CN112812097A - Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis - Google Patents

Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis Download PDF

Info

Publication number
CN112812097A
CN112812097A CN202110104563.5A CN202110104563A CN112812097A CN 112812097 A CN112812097 A CN 112812097A CN 202110104563 A CN202110104563 A CN 202110104563A CN 112812097 A CN112812097 A CN 112812097A
Authority
CN
China
Prior art keywords
pyridine
visible light
pyridyl
substituted pyrrole
visible
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110104563.5A
Other languages
Chinese (zh)
Other versions
CN112812097B (en
Inventor
江智勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Normal University
Original Assignee
Henan Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan Normal University filed Critical Henan Normal University
Priority to CN202110104563.5A priority Critical patent/CN112812097B/en
Publication of CN112812097A publication Critical patent/CN112812097A/en
Application granted granted Critical
Publication of CN112812097B publication Critical patent/CN112812097B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention belongs to the technical field of synthesis of pyrrole compounds, and particularly relates to a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis. The visible light catalysis synthesis method of 3- (2-pyridine) substituted pyrrole compounds is specifically to synthesize the compound shown in the formulaN-aryl-substituted glycine,βThe- (2-pyridine) -1, 3-eneyne, the visible light catalyst DPZ and the additive sodium dihydrogen phosphate are mixed evenly in a solvent, and the substituted pyrrole compound is obtained after the reaction under the irradiation of visible light and the separation and purification. The synthetic method has the advantages of simple reaction substrate, mild reaction conditions, no heavy metal participation and high yield.

Description

Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis
Technical Field
The invention belongs to the technical field of synthesis of pyrrole compounds, and particularly relates to a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis.
Background
The 3- (2-pyridine) substituted pyrrole compound has wide application in the fields of synthetic drugs, natural products, functional materials and the like. In the research of green organic synthesis chemistry, the development of a method for synthesizing 3- (2-pyridine) substituted pyrrole compounds in a green, environment-friendly and high-efficiency manner has important significance. The prior art methods for synthesizing 3- (2-pyridine) substituted pyrroles are mainly the serial cyclization reaction of 1-phenyl-3- (2-pyridine) enone, nitromethane and ammonium acetate (Coskun, A.; Yilmaz, M.D.; Akkaya, E.U.; Org.Lett.,2007,9,607-609) and the cycloaddition reaction of methyl benzenesulfonyl methylisonitrile and 2-vinylpyridine (Smith, N.D.; Huang, D.; Cosford, N.D.P.; Org.Lett.,2002,4, 3537-3539). It is noted that these processes have poor step economics and atom economics, generally low yields, and limited functional group compatibility.
In recent years, the visible light catalytic reaction is widely applied to the field of organic synthesis due to greenness, high efficiency and mildness. Because the reaction condition has no heavy metal residue, the product does not need to be removed by heavy metal, and the visible light is used for catalyzing the free radical addition-cyclization reaction of the N-aryl substituted glycine and the beta- (2-pyridine) -1, 3-eneyne.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis. The synthetic method has the advantages of simple reaction substrate, mild reaction conditions, no heavy metal participation and high yield.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for synthesizing 3- (2-pyridine) substituted pyrrole compounds by visible light catalysis is characterized by uniformly mixing N-aryl substituted glycine shown in a formula I, beta- (2-pyridine) -1, 3-eneyne shown in a formula II, a visible light catalyst DPZ and additive sodium dihydrogen phosphate in a solvent under the protection of inert gas, reacting under the irradiation of visible light, and separating and purifying to obtain substituted pyrrole compounds shown in a formula III;
Figure BDA0002917320800000011
in the formulae I, II and III, Ar represents an aryl group such as phenyl, p-methoxyphenyl, p-trifluoromethoxyphenyl, 3, 4-dimethoxyphenyl, 2-chloro-4-methoxyphenyl, 2-tert-butylphenyl, 2-methyl-4-bromophenyl, 1-naphthyl, 4-methoxyphenyl, 1, 4-diphenyl, R, R1And R2Represents H, alkyl or aryl, such as phenyl, 3-thienyl, 4-pentyl, 2-furan, 3-fluorophenyl.
Preferably, the reaction is carried out under the irradiation of visible light, the reaction temperature is 20-30 ℃, and the reaction time is 24-72 h; more preferably, the reaction temperature is 25 ℃ and the reaction time is 48 h.
Preferably, the solvent is a mixed solvent of 1, 2-dichloroethane and tetrahydrofuran, and the volume ratio of the 1, 2-dichloroethane to the tetrahydrofuran is (0.5-1.5): (0.5-1.5); further preferably 1: 1.
Preferably, the molar ratio of the N-aryl substituted glycine to the beta- (2-pyridine) -1, 3-enyne is (1-2) to (0.5-1.5); further preferably 1.5: 1.
Preferably, the molar ratio of the visible photocatalyst DPZ to beta- (2-pyridine) -1, 3-enyne is (0.001-0.01): 1; further preferably 0.005: 1.
Preferably, the mole ratio of the additive sodium dihydrogen phosphate to the beta- (2-pyridine) -1, 3-eneyne is (0.5-1.5) to (0.5-1.5); further preferably 1: 1.
Preferably, the ratio of the volume of the solvent to the amount of the beta- (2-pyridine) -1, 3-enyne material is 30-50mL:1 mmol; more preferably 40mL:1 mmol.
The visible-light-driven photocatalyst DPZ selected by the invention has small relative molecular mass, is easy to synthesize and has high catalytic efficiency.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses DPZ photocatalyst without metal in the reaction, the catalyst consumption is little, the catalytic efficiency is high, and the product conversion rate is high;
2. compared with the existing synthesis method, the synthesis method provided by the invention uses the DPZ photocatalyst without metal, is mild in reaction condition, rapid and efficient, high in yield, green and environment-friendly, and has great popularization and application values.
Drawings
FIG. 1 is a hydrogen spectrum of the product of example 1;
FIG. 2 is a carbon spectrum of the product of example 1;
FIG. 3 is a high resolution mass spectrum of the product of example 1;
FIG. 4 is a hydrogen spectrum of the product of example 2;
FIG. 5 is a carbon spectrum of the product of example 2;
FIG. 6 is a high resolution mass spectrum of the product of example 2.
Detailed Description
The invention is further illustrated, but not limited, by the following examples and the accompanying drawings.
The visible-light-emitting catalyst DPZ in the examples can be found in the literature (Yu Zhao,
Figure BDA0002917320800000032
Chenhao Zhang,
Figure BDA0002917320800000033
kek Foo Chin, Old ˇ rich Pytela, Guo Wei, Hongjun Liu, Filip Bures and Zhiyong Jiang RSC adv.,2014,4, 30062); sodium dihydrogen phosphate was purchased from carbofuran.
Example 1
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000031
the preparation method comprises the following specific steps: 1mg of visible light photocatalyst DPZ dissolved in 200. mu.L of toluene was taken out 35.5. mu.L (0.0005mmol,0.005 eq.) into a 25mL Schlenktube (Schlenktube) and the toluene was blown dry by an air pump; subsequently, 22.7mg (0.15mmol) of N-phenylglycine, 28.1mg (0.10mmol) of 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne, 12mg (0.10mmol) of sodium dihydrogenphosphate were added, followed by 4mL of purified dried solution in a volume ratio of 1:1 tetrahydrofuran and 1, 2-dichloroethane are subjected to vacuum-freezing (freezing at-200 ℃ for 20min) -room temperature (5min) -argon protection for three times in sequence, the reaction bottle is placed in a thermostat at 25 ℃, and is stirred for 48 hours under the irradiation condition of a 3W blue LED lamp; after the reaction is finished, evaporating tetrahydrofuran and 1, 2-dichloroethane by using a rotary evaporator, and directly separating by column chromatography, wherein an eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of gradient concentrations of the n-hexane and the ethyl acetate is 50-5: 1 (specifically, the volume ratio of the n-hexane to the ethyl acetate is 50:1, 40:1, 30:1, 20:1, 10:1 and 5:1 in sequence), so as to obtain 34mg of yellow oily liquid (product), and the yield is 88%.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3) δ 8.63(d, J ═ 4.0Hz,1H),7.48(t, J ═ 6.9Hz,1H), 7.35-7.29 (m,3H),7.23(d, J ═ 4.2Hz,4H),7.18(s,3H), 7.12-7.06 (m,2H),7.02(d, J ═ 6.2Hz,3H),6.90(s,1H), 6.78-6.67 (m,2H),4.24(s,2H) (as shown in fig. 1);13C NMR(75MHz,CDCl3) δ 155.6,149.2,140.1,139.7,135.7,135.4,132.1,128.9,128.2,128.1,128.1,127.9,127.6,126.7,125.7,125.6,125.5,124.3,121.8,120.8,120.6,30.6 (as shown in fig. 2).
The high resolution data is: HRMS (ESI) M/z 387.1854(M + H)+),calc.for C28H22N2387.1856 (shown in fig. 3).
Example 2
The visible light catalytic synthesis process of N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000041
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) glycine, and otherwise the same as in example 1, N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole was obtained in 38.3mg as a yellow oil in 92% yield.
Characterization data for the synthesized N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3) δ 8.64(dd, J ═ 5.3,1.8Hz,1H),7.49(td, J ═ 7.7,1.8Hz,1H),7.23(d, J ═ 3.9Hz,4H),7.18(dd, J ═ 5.1,3.5Hz,1H), 7.11-7.07 (m,4H),7.05(d, J ═ 7.2Hz,3H),6.85(dd, J ═ 7.1,1.6Hz,3H), 6.77-6.73 (m,2H),4.22(s,2H),3.83(s,3H) (as shown in fig. 4);13C NMR(75MHz,CDCl3) δ 158.9,155.6,149.1,140.2,135.8,135.5,132.6,132.4,128.2,128.1,128.0,127.9,125.7,125.6,125.5,123.9,121.0,120.6,114.0,55.5,30.5 (as shown in fig. 5).
The high resolution data is: HRMS (ESI) M/z 417.1959(M + H)+),calc.for C29H24N2O417.1961 (shown in fig. 6).
Example 3
The visible light catalytic synthesis process of N-p-trifluoro-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000042
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-trifluoromethoxyphenyl) glycine, and the same procedures as in example 1 were repeated to give N- (p-trifluoromethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole 40mg as a yellow oil in a yield of 85%.
Characterization data for the synthesized N-p-trifluoromethoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.64(dd,J＝5.1,1.8Hz,1H),7.50(td,J＝7.7,1.8Hz,1H),7.25–7.21(m,4H),7.20–7.16(m,5H),7.12–7.08(m,2H),7.03(dd,J＝5.8,4.2Hz,3H),6.87(s,1H),6.72(dd,J＝7.1,2.2Hz,2H),4.22(s,2H)；13C NMR(75MHz,CDCl3)δ155.3,149.3,148.2,139.7,138.3,135.8,135.1,132.2,128.3,128.2,128.1,128.1,128.0,125.8,125.7,124.7,121.4,120.8,120.6,30.7。
the high resolution data is: HRMS (ESI) M/z 471.1676(M + H)+),calc.for C29H21F3N2O 471.1679。
Example 4
The visible light catalytic synthesis process of N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000051
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (3, 4-dimethoxyphenyl) glycine in the same manner as in example 1 to give N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole 42.8mg as a yellow oil in a yield of 96%.
Characterization data for the synthesized N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.66–8.61(m,1H),7.49(td,J＝7.8,1.9Hz,1H),7.25–7.21(m,4H),7.20–7.15(m,1H),7.14–7.04(m,5H),6.93(s,1H),6.89–6.82(m,2H),6.43(t,J＝2.3Hz,1H),6.34(d,J＝2.3Hz,2H),4.26(s,2H),3.63(s,6H)；13C NMR(75MHz,CDCl3)δ160.7,155.5,149.3,141.3,140.5,135.7,135.3,131.6,128.2,128.1,128.0,125.6,125.6,125.5,124.2,120.6,104.8,100.5,55.3,30.7。
the high resolution data is: HRMS (ESI) M/z 447.2062(M + H)+),calc.for C30H26N2O2447.2067。
Example 5
The visible light catalytic synthesis process of N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000052
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (2-chloro-4-methoxyphenyl) glycine, and the same procedures as in example 1 were repeated to give 37.4mg of N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in 83% yield.
Characterization data for the synthesized N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.66(dd,J＝5.4,1.6Hz,1H),7.52(td,J＝7.7,1.6Hz,1H),7.23(d,J＝4.1Hz,4H),7.20–7.16(m,1H),7.15–7.10(m,2H),7.06–6.99(m,4H),6.96(d,J＝2.8Hz,1H),6.77(s,1H),6.76–6.70(m,3H),4.25(d,J＝16.1Hz,1H),4.04(d,J＝15.8Hz,1H),3.82(s,3H)；13C NMR(75MHz,CDCl3)δ159.7,155.6,149.3,139.6,135.6,135.4,133.4,133.00,130.6,129.9,128.3,128.1,127.8,125.7,125.6,125.5,124.0,120.9,120.5,114.9,112.8,55.7,30.7。
the high resolution data is: HRMS (ESI) M/z 447.2062(M + H)+),calc.for C30H26N2O2447.2067。
Example 6
The visible light catalytic synthesis process of N- (2-tert-butyl phenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000061
the preparation method comprises the following specific steps: in this example, the same procedures used in example 1 were repeated except for replacing N-phenylglycine used in example 1 with N- (2-tert-butylphenyl) glycine to give 38mg of N- (2-tert-butylphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 86%.
Characterization data for the synthesized N- (2-tert-butylphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.63(d,J＝4.1Hz,1H),7.58(dd,J＝8.1,1.2Hz,1H),7.48(td,J＝7.7,1.8Hz,1H),7.37–7.31(m,1H),7.23(t,J＝6.6Hz,4H),7.20–7.15(m,1H),7.09(dd,J＝11.3,5.1Hz,2H),7.03(dd,J＝7.1,3.3Hz,4H),6.85(s,1H),6.80–6.70(m,3H),4.43(d,J＝15.7Hz,1H),3.71(d,J＝15.8Hz,1H),1.22(s,9H)；13C NMR(75MHz,CDCl3)δ147.3,139.7,138.9,136.8,135.6,132.00,128.7,128.7,128.5,128.3,128.1,127.8,125.9,125.8,125.5,123.4,122.2,120.4,36.0,31.7,31.3。
the high resolution data is: HRMS (ESI) M/z 443.2479(M + H)+),calc.for C32H30N2443.2482。
Example 7
The visible light catalyzed process of synthesizing N- (2-methyl-4 bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000071
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (2-methyl-4-bromophenyl) glycine, and the procedure was otherwise as in example 1 to give 40.6mg of N- (2-methyl-4-bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a brown solid, melting point 82-83 ℃ and yield 85%.
Characterization data for the synthesized N- (2-methyl-4-bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.68(d,J＝4.2Hz,1H),7.53(td,J＝7.8,1.8Hz,1H),7.34(s,1H),7.31(dd,J＝8.1,2.1Hz,1H),7.26–7.21(m,4H),7.19(dd,J＝6.1,2.4Hz,1H),7.15(d,J＝3.2Hz,1H),7.13(s,1H),7.06–7.00(m,3H),6.96(d,J＝8.2Hz,1H),6.73–6.63(m,3H),4.08(s,2H),1.79(s,3H)；13C NMR(75MHz,CDCl3)δ155.3,149.1,139.4,138.8,137.5,135.9,135.3,133.5,132.7,130.0,129.5,129.3,128.4,128.3,128.2,127.9,125.8,125.7,125.7,124.3,122.2,120.7,120.2,116.3,30.7,17.1。
the high resolution data is: HRMS (ESI) M/z 479.1115(M + H)+),calc.for C29H23BrN2479.1117。
Example 8
The visible light catalytic synthesis process of N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000072
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (1-naphthyl) glycine, and the same procedures as in example 1 were repeated to give 34.4mg of N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 79%.
Characterization data for the synthesized N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.68(d,J＝4.8Hz,1H),7.87(d,J＝7.8Hz,2H),7.55(td,J＝8.0,1.3Hz,1H),7.48(dd,J＝7.7,5.7Hz,2H),7.42(d,J＝4.7Hz,1H),7.37(d,J＝8.1Hz,1H),7.26–7.23(m,4H),7.22(s,1H),7.18(d,J＝7.7Hz,2H),7.13(d,J＝7.6Hz,1H),6.94(s,1H),6.88–6.83(m,3H),6.53(dd,J＝6.1,2.5Hz,2H),4.30(d,J＝16.0Hz,1H),3.85(d,J＝15.9Hz,1H)；13C NMR(75MHz,CDCl3)δ155.63,149.18,139.81,135.99,135.43,133.85,131.05,128.72,128.29,128.18,128.12,127.73,127.61,127.09,126.45,125.84,125.62,125.33,124.87,124.04,123.44,121.79,120.63,77.42,77.00,76.58,30.82。
the high resolution data is: HRMS (ESI) M/z 437.2011(M + H)+),calc.for C32H24N2437.2012。
Example 9
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000081
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) alanine, and the same procedures as in example 1 were repeated to give 32.7mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 76%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.55(d,J＝4.9Hz,1H),7.40–7.34(m,1H),7.24–7.20(m,2H),7.16(d,J＝2.9Hz,2H),7.14(s,1H),6.99(dd,J＝4.9,2.1Hz,4H),6.96(s,1H),6.93(d,J＝2.1Hz,1H),6.89(d,J＝7.9Hz,1H),6.84–6.80(m,2H),6.68–6.63(m,2H),4.15(s,2H),3.80(s,3H),1.96(s,3H)；13C NMR(75MHz,CDCl3)δ159.1,155.7,148.6,140.5,136.2,135.7,131.2,131.0,130.3,129.8,128.3,127.9,127.7,127.1,125.4,125.3,125.3,120.4,120.1,114.0,55.4,30.9,11.5。
the high resolution data is: HRMS (ESI) M/z 431.2110(M + H)+),calc.for C30H26N2O 431.2118。
Example 10
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000082
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) butynoic acid, and the same procedures as in example 1 were repeated to give 36mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 81%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.61(d,J＝4.9Hz,1H),7.42(dd,J＝7.7,6.0Hz,1H),7.36(dd,J＝7.2,4.6Hz,1H),7.32–7.30(m,1H),7.29(s,1H),7.28–7.22(m,3H),7.08(s,1H),7.05(dd,J＝4.8,2.0Hz,3H),7.02(s,1H),6.93(d,J＝8.0Hz,1H),6.91–6.85(m,2H),6.73(dd,J＝7.1,2.2Hz,2H),4.21(s,2H),3.89(s,3H),2.47(q,J＝7.4Hz,2H),0.84(t,J＝7.4Hz,3H)；13C NMR(75MHz,CDCl3)δ159.1,156.0,148.9,140.6,136.5,135.4,133.2,131.7,131.1,130.9,130.4,130.2,128.3,127.9,127.7,125.4,125.3,125.2,120.3,119.9,113.8,55.4,30.8,18.1,15.1。
the high resolution data is: HRMS (ESI) M/z 445.2267(M + H)+),calc.for C31H28N2O 445.2274。
Example 11
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole has the following reaction formula:
Figure BDA0002917320800000091
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -DL- β -homophenylalanine, and the same procedures as in example 1 were repeated to give 41.5mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole as a yellow oil in a yield of 82%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.59(d,J＝4.1Hz,1H),7.41(dd,J＝7.6,6.4Hz,1H),7.24(d,J＝4.3Hz,4H),7.19(dd,J＝8.8,4.9Hz,2H),7.02(dd,J＝4.5,2.8Hz,6H),6.99(d,J＝1.7Hz,2H),6.92(d,J＝8.0Hz,1H),6.71–6.67(m,2H),6.64(d,J＝3.3Hz,4H),4.18(s,2H),3.81(s,2H),3.76(s,3H)；13C NMR(75MHz,CDCl3)δ158.9,140.4,140.2,136.0,130.5,130.4,130.0,129.6,128.2,128.1,128.1,127.8,127.7,125.7,125.5,125.4,125.3,122.3,120.1,113.5,55.4,30.9。
the high resolution data is: HRMS (ESI) M/z 507.2424(M + H)+),calc.for C36H30N2O 507.2431。
Example 12
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenyl pyrrole has the following reaction formula:
Figure BDA0002917320800000101
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -phenylacetic acid, and the same procedures as in example 1 were repeated to give 38.4mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenylpyrrole as a yellow oil in 78% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenylpyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.61(d,J＝4.9Hz,1H),7.42(td,J＝7.7,1.8Hz,1H),7.12–7.06(m,6H),7.02(dd,J＝6.8,4.1Hz,6H),6.94(dd,J＝11.6,5.8Hz,3H),6.88–6.82(m,4H),6.68–6.65(m,2H),4.21(s,2H),3.74(s,3H)；13C NMR(75MHz,CDCl3)δ158.7,155.8,149.1,140.5,135.6,135.5,132.3,131.9,131.2,130.8,130.3,128.3,127.9,127.6,127.4,126.2,125.7,125.5,125.3,122.1,120.4,116.4,114.8,113.4,55.3,30.8。
the high resolution data is: HRMS (ESI) M/z 493.2261(M + H)+),calc.for C35H28N2O 493.2274。
Example 13
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole has the following reaction formula:
Figure BDA0002917320800000102
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -4-fluorophenylacetic acid, and the same procedures as in example 1 were repeated to give 40.3mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole as a yellow oil in 79% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.61(d,J＝4.4Hz,1H),7.44(t,J＝7.0Hz,1H),7.08(dd,J＝8.9,4.4Hz,7H),7.01(dd,J＝6.8,2.6Hz,2H),6.96(d,J＝7.9Hz,1H),6.89(d,J＝2.9Hz,1H),6.84(dd,J＝10.6,4.4Hz,5H),6.75–6.66(m,4H),4.21(s,2H),3.76(s,3H)；13C NMR(75MHz,CDCl3)δ163.0,159.7,158.8,140.3,135.8,135.3,132.8,132.7,130.9,130.7,130.3,128.3,127.9,127.7,125.8,125.5,122.2,120.5,114.7,114.4,113.5,55.3,30.8。
the high resolution data is: HRMS (ESI) M/z 511.2172(M + H)+),calc.for C35H27FN2O 511.2180。
Example 14
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole has the following reaction formula:
Figure BDA0002917320800000111
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -3-chlorophenylacetic acid, and the same procedures as in example 1 were repeated to give 43.1mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole as a yellow oil in 82% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.61(dd,J＝4.9,0.8Hz,1H),7.44(td,J＝7.8,1.6Hz,1H),7.11(dd,J＝5.1,3.1Hz,4H),7.07(s,2H),7.05–7.00(m,3H),7.00–6.97(m,1H),6.95(s,1H),6.93–6.90(m,2H),6.85(dd,J＝5.4,3.4Hz,4H),6.79(dd,J＝7.5,1.4Hz,1H),6.70(d,J＝8.9Hz,2H),4.22(s,2H),3.76(s,3H)；13C NMR(75MHz,CDCl3)δ158.9,140.2,135.0,134.1,133.2,131.0,130.7,130.7,130.4,130.2,129.3,128.7,128.3,127.9,127.8,126.5,125.8,125.8,125.6,122.8,120.6,113.6,55.4,30.8。
the high resolution data is: HRMS (ESI) M/z 527.1876(M + H)+),calc.for C35H27ClN2O 527.1885。
Example 15
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole has the following reaction formula:
Figure BDA0002917320800000121
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -4-methoxyphenylacetic acid, and the same procedures as in example 1 were repeated to give 45.9mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole as a yellow oil in 88% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.61(d,J＝4.9Hz,1H),7.45–7.39(m,1H),7.11–7.06(m,6H),7.05–7.02(m,3H),6.96(d,J＝7.9Hz,1H),6.85(dd,J＝8.7,3.7Hz,6H),6.67(d,J＝8.9Hz,2H),6.56(d,J＝8.8Hz,2H),4.21(s,2H),3.75(s,3H),3.67(s,3H)；13C NMR(75MHz,CDCl3)δ158.6,157.9,155.8,148.9,140.5,135.7,135.6,132.3,132.0,131.7,131.2,130.8,130.3,128.3,127.9,127.6,125.7,125.4,125.2,124.7,121.6,120.3,113.4,112.9,55.3,54.9,30.8。
the high resolution data is: HRMS (ESI) M/z 523.2366(M + H)+),calc.for C36H30N2O2523.2380。
Example 16
The visible light catalytic synthesis process of 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thiophen methylene) pyrrole has the following reaction formula:
Figure BDA0002917320800000122
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1-phenyl-4- (3-thiophene) -1, 3-enyne, and the same procedure as in example 1 was repeated except for obtaining 31mg of 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thienylmethylene) pyrrole as a yellow oil in a yield of 79%.
Characterization data for the synthesized 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thienylmethylene) pyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.66(d,J＝4.2Hz,1H),7.50(td,J＝7.7,1.7Hz,1H),7.38(t,J＝5.9Hz,3H),7.25(s,2H),7.24–7.21(m,4H),7.19–7.15(m,1H),7.10(dd,J＝11.3,6.4Hz,2H),7.01(dd,J＝4.9,3.0Hz,1H),6.89(s,1H),6.46(dd,J＝20.2,3.3Hz,2H),4.21(s,2H)；13C NMR(75MHz,CDCl3)δ155.5,149.1,140.3,139.7,135.8,135.3,132.0,129.00,128.3,128.2,128.00,127.7,126.7,125.7,124.7,124.3,120.7,120.7,120.6,25.6。
the high resolution data is: HRMS (ESI) M/z 393.1414(M + H)+),calc.for C26H20N2S 393.1420。
Example 17
A method for synthesizing 1, 4-diphenyl-3- (2-pyridyl) -2-hexyl pyrrole under visible light catalysis has the following reaction formula:
Figure BDA0002917320800000131
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1-phenyl-4-pentyl-1, 3-enyne, and the same procedure as in example 1 was repeated except for using 34.2mg of 1, 4-diphenyl-3- (2-pyridyl) -2-hexylpyrrole as a yellow oil in a yield of 90%.
Characterization data for the synthesized 1, 4-diphenyl-3- (2-pyridyl) -2-hexylpyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.64(d,J＝4.1Hz,1H),7.53–7.47(m,1H),7.23(s,1H),7.21(d,J＝2.6Hz,3H),7.19–7.17(m,1H),7.15(s,1H),7.12(s,1H),7.08(dd,J＝6.3,2.6Hz,2H),7.02(dd,J＝4.9,3.0Hz,1H),6.89(d,J＝8.9Hz,2H),6.83(s,1H),6.51(dd,J＝4.9,1.0Hz,1H),6.45(d,J＝1.8Hz,1H),4.16(s,2H),3.85(s,3H)；13C NMR(75MHz,CDCl3)δ159.0,155.8,149.4,140.5,135.6,135.5,132.6,132.2,128.2,128.1,128.1,128.0,125.6,125.5,124.7,123.9,120.9,120.7,120.5,114.8,114.0,55.5,26.0。
the high resolution data is: HRMS (ESI) M/z 423.1523(M + H)+),calc.for C27H22N2OS 423.1526。
Example 18
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thiophen methylene) -4- (2-furan) pyrrole has the following reaction formula:
Figure BDA0002917320800000132
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (p-methoxyphenyl) glycine, and 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne was replaced with 2- (2-pyridine) -1- (2-furan) -4- (3-thiophene) -1, 3-enyne, and otherwise the same as in example 1 was conducted to obtain 28mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thienylmethylene) -4- (2-furan) pyrrole as a black solid, a melting point of 127.0 to 129.0 ℃ and a yield of 83%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thienylmethylene) -4- (2-furan) pyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.68(d,J＝5.0Hz,1H),7.66(td,J＝7.7,1.6Hz,1H),7.35(d,J＝7.9Hz,1H),7.28(d,J＝1.1Hz,1H),7.19(s,1H),7.11(d,J＝8.8Hz,2H),7.04(s,1H),7.04–7.01(m,1H),6.88(t,J＝5.9Hz,2H),6.54(d,J＝4.8Hz,1H),6.49(s,1H),6.28(dd,J＝3.2,1.9Hz,1H),5.90(d,J＝3.2Hz,1H),4.04(s,2H),3.83(s,3H)；13C NMR(75MHz,CDCl3)δ159.1,150.0,140.1,132.3,128.0,127.9,125.4,124.9,121.2,120.9,120.4,114.3,114.1,110.8,104.6,55.5,25.6。
the high resolution data is: HRMS (ESI) M/z 413.1315(M + H)+),calc.for C25H20N2O2S 413.1318。
Example 19
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole has the following reaction formula:
Figure BDA0002917320800000141
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1- (3-fluorophenyl) -4-phenyl-1, 3-enyne, and the same procedure as in example 1 was repeated except for using 30.3mg of N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole as a yellow oily liquid in a yield of 75%.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole are as follows:
the nuclear magnetic data are:1H NMR(300MHz,CDCl3)δ8.66(dd,J＝5.2,1.9Hz,1H),7.53(td,J＝7.7,1.8Hz,1H),7.36–7.33(m,3H),7.21–7.16(m,3H),7.14–7.11(m,2H),7.03(dd,J＝5.9,4.5Hz,3H),6.99(d,J＝7.8Hz,1H),6.95–6.90(m,2H),6.85(dd,J＝8.4,6.1Hz,1H),6.72(dd,J＝7.2,2.0Hz,2H),4.21(s,2H)；13C NMR(75MHz,CDCl3)δ164.4,161.1,155.2,149.4,139.9,139.5,137.8,137.6,135.9,132.2,129.5,129.4,129.00,128.1,127.9,127.7,126.7,125.6,123.8,123.8,123.2,123.2,121.0,120.9,114.9,114.6,112.5,112.2,30.5。
the high resolution data is: HRMS (ESI) M/z 405.1756(M + H)+),calc.for C28H21FN2405.1762。
Example 20
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole has the following reaction formula:
Figure BDA0002917320800000151
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1- (2-thiophene) -4-pentyl-1, 3-enyne, and the other procedures were repeated in the same manner as in example 1 to obtain 31.3mg of N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole as a yellow oil in a yield of 81%.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole are as follows:
the nuclear magnetic data are:1HNMR(300MHz,CDCl3)δ8.69(d,J＝4.1Hz,1H),7.61(td,J＝7.7,1.8Hz,1H),7.49(dd,J＝7.3,1.5Hz,1H),7.45(s,1H),7.43–7.37(m,3H),7.28–7.24(m,1H),7.20–7.15(m,1H),7.06(dd,J＝5.1,1.0Hz,1H),6.92(s,1H),6.88(dd,J＝5.1,3.6Hz,1H),6.67(dd,J＝3.5,0.9Hz,1H),2.79–2.71(m,2H),1.19–1.12(m,2H),1.05(dd,J＝13.3,6.6Hz,2H),0.99–0.92(m,4H),0.72(t,J＝7.0Hz,3H)；13C NMR(75MHz,CDCl3)δ155.3,148.9,139.8,137.6,135.9,134.4,129.2,127.7,127.1,126.5,125.8,123.9,122.8,120.9,120.3,117.2,31.0,29.4,28.6,24.4,22.3,13.9。
the high resolution data is: HRMS (ESI) M/z 387.1883(M + H)+),calc.for C25H26N2S 387.1889。

Claims (7)

1. A method for synthesizing 3- (2-pyridine) substituted pyrrole compounds by visible light catalysis is characterized in that N-aryl substituted glycine shown in a formula I, beta- (2-pyridine) -1, 3-eneyne shown in a formula II, a visible light catalyst DPZ and additive sodium dihydrogen phosphate are uniformly mixed in a solvent under the protection of inert gas, and the substituted pyrrole compounds shown in a formula III are obtained after separation and purification after reaction under the irradiation of visible light;
Figure FDA0002917320790000011
in the formulae I, II and III, Ar represents aryl R, R1And R2Represents H, alkyl or aryl.
2. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the reaction temperature is 20-30 ℃ and the reaction time is 24-72 h.
3. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the solvent is a mixed solvent of 1, 2-dichloroethane and tetrahydrofuran, and the volume ratio of 1, 2-dichloroethane to tetrahydrofuran is (0.5-1.5): (0.5-1.5).
4. The process for the visible-light catalytic synthesis of 3- (2-pyridine) substituted pyrroles according to claim 1, wherein the molar ratio of the N-aryl substituted glycine to the β - (2-pyridine) -1, 3-enyne is (1-2) to (0.5-1.5).
5. The method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis according to claim 1, wherein the molar ratio of the visible light catalyst DPZ to the beta- (2-pyridine) -1, 3-eneyne is (0.001-0.01): 1.
6. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compound according to claim 1, wherein the molar ratio of the additive sodium dihydrogen phosphate to the beta- (2-pyridine) -1, 3-eneyne is (0.5-1.5): (0.5-1.5).
7. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the ratio of the volume of the solvent to the amount of beta- (2-pyridine) -1, 3-enyne substances is 30-50mL:1 mmol.
CN202110104563.5A 2021-01-26 2021-01-26 Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis Active CN112812097B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110104563.5A CN112812097B (en) 2021-01-26 2021-01-26 Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110104563.5A CN112812097B (en) 2021-01-26 2021-01-26 Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis

Publications (2)

Publication Number Publication Date
CN112812097A true CN112812097A (en) 2021-05-18
CN112812097B CN112812097B (en) 2023-01-13

Family

ID=75859291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110104563.5A Active CN112812097B (en) 2021-01-26 2021-01-26 Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis

Country Status (1)

Country Link
CN (1) CN112812097B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429407A (en) * 2021-06-28 2021-09-24 河南师范大学 Simple synthesis method of 1-alkyl-3-aryl substituted indolizine compound
CN114874119A (en) * 2022-03-06 2022-08-09 昆明学院 Method for photocatalytic synthesis of 3, 4-dialkyl-4-pyrroline-2-one derivative

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016082583A1 (en) * 2014-11-28 2016-06-02 浙江九洲药业股份有限公司 Kinetic resolution of asymmetric catalytic hydrogenation of racemic δ-hydroxy ester and application thereof
WO2016184160A1 (en) * 2015-05-15 2016-11-24 浙江九洲药业股份有限公司 Chiral spiro phosphorus-nitrogen-sulphur tridentate ligand, and preparation method and application thereof
CN108017579A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound
CN108017580A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible light catalytic amino acid decarboxylase synthesis 1,2,3,4- Tetrahydroquinolinesas
CN109369496A (en) * 2018-11-26 2019-02-22 河南师范大学 A kind of synthetic method of 3- aryl substituted pyrroles class compound
CN109369497A (en) * 2018-11-26 2019-02-22 河南师范大学 A kind of synthetic method of N- pyrrole radicals piperidines
CN109485594A (en) * 2018-11-26 2019-03-19 河南师范大学 A kind of synthetic method of 3- alkynyl azoles
CN110194735A (en) * 2018-02-27 2019-09-03 河南大学 A kind of chirality 3-(2- pyridine) -3- aryl substitutional amine-group compound visible light asymmetry catalysis synthetic method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016082583A1 (en) * 2014-11-28 2016-06-02 浙江九洲药业股份有限公司 Kinetic resolution of asymmetric catalytic hydrogenation of racemic δ-hydroxy ester and application thereof
WO2016184160A1 (en) * 2015-05-15 2016-11-24 浙江九洲药业股份有限公司 Chiral spiro phosphorus-nitrogen-sulphur tridentate ligand, and preparation method and application thereof
CN108017579A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound
CN108017580A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible light catalytic amino acid decarboxylase synthesis 1,2,3,4- Tetrahydroquinolinesas
CN110194735A (en) * 2018-02-27 2019-09-03 河南大学 A kind of chirality 3-(2- pyridine) -3- aryl substitutional amine-group compound visible light asymmetry catalysis synthetic method
CN109369496A (en) * 2018-11-26 2019-02-22 河南师范大学 A kind of synthetic method of 3- aryl substituted pyrroles class compound
CN109369497A (en) * 2018-11-26 2019-02-22 河南师范大学 A kind of synthetic method of N- pyrrole radicals piperidines
CN109485594A (en) * 2018-11-26 2019-03-19 河南师范大学 A kind of synthetic method of 3- alkynyl azoles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BARTOLO GABRIELE ET AL.: "General and Regioselective Synthesis of Substituted Pyrroles by Metal-Catalyzed or Spontaneous Cycloisomerization of (Z)-(2-En-4-ynyl)amines", 《JOURNAL OF ORGANIC CHEMISTRY 》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429407A (en) * 2021-06-28 2021-09-24 河南师范大学 Simple synthesis method of 1-alkyl-3-aryl substituted indolizine compound
CN114874119A (en) * 2022-03-06 2022-08-09 昆明学院 Method for photocatalytic synthesis of 3, 4-dialkyl-4-pyrroline-2-one derivative
CN114874119B (en) * 2022-03-06 2023-06-06 昆明学院 Method for synthesizing 3, 4-dialkylated-4-pyrroline-2-one derivative by photocatalysis

Also Published As

Publication number Publication date
CN112812097B (en) 2023-01-13

Similar Documents

Publication Publication Date Title
CN112812097B (en) Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis
Karpov et al. A diversity oriented four-component approach to tetrahydro-β-carbolines initiated by Sonogashira coupling
CN108947945B (en) 1, 3-dihydroisobenzofuran derivative and synthetic method and application thereof
Cherry et al. Regioselective synthesis of 5-alkylidene and 5-(iodoalkylidene)-pyrrol-2 (5H)-ones by halolactamisation of (2Z, 4E)-dienamides and (Z)-alk-2-en-4-ynamides
CN111517964B (en) Method for splitting chiral compound
Bouet et al. Preparation of new axially chiral bridged 2, 2′-bipyridines and pyridyl monooxazolines (pymox). Evaluation in copper (i)-catalyzed enantioselective cyclopropanation
CN110156800B (en) Synthesis method of pyrano [3,2-b ] indole-2-ketone compound
Groenendaal et al. Oligoheterocycles by the Stille-coupling reaction
CN110590644A (en) Chiral 1, 2-dihydropyridine compounds and preparation method and application thereof
CN105820174A (en) Polysubstituted thienoindole derivative and preparation method thereof
CN112939903B (en) Method for preparing furan compounds from bromoaryl ketone
CN109503387B (en) Method for catalyzing asymmetric synthesis of binaphthyl diamine
Kündig et al. Synthesis of [6, n] cis-fused ring compounds via Cr-mediated dearomatisation–ring-closing metathesis
Loim et al. Regio-and Enantioselective Synthesis of Planarly Chiral Cyclopentadienylmanganese Tricarbonyl Complexes via 2-Cymantrenyl-1, 3-dioxolanes
CN113200905A (en) Chiral indolone derivative and synthesis method thereof
CN112341444B (en) 3- (2, 3-dihydropyrrole) indole compound and preparation method thereof
CN114075150A (en) Method for preparing chiral amino alcohol derivative through nonmetal-catalyzed asymmetric carbon-hydrogen bond amination
CN111499542A (en) Preparation method of cycloenone compound containing α -cyano substituted quaternary carbon center
CN109180406B (en) Synthesis method of (4R, 5R) -5-benzyl-4-hydroxy-2-cyclopentene-1-ketone compound
CN112430212B (en) Method for synthesizing asymmetric N-diarylmethyl substituted heterocyclic compound catalyzed by recyclable bismuth complex
CN115477575B (en) Synthesis method of diaryl ketone
CN114181182B (en) Synthesis method of polysubstituted 4H-pyran compound
CN113636972B (en) Polysubstituted benzene compound and synthesis method thereof
CN115353514B (en) Fluoro-pyridopyrimidinone compounds and synthesis method thereof
CN111732541B (en) Method for efficiently synthesizing 6-alkenyl phenanthridine derivative through ruthenium-catalyzed C-H activation/cyclization reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant