toluene, dichloromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide or diethyl ether.
Furthermore, the irradiation time in step S2 is 12-72 h.
In conclusion, the invention has the following beneficial effects:
the invention provides a method for synthesizing indole spiro cyclopropane compounds by visible light catalysis, which takes 3-diazoindole and olefin or olefin derivatives as raw materials, and the raw materials undergo a cycloaddition reaction under the irradiation of visible light to generate the indole spiro cyclopropane compounds. The reaction condition is very mild, the operation is simple and convenient, the yield is high, and the product is easy to separate and purify. Provides a green, environment-friendly, economic and safe way for synthesizing the compounds, and the method has wide application prospect in the technical fields of chemical pharmacy and fine chemical preparation.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the specific embodiments, features and effects of the method for synthesizing indole spiro cyclopropane compounds under visible light catalysis proposed by the present invention are described in detail below.
Example 1: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, getting 35mg
Figure BDA0003625151850000051
Dissolved in 2ml of 1, 2-dichloroethane, to which 180. mu.L of methyl acrylate was added;
s2, placing the mixed solution obtained in the step S1 under the 470nm blue light irradiation condition, and reacting for 24 hours at room temperature;
s3, concentrating the reaction solution obtained in the step S2Purifying by column chromatography to obtain the product
Figure BDA0003625151850000052
Figure BDA0003625151850000053
Figure BDA0003625151850000054
As a pink solid, the yield was 48%; 1 H NMR(500MHz,CDCl 3 ):δ7.35(d,J＝7.5Hz,1H),7.28(td,J 1 ＝7.7Hz,J 2 ＝1.3Hz,1H),7.02(t,J＝7.6Hz,1H),6.89(d,J＝7.8Hz,1H),3.66(s,3H),3.27(s,3H),2.70(dd,J 1 ＝8.6Hz,J 2 ＝7.4Hz,1H),2.14(dd,J 1 ＝7.4Hz,J 2 ＝4.4Hz,1H),2.02(dd,J 1 ＝8.6Hz,J 2 ＝4.4Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ174.7,169.3,144.4,127.8,125.9,122.7,122.4,108.2,52.3,33.7,32.6,26.8,20.8.HRMS(ESI)m/z:C 13 H 14 NO 3 (M+H) + theoretical 232.0968, found 232.0970.
Figure BDA0003625151850000055
As a yellow solid, yield 34%; 1 H NMR(400MHz,CDCl 3 ):δ7.29(t,J＝7.7Hz,1H),7.04(t,J＝7.6Hz,1H),6.89(d,J＝7.8Hz,1H),6.84(d,J＝7.4Hz,1H),3.75(s,3H),3.26(s,3H),2.65(t,J＝8.3Hz,1H),2.38(dd,J 1 ＝8.0Hz,J 2 ＝5.0Hz,1H),1.81(dd,J 1 ＝8.6Hz,J 2 ＝5.0Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ173.3,167.6,143.7,128.8,127.9,122.3,118.5,108.2,52.5,32.9,32.6,26.7,21.1.HRMS(ESI)m/z:C 13 H 14 NO 3 (M+H) + theoretical 232.0968, found 232.0970.
Example 2: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, getting 35mg
Figure BDA0003625151850000061
Dissolving in 2ml methyl acrylate, and mixing;
s2, placing the reaction system in the step S1 under 470nm blue light irradiation, and reacting for 24 hours at room temperature;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structural formula of
Figure BDA0003625151850000062
Wherein the content of the first and second substances,
Figure BDA0003625151850000063
as a pink solid, with a yield of 53%, the characterization data were the same as in example 1;
Figure BDA0003625151850000064
the yellow solid showed a difference of 43%, and the characterization data were the same as in example 1.
Example 3: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, getting 35mg
Figure BDA0003625151850000065
Dissolving in 2ml methyl acrylate, and mixing;
s2, placing the reaction system in the step S1 under the irradiation of white light, and reacting for 72 hours at room temperature;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structural formula of
Figure BDA0003625151850000071
Wherein the content of the first and second substances,
Figure BDA0003625151850000072
as a pink solid, with a yield of 52%, the characterization data were the same as in example 1;
Figure BDA0003625151850000073
the yellow solid showed a difference of 42%, and the characterization data were the same as in example 1.
Example 4: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, getting 35mg
Figure BDA0003625151850000074
Dissolving in 2ml methyl acrylate, and mixing;
s2, placing the reaction system in the step S1 under the green light irradiation of 525nm, and reacting for 24 hours at room temperature;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structural formula of
Figure BDA0003625151850000075
Wherein the content of the first and second substances,
Figure BDA0003625151850000076
as a pink solid, with a yield of 35%, the characterization data were the same as in example 1;
Figure BDA0003625151850000077
the yellow solid showed a difference of 36%, and the characterization data were the same as in example 1.
Example 5: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 32mg
Figure BDA0003625151850000081
Dissolved in 2ml of 1, 2-dichloroethane, to which 180. mu.L of methyl acrylate was added;
s2, placing the reaction solution in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structural formula of
Figure BDA0003625151850000082
Wherein the content of the first and second substances,
Figure BDA0003625151850000083
is white solid, the yield is 48 percent, 1 H NMR(500MHz,CDCl 3 ):δ8.79(s,1H),7.34(d,J＝7.6Hz,1H),7.23(td,J 1 ＝7.7Hz,J 2 ＝1.3Hz,1H),7.01(td,J 1 ＝7.6Hz,J 2 ＝1.1Hz,1H),6.97(d,J＝7.8Hz,1H),3.69(s,3H),2.72(td,J 1 ＝8.7Hz,J 2 ＝7.4Hz,1H),2.17(dd,J 1 ＝7.5Hz,J 2 ＝4.5Hz,1H),2.04(dd,J 1 ＝8.7Hz,J 2 ＝4.5Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ177.0,169.2,141.5,127.9,126.3,123.1,122.5,110.1,52.4,34.2,32.9,21.1.HRMS(ESI)m/z:C 12 H 12 NO 3 (M+H) + theoretical 218.0812, found 218.0811.
Figure BDA0003625151850000084
Is yellow solid, the yield is 32 percent, 1 H NMR(500MHz,CDCl 3 ):δ8.60(s,1H),7.22(td,J 1 ＝7.8Hz,J 2 ＝1.2Hz,1H),7.02(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),6.96(d,J＝7.8Hz,1H),6.83(d,J＝7.4Hz,1H),3.74(s,3H),2.67(t,J＝8.3Hz,1H),2.39(dd,J 1 ＝8.0Hz,J 2 ＝5.0Hz,1H),1.84(dd,J 1 ＝8.6Hz,J 2 ＝5.0Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ175.7,167.6,140.8,129.4,127.9,122.4,119.0,110.2,52.6,33.5,32.8,21.3.HRMS(ESI)m/z:C 12 H 12 NO 3 (M+H) + theoretical 218.0812, found 218.0811.
Example 6: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing indole spiro cyclopropane compounds under the catalysis of visible light provided by the embodiment specifically comprises the following operation steps:
s1, mixing 32mg
Figure BDA0003625151850000091
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound, wherein the molecular structure is as follows:
Figure BDA0003625151850000092
white and yellow solids, 57% and 38% yield, respectively. The characterization data are the same as in example 3.
Example 7: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 40.2mg
Figure BDA0003625151850000093
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000094
wherein
Figure BDA0003625151850000095
For red solids, the yield is 54%, 1H NMR (400MHz, CDCl3): δ 8.30(d, J ═ 8.4Hz,1H), 7.37-7.29 (M,2H),7.16(td, J1 ═ 7.6Hz, J2 ═ 1.1Hz,1H),3.68(s,3H),2.75(dd, J1 ═ 8.8Hz, J2 ═ 7.6Hz,1H),2.68(s,3H),2.21(dd, J1 ═ 7.7Hz, J2 ═ 4.7Hz,1H),2.10(dd, J1 ═ 8.8Hz, J2 ═ 4.6Hz,1H) · 13C NMR (100MHz, cdesi 3 δ,52.6, 52.34, 2.34, 2.3814H, 2.73714H, theoretical M + 14H), (hrz, M, 14H), (H, M, 14, M.
Figure BDA0003625151850000101
As a white solid, yield 35%; 1 H NMR(500MHz,CDCl 3 ):δ8.28(d,J＝8.2Hz,1H),7.33(td,J 1 ＝7.8Hz,J 2 ＝1.4Hz,1H),7.19(td,J 1 ＝7.6Hz,J 2 ＝1.2Hz,1H),6.84(dd,J 1 ＝7.7Hz,J 2 ＝1.5Hz,1H),3.76(s,3H),2.72(t,J＝8.5Hz,1H),2.66(s,3H),2.46(dd,J 1 ＝8.3Hz,J 2 ＝5.1Hz,1H),1.89(dd,J 1 ＝8.7Hz,J 2 ＝5.0Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ174.3,170.9,167.0,139.9,128.4,127.9,125.3,118.2,116.8,52.7,35.1,33.0,26.8,23.2.HRMS(ESI)m/z:C 14 H 14 NO 4 (M+H) + theoretical 260.0917, found 260.0919.
Example 8: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 63mg
Figure BDA0003625151850000102
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000103
Figure BDA0003625151850000104
as a red solid, the yield was 53%, 1 H NMR(300MHz,CDCl 3 ):δ8.03–7.96(m,3H),7.38–7.29(m,4H),7.13(td,J 1 ＝7.5Hz,J 2 ＝1.1Hz,1H),3.66(s,3H),2.69(dd,J 1 ＝8.9Hz,J 2 ＝7.7Hz,1H),2.42(s,3H),2.11(dd,J 1 ＝7.7Hz,J 2 ＝4.7Hz,1H),2.02(dd,J 1 ＝8.9Hz,J 2 ＝4.7Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.2,168.3,145.9,139.7,135.2,130.0,128.5,128.1,124.8,124.7,122.9,113.5,52.5,34.6,33.8,22.2,21.9.HRMS(ESI)m/z:C 19 H 18 NO 5 S(M+H) + theoretical 372.0900, found 372.0903.
Figure BDA0003625151850000111
Is yellow solid, the yield is 32 percent, 1 H NMR(400MHz,CDCl 3 ):δ8.00–7.94(m,3H),7.37–7.28(m,3H),7.15(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),6.79(dd,J 1 ＝7.7Hz,J 2 ＝1.3Hz,1H),3.64(s,3H),2.61(t,J＝8.5Hz,1H),2.41(s,3H),2.37(dd,J 1 ＝8.3Hz,J 2 ＝5.2Hz,1H),1.80(dd,J 1 ＝8.7Hz,J 2 ＝5.2Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ171.6,166.5,145.7,139.1,135.3,129.8,128.6,128.1,127.8,124.9,118.9,113.9,52.7,35.3,32.6,22.9,21.8.HRMS(ESI)m/z:C 19 H 18 NO 5 S(M+H) + theoretical 372.0900, found 372.0903.
Example 9: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 53mg
Figure BDA0003625151850000112
Dissolved in 2ml of methyl acrylate;
s2, reacting the steps for 72 hours at room temperature under 470nm blue light irradiation;
s3, concentrating the reaction solution obtained in the step S3, and separating the residue by column chromatography to obtain a compound; the molecular structure is as follows:
Figure BDA0003625151850000113
wherein the content of the first and second substances,
Figure BDA0003625151850000121
as a red solid, yield was 58%; 1 H NMR(300MHz,CDCl 3 ):δ7.89(d,J＝8.1Hz,1H),7.77–7.72(m,2H),7.64–7.57(m,1H),7.52–7.33(m,4H),7.19(td,J 1 ＝7.7Hz,J 2 ＝1.1Hz,1H),3.71(s,3H),2.72(dd,J 1 ＝8.8Hz,J 2 ＝7.6Hz,1H),2.23(dd,J 1 ＝7.6Hz,J 2 ＝4.7Hz,1H),2.08(dd,J 1 ＝8.8Hz,J 2 ＝4.6Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.6,169.2,168.5,140.8,134.2,133.1,129.5,128.3,128.3,125.4,124.9,122.6,115.0,52.6,34.5,34.2,22.1.HRMS(ESI)m/z:C 19 H 16 NO 4 (M+H) + theoretical 322.1074, found 322.1077.
Figure BDA0003625151850000122
As a yellow solid, yield 35%; 1 H NMR(500MHz,CDCl 3 ):δ7.90(d,J＝8.1Hz,1H),7.75–7.70(m,2H),7.59–7.54(m,1H),7.44(t,J＝7.9Hz,2H),7.37(td,J 1 ＝7.9Hz,J 2 ＝1.3Hz,1H),7.21(td,J 1 ＝7.6Hz,J 2 ＝1.1Hz,1H),6.91(dd,J 1 ＝7.6Hz,J 2 ＝1.3Hz,1H),3.71(s,3H),2.73(t,J＝8.5Hz,1H),2.41(dd,J 1 ＝8.2Hz,J 2 ＝5.2Hz,1H),1.92(dd,J 1 ＝8.7Hz,J 2 ＝5.2Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ173.1,169.4,167.0,140.1,134.1,133.1,129.6,128.3,128.3,128.3,125.0,118.6,115.1,52.7,35.2,32.9,22.4.HRMS(ESI)m/z:C 19 H 16 NO 4 (M+H) + theoretical 322.1074, found 322.1077.
Example 10: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 50mg
Figure BDA0003625151850000123
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000131
wherein the content of the first and second substances,
Figure BDA0003625151850000132
is yellow solid, the yield is 56 percent, 1 H NMR(400MHz,CDCl 3 ):δ7.37(d,J＝7.7Hz,1H),7.35–7.22(m,5H),7.17(td,J 1 ＝7.7Hz,J 2 ＝1.3Hz,1H),6.99(td,J 1 ＝7.7Hz,J 2 ＝1.1Hz,1H),6.80(d,J＝7.8Hz,1H),4.97(s,2H),3.69(s,3H),2.78(dd,J 1 ＝8.7Hz,J 2 ＝7.4Hz,1H),2.19(dd,J 1 ＝7.4Hz,J 2 ＝4.4Hz,1H),2.09(dd,J 1 ＝8.7Hz,J 2 ＝4.4Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ175.0,169.4,143.5,135.9,128.9,127.8,127.5,126.0,122.8,122.5,109.2,52.4,44.4,33.7,32.9,21.2.HRMS(ESI)m/z:C 19 H 18 NO 3 (M+H) + theoretical 308.1281, found 308.1283.
Figure BDA0003625151850000133
As a yellow solid, yield 39%; 1 H NMR(500MHz,CDCl 3 ):δ7.36–7.28(m,4H),7.28–7.22(m,1H),7.17(td,J 1 ＝7.8Hz,J 2 ＝1.2Hz,1H),7.00(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),6.85(d,J＝7.5Hz,1H),6.78(d,J＝7.8Hz,1H),4.96(d,J＝1.4Hz,2H),3.77(s,3H),2.70(t,J＝8.4Hz,1H),2.45(dd,J 1 ＝8.0Hz,J 2 ＝5.0Hz,1H),1.87(dd,J 1 ＝8.6Hz,J 2 ＝5.0Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ173.6,167.7,142.8,136.0,128.9,128.9,127.8,127.7,127.5,122.4,118.7,109.3,52.6,44.2,33.5,32.4,21.1.HRMS(ESI)m/z:C 19 H 18 NO 3 (M+H) + theoretical 308.1281, found 308.1283.
Example 11: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 51.9mg
Figure BDA0003625151850000141
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000142
wherein the content of the first and second substances,
Figure BDA0003625151850000143
is yellowA colored solid, yield 57%; 1 H NMR(500MHz,CDCl 3 ):δ7.91(d,J＝8.2Hz,1H),7.35–7.27(m,2H),7.11(td,J 1 ＝7.7Hz,J 2 ＝1.1Hz,1H),3.66(s,3H),2.75(t,J＝8.2Hz,1H),2.16(dd,J 1 ＝7.6Hz,J 2 ＝4.6Hz,1H),2.09(dd,J 1 ＝8.7Hz,J 2 ＝4.6Hz,1H),1.64(s,9H). 13 C NMR(125MHz,CDCl 3 ):δ173.6,168.6,149.1,140.3,128.1,124.8,124.3,122.3,115.0,84.7,52.5,34.7,34.1,28.2,22.0.HRMS(ESI)m/z:C 17 H 19 NNaO 5 (M+Na) + theoretical 340.1155, found 340.1158.
Figure BDA0003625151850000144
Is yellow solid, the yield is 37 percent, 1 H NMR(500MHz,CDCl 3 ):δ7.86(d,J＝8.2Hz,1H),7.30(td,J 1 ＝7.9Hz,J 2 ＝1.3Hz,1H),7.13(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),6.81(d,J＝7.6Hz,1H),3.75(s,3H),2.66(t,J＝8.4Hz,1H),2.43(dd,J 1 ＝8.2Hz,J 2 ＝5.0Hz,1H),1.82(dd,J 1 ＝8.7Hz,J 2 ＝5.0Hz,1H),1.63(s,9H). 13 C NMR(125MHz,CDCl 3 ):δ171.8,167.1,149.2,139.7,128.1,127.8,124.5,118.3,115.2,84.6,52.7,34.7,32.9,28.2,23.1.HRMS(ESI)m/z:C 17 H 19 NNaO 5 (M+Na) + theoretical 340.1155, found 340.1158.
Example 12: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 42mg
Figure BDA0003625151850000151
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, mixing the reaction solution obtained in the step S2Concentrating, separating the residue by column chromatography to obtain compounds 3h and 3h', the molecular structure is:
Figure BDA0003625151850000152
wherein the content of the first and second substances,
Figure BDA0003625151850000153
is white solid, the yield is 48 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.20(t,J＝8.0Hz,1H),6.96(dd,J 1 ＝8.2Hz,J 2 ＝1.0Hz,1H),6.82(dd,J 1 ＝7.9Hz,J 2 ＝0.9Hz,1H),3.68(s,3H),3.26(s,3H),2.79(dd,J 1 ＝8.2Hz,J 2 ＝4.4Hz,1H),2.68(dd,J 1 ＝9.7Hz,J 2 ＝8.2Hz,1H),1.86(dd,J 1 ＝9.7Hz,J 2 ＝4.4Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.7,168.7,146.2,129.0,128.7,123.8,122.8,107.2,52.8,32.8,32.6,27.1,16.7.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0580.
Figure BDA0003625151850000154
White bottom, yield 32%; 1 H NMR(400MHz,CDCl 3 ):δ7.20(t,J＝8.0Hz,1H),6.95(d,J＝8.3Hz,1H),6.80(d,J＝7.8Hz,1H),3.75(s,3H),3.47(t,J＝8.5Hz,1H),3.26(s,3H),2.49(dd,J 1 ＝8.9Hz,J 2 ＝4.8Hz,1H),2.19(dd,J 1 ＝8.1Hz,J 2 ＝4.8Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ173.1,168.3,145.7,128.7,127.8,123.7,123.5,107.0,52.6,33.1,29.1,27.0,17.9.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0580.
Example 13: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
S142mg of the total weight of the powder
Figure BDA0003625151850000161
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000162
wherein the content of the first and second substances,
Figure BDA0003625151850000163
as a white solid, with a yield of 47%, 1 H NMR(400MHz,CDCl 3 ):δ7.37(d,J＝2.1Hz,1H),7.29–7.23(m,1H),6.80(d,J＝8.3Hz,1H),3.70(s,3H),3.26(s,3H),2.72(t,J＝8.1Hz,1H),2.13(dd,J 1 ＝7.4Hz,J 2 ＝4.5Hz,1H),2.04(dd,J 1 ＝8.7Hz,J 2 ＝4.5Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ174.3,169.1,142.9,127.9,127.8,127.6,123.3,109.0,52.5,33.7,32.9,26.9,21.3.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0577.
Figure BDA0003625151850000164
Is yellow solid, the yield is 32 percent, 1 H NMR(400MHz,CDCl 3 ):δ7.28–7.22(m,1H),6.83–6.78(m,2H),3.75(s,3H),3.24(s,3H),2.66(t,J＝8.4Hz,1H),2.40(dd,J 1 ＝8.1Hz,J 2 ＝5.0Hz,1H),1.82(dd,J 1 ＝8.7Hz,J 2 ＝5.0Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ173.0,167.3,142.3,130.6,127.8,127.8,119.2,109.2,52.7,33.3,32.3,26.9,21.4.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0577.
Example 14: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 42mg
Figure BDA0003625151850000171
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000172
Figure BDA0003625151850000173
as a white solid, yield 53%; 1 H NMR(400MHz,CDCl 3 ):δ7.30(d,J＝8.0Hz,1H),7.01(dd,J 1 ＝8.0Hz,J 2 ＝1.8Hz,1H),6.91(d,J＝1.9Hz,1H),3.70(s,3H),3.28(s,3H),2.73(t,J＝8.0Hz,1H),2.16(dd,J 1 ＝7.4Hz,J 2 ＝4.5Hz,1H),2.06(dd,J 1 ＝8.7Hz,J 2 ＝4.4Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ174.7,169.2,145.5,133.8,124.2,123.7,122.2,108.9,52.4,33.5,32.8,26.9,21.0.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0579.
Figure BDA0003625151850000174
As a yellow solid, yield 35%; 1 H NMR(300MHz,CDCl 3 ):δ7.00(dd,J 1 ＝8.0Hz,J 2 ＝1.8Hz,1H),6.88(d,J＝1.8Hz,1H),6.74(d,J＝8.0Hz,1H),3.74(s,3H),3.23(s,3H),2.64(t,J＝8.3Hz,1H),2.38(dd,J 1 ＝8.1Hz,J 2 ＝5.0Hz,1H),1.81(dd,J 1 ＝8.6Hz,J 2 ＝5.0Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.3,167.4,144.8,133.7,127.2,122.1,119.5,109.1,52.6,33.1,32.1,26.8,21.3.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0579.
Example 15: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 42mg
Figure BDA0003625151850000181
Dissolving in 2ml methyl acrylate, reacting at room temperature under 470nm blue light irradiation for 72h, concentrating the reaction solution, and separating the residue by column chromatography to obtain a compound with a molecular structure:
Figure BDA0003625151850000182
wherein the content of the first and second substances,
Figure BDA0003625151850000183
as a yellow solid, yield 52%; 1 H NMR(300MHz,CDCl 3 ):δ7.25–7.16(m,2H),6.91(dd,J 1 ＝8.3Hz,J 2 ＝7.5Hz,1H),3.66(s,3H),3.65(s,3H),2.72(dd,J 1 ＝8.7Hz,J 2 ＝7.5Hz,1H),2.14(dd,J 1 ＝7.5Hz,J 2 ＝4.5Hz,1H),2.05(dd,J 1 ＝8.6Hz,J 2 ＝4.5Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ175.1,168.9,140.1,130.2,128.6,123.1,121.0,115.7,52.4,33.7,33.5,30.4,21.4.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0581.
Figure BDA0003625151850000184
As a yellow solid, yield 34%; 1 H NMR(300MHz,CDCl 3 ):δ7.20(dd,J 1 ＝8.2Hz,J 2 ＝1.2Hz,1H),6.93(dd,J 1 ＝8.2Hz,J 2 ＝7.4Hz,1H),6.69(dd,J 1 ＝7.4Hz,J 2 ＝1.2Hz,1H),3.75(s,3H),3.62(s,3H),2.64(t,J＝8.4Hz,1H),2.40(dd,J 1 ＝8.1Hz,J 2 ＝5.0Hz,1H),1.80(dd,J 1 ＝8.7Hz,J 2 ＝5.0Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.6,167.3,139.6,131.6,130.2,123.1,117.0,115.9,52.7,33.8,32.2,30.0,21.9.HRMS(ESI)m/z:C 13 H 13 ClNO 3 (M+H) + theoretical 266.0579, found 266.0581.
Example 16: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 37.5mg
Figure BDA0003625151850000191
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution, and separating the residue by column chromatography to obtain a compound with a molecular structure:
Figure BDA0003625151850000192
Figure BDA0003625151850000193
wherein the content of the first and second substances,
Figure BDA0003625151850000194
is yellow solid, the yield is 49 percent, 1 H NMR(400MHz,CDCl 3 ):δ7.00(d,J＝7.7,1H),6.91(t,J＝7.5Hz,1H),6.65(d,J＝7.4Hz,1H),3.74(s,3H),3.54(s,3H),2.63–2.56(m,4H),2.37(dd,J 1 ＝8.0Hz,J 2 ＝4.8Hz,1H),1.77(dd,J 1 ＝8.6Hz,J 2 ＝4.9Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.2,167.7,141.6,131.6,129.5,122.3,120.1,116.4,52.5,33.5,32.1,30.0,21.6,19.1.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1127.
Figure BDA0003625151850000195
As a yellow solid, yield 42%; 1 H NMR(300MHz,CDCl 3 ):δ7.17(d,J＝7.6,1H),7.01(d,J＝7.5Hz,1H),6.90(t,J＝7.6Hz,1H),3.66(s,3H),3.56(s,3H),2.69(dd,J 1 ＝8.6Hz,J 2 ＝7.4Hz,1H),2.60(s,3H),2.11(dd,J 1 ＝7.5Hz,J 2 ＝4.4Hz,1H),2.01(dd,J 1 ＝8.6Hz,J 2 ＝4.5Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ175.6,169.2,142.2,131.7,126.5,122.3,120.3,119.9,52.3,33.4,33.3,30.3,21.1,19.3.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1127.
Example 17: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing indole spiro cyclopropane compounds under the catalysis of visible light provided by the embodiment specifically comprises the following operation steps:
s1, mixing 37.5mg
Figure BDA0003625151850000201
Dissolving in 2ml of methyl acrylate;
s2, reacting the reaction solution obtained in the step S1 for 72 hours at room temperature under 470nm blue light, concentrating the reaction solution, and separating the residue by column chromatography to obtain a compound with a molecular structure:
Figure BDA0003625151850000202
Figure BDA0003625151850000203
wherein, the first and the second end of the pipe are connected with each other,
Figure BDA0003625151850000204
is a red solidThe yield was 51%, 1 H NMR(400MHz,CDCl 3 ):δ7.17(s,1H),7.09(d,J＝8.5Hz,1H),6.78(d,J＝7.9Hz,1H),3.68(s,3H),3.26(s,3H),2.69(dd,J 1 ＝8.6Hz,J 2 ＝7.4Hz,1H),2.33(s,3H),2.11(dd,J 1 ＝7.4Hz,J 2 ＝4.4Hz,1H),2.00(dd,J 1 ＝8.6Hz,J 2 ＝4.4Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ174.7,169.4,142.0,132.0,128.1,126.0,123.5,107.9,52.3,33.8,32.6,26.8,21.4,20.8.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1119.
Figure BDA0003625151850000205
Is yellow solid, the yield is 42 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.08(d,J＝7.9Hz,1H),6.77(d,J＝7.9Hz,1H),6.65(s,1H),3.74(s,3H),3.23(s,3H),2.62(t,J＝8.2Hz,1H),2.35(dd,J 1 ＝8.0Hz,J 2 ＝4.9Hz,1H),2.32(s,3H),1.77(dd,J 1 ＝8.6Hz,J 2 ＝4.9Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ173.4,167.8,141.4,132.0,128.9,128.1,119.4,108.0,52.5,32.9,32.4,26.7,21.2,21.1.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1119.
Example 18: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 50.5mg
Figure BDA0003625151850000211
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S1, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000212
wherein the content of the first and second substances,
Figure BDA0003625151850000213
is yellow solid, the yield is 50 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.18–7.07(m,2H),6.86(dd,J 1 ＝5.6Hz,J 2 ＝3.2Hz,1H),3.68(s,3H),3.26(s,3H),2.93(dd,J 1 ＝8.2Hz,J 2 ＝4.7Hz,1H),2.65(dd,J 1 ＝10.1Hz,J 2 ＝8.2Hz,1H),1.84(dd,J 1 ＝10.1Hz,J 2 ＝4.7Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.7,168.6,146.4,128.9,127.1,124.3,117.1,107.7,52.9,32.4,32.8,27.0,16.4.HRMS(ESI)m/z:C 13 H 13 BrNO 3 (M+H) + theoretical 310.0074, found 310.0075.
Figure BDA0003625151850000214
Is yellow solid, the yield is 34 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.19–7.04(m,2H),6.9–6.79(m,1H),3.75(s,3H),3.55(t,J＝8.5Hz,1H),3.24(s,3H),2.56(dd,J 1 ＝9.0Hz,J 2 ＝4.8Hz,1H),2.13(dd,J 1 ＝8.1Hz,J 2 ＝4.8Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.1,168.3,145.9,129.0,126.6,125.0,115.5,107.6,52.6,33.7,29.0,26.9,17.8.HRMS(ESI)m/z:C 13 H 13 BrNO 3 (M+H) + theoretical 310.0074, found 310.0075.
Example 19: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing the above 38.5mg
Figure BDA0003625151850000221
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 h;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000222
wherein the content of the first and second substances,
Figure BDA0003625151850000223
as a white solid, the yield was 57%, 1 H NMR(300MHz,CDCl 3 ):δ7.30–7.18(m,1H),6.77–6.66(m,2H),3.68(s,3H),3.27(s,3H),2.68(dd,J 1 ＝9.3Hz,J 2 ＝7.9Hz,1H),2.43(dd,J 1 ＝7.9Hz,J 2 ＝4.6Hz,1H),1.94(dd,J 1 ＝9.3Hz,J 2 ＝4.6Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.5,168.8,159.2,156.0,146.6,146.5,129.4,129.3,111.9,111.7,110.4,110.1,104.7,104.7,52.6,32.3,32.3,27.2,18.1,18.1.HRMS(ESI)m/z:C 13 H 13 FNO 3 (M+H) + theoretical 250.0874, found 250.0866.
Figure BDA0003625151850000224
Is a white solid with a yield of 31%, 1 H NMR(400MHz,CDCl 3 ):δ7.29–7.18(m,1H),6.75–6.67(m,2H),3.75(s,3H),3.25(s,3H),3.08(t,J＝8.4Hz,1H),2.29(dd,J 1 ＝8.0Hz,J 2 ＝4.7Hz,1H),2.16(dd,J 1 ＝8.7Hz,J 2 ＝4.8Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ173.0,167.9,158.6,156.2,145.9,129.2,129.1,114.1,109.9,109.7,104.7,104.6,52.6,31.5,30.6,30.6,27.2,19.3.HRMS(ESI)m/z:C 13 H 13 FNO 3 (M+H) + theoretical 250.0874, found 250.0866.
Example 20: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, 43.6mg
Figure BDA0003625151850000231
Dissolving in 2ml of methyl acrylate;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000232
wherein the content of the first and second substances,
Figure BDA0003625151850000233
is yellow solid, the yield is 31 percent, 1 H NMR(300MHz,CDCl 3 ):δ8.33–8.24(m,2H),6.97(d,J＝8.5Hz,1H),3.72(s,3H),3.35(s,3H),2.79(dd,J 1 ＝8.8Hz,J 2 ＝7.5Hz,1H),2.29(dd,J 1 ＝7.5Hz,J 2 ＝4.6Hz,1H),2.14(dd,J 1 ＝8.8Hz,J 2 ＝4.6Hz,1H). 13 C NMR(100MHz,CDCl 3 ):δ174.9,168.7,149.8,143.4,126.8,125.0,119.0,107.7,52.7,33.5,33.5,27.3,21.8.HRMS(ESI)m/z:C 13 H 13 N 2 O 5 (M+H) + theoretical value 277.0819, found value 277.0815
Figure BDA0003625151850000234
Is yellow solid, the yield is 19 percent, 1 H NMR(300MHz,CDCl 3 ):δ8.28(dd,J 1 ＝8.6Hz,J 2 ＝2.2Hz,1H),7.76(d,J＝2.2Hz,1H),6.97(d,J＝8.7Hz,1H),3.76(s,3H),3.33(s,3H),2.81(t,J＝8.5Hz,1H),2.49(dd,J 1 ＝8.2Hz,J 2 ＝5.2Hz,1H),1.97(dd,J 1 ＝8.8Hz,J 2 ＝5.2Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.5,166.8,149.2,143.3,129.9,125.1,114.7,107.8,52.8,33.8,32.1,27.2,22.0.HRMS(ESI)m/z:C 13 H 13 N 2 O 5 (M+H) + theoretical 277.0819, found 277.0815.
Example 21: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000241
Dissolving in 2ml of styrene;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a mixture of compounds 3q and 3q', wherein the molecular structure is as follows:
Figure BDA0003625151850000242
as a red oil, 99% yield (3q:3q' ═ 2: 1). 1 H NMR(500MHz,CDCl 3 ):δ7.36–7.24(m,6.5H),7.22–7.14(m,3H),7.09(td,J 1 ＝7.6Hz,J 2 ＝1.1Hz,0.5H),6.99(d,J＝7.5Hz,0.5H),6.88(t,J＝7.6Hz,1.5H),6.70(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),5.97(d,J＝7.5Hz,1H),3.36(d,J＝8.5Hz,1H),3.34(s,3H),3.18(s,1.5H),3.16(d,J＝8.8Hz,0.5H),2.42(dd,J 1 ＝8.7Hz,J 2 ＝4.9Hz,0.5H),2.20(dd,J 1 ＝9.1Hz,J 2 ＝4.5Hz,1H),2.08(dd,J 1 ＝9.1Hz,J 2 ＝4.9Hz,0.5H),2.01(dd,J 1 ＝8.0Hz,J 2 ＝4.5Hz,1H). 13 C NMR(125MHz,CDCl 3 ):δ176.6,173.9,143.9,143.6,135.3,134.4,130.9,130.0,129.4,128.5,128.0,127.6,127.5,127.3,126.9,126.7,122.0,121.6,120.8,118.2,107.9,107.9,38.2,35.9,34.0,33.4,26.8,26.6,22.6,22.6.HRMS(ESI)m/z:C 17 H 16 NO(M+H) + Theoretical 250.1227, found 250.1228.
Example 22: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000251
Dissolved in 2ml
Figure BDA0003625151850000252
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000253
wherein the content of the first and second substances,
Figure BDA0003625151850000254
is yellow solid, the yield is 62 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.27(td,J 1 ＝7.6Hz,J 2 ＝1.5Hz,1H),7.07–6.93(m,2H),6.89(d,J＝7.8Hz,1H),4.72(dd,J 1 ＝7.0Hz,J 2 ＝5.1Hz,1H),3.27(s,3H),2.10(t,J＝6.6Hz,1H),2.02(s,3H),1.87(dd,J 1 ＝6.3Hz,J 2 ＝5.1Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.7,170.2,144.3,127.5,126.0,122.0,120.6,108.4,60.1,32.3,26.7,21.0,20.5.HRMS(ESI)m/z:C 13 H 14 NO 3 (M+H) + theoretical 232.0968, found 232.0965.
Figure BDA0003625151850000255
Is yellow solid, the yield is 31 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.27(td,J 1 ＝7.7Hz,J 2 ＝1.2Hz,1H),7.02(td,J 1 ＝7.6Hz,J 2 ＝1.0Hz,1H),6.88(d,J＝7.8Hz,1H),6.80(d,J＝7.4Hz,1H),4.49(dd,J 1 ＝6.8Hz,J 2 ＝5.5Hz,1H),3.25(s,3H),2.24(dd,J 1 ＝6.4Hz,J 2 ＝5.5Hz,1H),2.11(s,3H),1.91(t,J＝6.6Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ172.7,171.3,143.4,128.8,127.6,122.2,118.5,108.2,60.5,31.9,26.7,22.1,20.7.HRMS(ESI)m/z:C 13 H 14 NO 3 (M+H) + theoretical 232.0968, found 232.0965.
Example 23: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000261
Dissolved in 2ml
Figure BDA0003625151850000262
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000263
wherein the content of the first and second substances,
Figure BDA0003625151850000264
is red solid, the yield is 62 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.31–7.17(m,1H),7.04–6.91(m,2H),6.86(d,J＝7.8Hz,1H),3.62(s,3H),3.26(s,3H),2.39(d,J＝5.0Hz,1H),1.86(d,J＝5.0Hz,1H),1.73(s,3H). 13 C NMR(75MHz,CDCl 3 ):δ173.7,170.8,143.9,127.5,127.0,122.0,120.7,108.0,52.5,39.0,35.5,26.7,26.3,14.0.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1125.
Figure BDA0003625151850000265
Is yellow solid, the yield is 36 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.30(td,J 1 ＝7.7Hz,J 2 ＝1.4Hz,1H),7.04(td,J 1 ＝7.5Hz,J 2 ＝1.0Hz,1H),6.97(dd,J 1 ＝7.5Hz,J 2 ＝1.4Hz,1H),6.91(d,J＝7.8Hz,1H),3.75(s,3H),3.24(s,3H),2.46(d,J＝5.1Hz,1H),1.61(s,3H),1.57(d,J＝5.1Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ174.3,171.7,144.8,127.7,126.4,121.8,108.4,52.6,38.3,36.5,27.2,26.7,17.1.HRMS(ESI)m/z:C 14 H 16 NO 3 (M+H) + theoretical 246.1125, found 246.1125.
Example 24: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000271
Dissolved in 2ml
Figure BDA0003625151850000272
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000273
wherein the content of the first and second substances,
Figure BDA0003625151850000274
red oil, yield 62%, 1 H NMR(400MHz,CDCl 3 ):δ7.34(d,J＝7.6Hz,1H),7.27(t,J＝7.8Hz,1H),7.00(t,J＝7.6Hz,1H),6.89(d,J＝7.8Hz,1H),3.28(s,3H),2.63(t,J＝8.0Hz,1H),2.08(dd,J 1 ＝7.8Hz,J 2 ＝4.5Hz,1H),1.93(dd,J 1 ＝8.7Hz,J 2 ＝4.5Hz,1H),1.37(s,9H). 13 C NMR(75MHz,CDCl 3 ):δ175.1,167.8,144.3,127.6,126.1,122.5,122.2,108.1,81.9,33.9,33.3,28.2,26.8,20.6.HRMS(ESI)m/z:C 16 H 20 NO 3 (M+H) + theoretical 274.1438, found 274.1436.
Figure BDA0003625151850000275
As a yellow oil, yield 36%; 1 H NMR(400MHz,CDCl 3 ):δ7.31–7.24(m,1H),7.03(t,J＝7.5Hz,1H),6.88(d,J＝7.8Hz,1H),6.82(d,J＝7.4Hz,1H),3.26(s,3H),2.58(t,J＝8.3Hz,1H),2.30(dd,J 1 ＝7.9Hz,J 2 ＝4.9Hz,1H),1.73(dd,J 1 ＝8.5Hz,J 2 ＝4.8Hz,1H),1.46(s,9H). 13 C NMR(75MHz,CDCl 3 ):δ173.4,166.2,143.8,129.4,127.6,122.1,118.5,108.1,81.7,34.3,32.4,28.2,26.7,21.3.HRMS(ESI)m/z:C 16 H 20 NO 3 (M+H) + theoretical 274.1438, found 274.1436.
Example 25: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000281
Dissolved in 2ml
Figure BDA0003625151850000282
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000283
it was a white oil, 69% yield, 1 H NMR(400MHz,CDCl 3 ):δ7.62(d,J＝7.7Hz,1H),7.28(t,J＝7.8Hz,1H),7.04(t,J＝7.7Hz,1H),6.88(d,J＝7.8Hz,1H),3.65(s,3H),3.25(s,3H),2.77(s,1H),1.58(d,J＝4.8Hz,6H). 13 C NMR(75MHz,CDCl 3 ):δ174.0,169.4,144.4,127.3,125.8,125.1,121.7,108.0,51.8,42.0,40.9,35.1,26.7,20.7,17.1.HRMS(ESI)m/z:C 15 H 18 NO 3 (M+H) + theoretical 260.1281, found 260.1284.
Example 26: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000284
Dissolved in 2ml
Figure BDA0003625151850000285
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000286
wherein
Figure BDA0003625151850000291
Is yellow solid, the yield is 60 percent, 1 H NMR(400MHz,CDCl 3 ):δ7.39(t,J＝7.7Hz,1H),7.20(d,J＝7.4Hz,1H),7.15(t,J＝7.5Hz,1H),6.97(d,J＝7.8Hz,1H),3.30(s,3H),2.45(dd,J 1 ＝9.4Hz,J 2 ＝7.0Hz,1H),2.13(dd,J 1 ＝9.5Hz,J 2 ＝5.0Hz,1H),1.90(dd,J 1 ＝7.0Hz,J 2 ＝5.0Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ173.1,144.2,129.0,124.2,123.0,121.0,117.0,108.8,31.8,27.0,21.4,14.9.HRMS(ESI)m/z:C 12 H 11 N 2 O(M+H) + theoretical 199.0866, found 199.0873.
Figure BDA0003625151850000292
Is yellow solid, the yield is 24 percent, 1 H NMR(300MHz,CDCl 3 ):δ7.35(td,J 1 ＝7.8Hz,J 2 ＝1.2Hz,1H),7.06(t,J＝7.5Hz,1H),6.95(d,J＝7.8Hz,1H),6.83(d,J＝7.4Hz,1H),3.34(s,3H),2.32(dd,J 1 ＝9.1Hz,J 2 ＝7.4Hz,1H),2.19(dd,J 1 ＝7.4Hz,J 2 ＝5.0Hz,1H),1.99(dd,J 1 ＝9.1Hz,J 2 ＝5.0Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ171.6,144.2,129.0,126.1,122.7,119.0,116.0,108.9,32.0,27.0,21.3,15.2.HRMS(ESI)m/z:C 12 H 11 N 2 O(M+H) + theoretical 199.0866, found 199.0873.
Example 27: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000293
Dissolved in 2ml
Figure BDA0003625151850000294
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature;
s3, concentrating the reaction liquid obtained in the step S2, and separating the residue by column chromatography to obtain the compound.
The molecular structure is as follows:
Figure BDA0003625151850000295
as a yellow solid, 42% yield. 3w of 1 H NMR(400MHz,CDCl 3 ):δ8.61(d,J＝4.7Hz,1H),7.55(td,J 1 ＝7.7Hz,J 2 ＝1.8Hz,1H),7.20(d,J＝7.8Hz,1H),7.15(t,J＝6.9Hz,2H),6.84(d,J＝7.8Hz,1H),6.75(t,J＝7.5Hz,1H),6.69(d,J＝7.5Hz,1H),3.34(d,J＝8.3Hz,1H),3.30(s,3H),2.63(dd,J 1 ＝7.8Hz,J 2 ＝4.3Hz,1H),2.21(dd,J 1 ＝8.9Hz,J 2 ＝4.3Hz,1H). 13 C NMR(75MHz,CDCl 3 ):δ176.0,155.1,149.0,144.1,136.4,127.4,126.9,125.6,122.3,121.7,121.7,107.9,38.0,35.4,26.7,21.2.HRMS(ESI)m/z:C 16 H 15 N 2 O(M+H) + Theoretical 251.1179, found 251.1181.
Example 28: method for synthesizing indole spiro cyclopropane compound by visible light catalysis
The method for synthesizing the indole spiro cyclopropane compound by visible light catalysis provided by the embodiment specifically comprises the following operation steps:
s1, mixing 35mg
Figure BDA0003625151850000301
Dissolved in 2ml
Figure BDA0003625151850000302
Performing the following steps;
s2, placing the reaction solution obtained in the step S1 under 470nm blue light irradiation for reaction at room temperature for 72 hours;
s3, concentrating the reaction solution obtained in the step S2, and separating the residue by column chromatography to obtain a compound with a molecular structure as follows:
Figure BDA0003625151850000303
wherein the content of the first and second substances,
Figure BDA0003625151850000304
as a yellow solid, yield was 12%; 1 H NMR(400MHz,CDCl 3 ):δ7.44(d,J＝7.7Hz,1H),7.34(t,J＝7.6Hz,1H),7.06(t,J＝7.8Hz,1H),6.92(d,J＝7.9Hz,1H),3.74(s,6H),3.28(s,3H),2.94(s,2H). 13 C NMR(75MHz,CDCl 3 ):δ171.6,167.6,166.3,144.4,128.6,124.1,122.6,122.5,108.4,52.7,52.6,37.6,35.2,34.9,26.7.HRMS(ESI)m/z:C 15 H 16 NO 5 (M+H) + theoretical 290.1023, found 290.1027.
Figure BDA0003625151850000311
As a yellow solid, the yield was 43%, 1 H NMR(400MHz,CDCl 3 ):δ7.32(t,J＝7.3Hz,2H),7.04(t,J＝7.6Hz,1H),6.89(d,J＝7.9Hz,1H),3.75(s,3H),3.69(s,3H),3.30(t,J＝7.1Hz,2H),3.25(s,3H). 13 C NMR(75MHz,CDCl 3 ):δ171.7,167.8,166.4,144.5,128.7,124.2,122.8,122.7,108.5,52.8,52.7,37.7,35.3,35.1,26.9.HRMS(ESI)m/z:C 15 H 16 NO 5 (M+H) + theoretical 290.1023, found 290.1027.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A method for synthesizing indole spiro cyclopropane compounds by visible light catalysis is characterized in that under the irradiation of visible light, 3-diazoindole and olefin or olefin derivatives undergo a cycloaddition reaction to generate the indole spiro cyclopropane compounds.
2. The visible light catalytic synthesis method of indole spiro cyclopropane compounds according to claim 1, wherein the structural formula of the 3-diazoindole is as follows:
Figure FDA0003625151840000011
wherein R is 1 Is any one of alkyl, alkoxy, alkenyl, aryl, halogen, amino, nitro, carbonyl or trifluoromethyl; r 2 Is any one of alkyl, alkenyl, aryl, alkynyl or acyl.
3. The visible light catalytic synthesis method of indole spiro cyclopropane compound according to claim 2, characterized in that the structural formula of the olefin or the olefin derivative is as follows:
Figure FDA0003625151840000012
wherein R is 3 、R 4 And R 5 Respectively is any one of hydrogen, alkyl, aryl, alkoxy, alkenyl, alkynyl, ester group, cyano or trifluoromethyl; r 6 Is any one of aryl, alkenyl, ester group, amido, cyano or trifluoromethyl.
4. The process for the visible-light catalytic synthesis of indole spiro cyclopropane compounds according to claim 2 or 3, wherein the aryl group is any one of phenyl, naphthyl, pyridyl, furyl, thienyl, pyrazolyl, thiazolyl or triazolyl.
5. The visible light catalytic synthesis method of indole spiro cyclopropane compounds according to claim 3, characterized in that the ester group is any one of carboxylate, phosphate, carbonate, sulfate or sulfite.
6. The method for visible light catalytic synthesis of indole spiro cyclopropane compounds according to claim 1, wherein the visible light is white light or a single wavelength LED light source with a wavelength range of 400-780 nm.
7. The visible light catalytic synthesis method of indole spiro cyclopropane compound according to claim 1, which is characterized in that the specific operation comprises the following steps:
s1, uniformly mixing the 3-diazoindole and the olefin or the olefin derivative;
s2, placing the reaction system in the step S1 under visible light for irradiation;
s3, after the reaction in the step S2 is finished, purifying the crude product to obtain the indole spiro cyclopropane compound.
8. The method for visible-light catalytic synthesis of indole spiro cyclopropane compound of claim 7, wherein in step S1, 3-diazoindole is dissolved in organic solvent and then mixed with olefin or olefin derivative uniformly.
9. The visible light catalytic synthesis method of indole spiro cyclopropane compound of claim 8, wherein the organic solvent comprises any one or a mixture of toluene, dichloromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide or diethyl ether.
10. The method for visible light catalytic synthesis of indole spiro cyclopropane compound according to claim 7, wherein the irradiation time in step S2 is 12-72 h.
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