Method for synthesizing pyrrole by photocatalysis of N-arylglycine and 1, 3-eneyne

Abstract

The invention discloses a method for synthesizing functional pyrrole through photocatalysis of N-arylglycine and 1, 3-eneyne. According to the method, N-arylglycine is decarboxylated through photocatalysis to form an alpha-amino alkyl free radical, and the free radical and 1, 3-eneyne are subjected to free radical addition, cyclization and oxidative aromatization reaction to construct polysubstituted pyrrole. Pyrrole serves as a heterocyclic compound with great importance, widely exists in numerous drug compounds and bioactive molecules, shows electronic characteristics with great prospects in organic photovoltaic devices (OPVs) and organic field effect transistors (OFETs), is also a key structural unit in synthesis of pesticides, natural products and dyes, and has a broad application prospect. Powerful support is provided for multi-industry development, and the application prospect is wide. The polysubstituted pyrrole compound is synthesized through a one-pot method, and a new method is provided for preparing the novel polysubstituted pyrrole compound.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne. Background Technology

[0002] In recent years, visible light photocatalysis has emerged as a robust and rapidly developing methodology in the field of organic transformation, aligning closely with contemporary principles of sustainable green chemistry. 1 Significant progress has been made in the field of photochemistry, with numerous green and sustainable free radical transformation reactions enabling the efficient synthesis of high-value molecules. 2 .

[0003] Pyrrole, as a highly important heterocyclic compound, is widely found in numerous pharmaceutical compounds and bioactive molecules. 3 It is also a key structural unit in the synthesis of pesticides, natural products, and dyes. 4 Many compounds containing pyrrole have been widely used in drug development, such as sunitinib. 3 Isamoltane 3 Lamelarin 3 Pyrvinium 3 wait.

[0004] As an abundant non-fossil carbon source, α-amino acids have been widely used in visible light-driven photo-oxidation-reduction catalysis systems. 5 The synthesis of high-value molecules via photocatalytic α-amino acid decarboxylation has fundamental advantages: its redox neutrality, mild reaction conditions, and the fact that only carbon dioxide is produced as a byproduct. 6 . In recent years, a large number of publications have reported on the photocatalytic decarboxylation of N-arylglycine, as listed below:

[0005] Rueping Research Group 7 This paper reports for the first time a mild method for the decarboxylation and aminomethylation of aryl sulfonates via photo-oxidation-reduction of CO bond cleavage and nickel catalysis.

[0006] Zeng Xiaofei's research group 8 A visible-light photocatalytic decarboxylation reaction of aryl amino acids and aldehydes was achieved at room temperature using water as a solvent, which can be used to synthesize various 1,2-amino alcohols.

[0007] Zhou Lei and others 9A metal-free, visible light-induced decarboxylation cyclization reaction of α-arylglycine and diazo compounds is reported to synthesize monosubstituted azacyclopropanes.

[0008] Yang Jingya's research group 10 A visible light-promoted decarboxylation and cyclization reaction of arylglycine and azobenzene was reported, yielding the product 1,2,4-triaryltriazolidine.

[0009] Yuan and his research team 11 A photocatalytic intermolecular 1,4-hydroxyaminoalkylation reaction involving N-arylglycine is reported for the construction of a bridging benzozazaporide skeleton.

[0010] In summary, visible light is a renewable resource with advantages such as being green, clean, abundant, and readily available. Its catalytic reaction conditions are mild, and it exhibits good chemoselectivity and functional group compatibility. Meanwhile, α-amino acids, as readily available, stable, inexpensive, and renewable carbon sources, are used to construct C-C bonds and carbon-heteroatom bonds. As a nitrogen source, amino acids can selectively remove the carboxyl group from the α-carbon under extremely mild conditions, generating α-aminoalkyl radicals, which can further initiate radical addition or coupling reactions. This reaction has broad substrate applicability and good functional group tolerance, and can serve as a starting material for the preparation of various nitrogen-containing compounds. Summary of the Invention

[0011] The technical problem to be solved by this invention is to use N-arylglycine, which is stable, has low toxicity and is not sensitive to air, as a carbon and nitrogen source, to decarboxylate under light conditions to form α-aminoalkyl free radicals, and to conduct free radical addition, [3+2] cyclization and oxidative aromatization reactions with 1,3-enyne to construct multi-substituted pyrrole compounds.

[0012] To solve the above-mentioned technical problems, the technical solution adopted in this invention is as follows: using N-arylglycine and 1,3-enyne compounds as substrates, a multi-substituted pyrrole compound is prepared. The process includes the following steps: adding a compound having general formula I, a compound having general formula II, a photocatalyst, a base, an additive, and a solvent to a pressure-resistant tube; reacting at 18-25℃ for 8 h; monitoring the reaction progress by thin-layer chromatography until the reaction is complete; extracting with ethyl acetate and saturated brine; drying with anhydrous sodium sulfate; distilling off the solvent under reduced pressure; and purifying the residue by silica gel column chromatography using petroleum ether / ethyl acetate as the mobile phase to obtain compound III. The reaction equation is as follows: In the equation: R1 is hydrogen atom, methyl, ethyl, tert-butyl, fluorine atom, methoxy; R2 is hydrogen atom, methyl, ethyl, fluorine atom, bromine atom, trifluoromethyl, methoxy; R3 is hydrogen atom, methyl, ethyl.

[0013] The above-described photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the molar ratio of compound A, compound B, and catalyst is 2.0~3.0 : 1 : 0.04.

[0014] The above-mentioned photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the reaction illumination wavelength is blue light (455-465 nm).

[0015] The above-described photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the reaction temperature is 18-25℃.

[0016] The above-mentioned photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that: the photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, 2,4,6-tris(diphenylamino)-3,5-difluorobenzylonitrile, or 10-phenylphenthiazide.

[0017] The above-described photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the base is dipotassium hydrogen phosphate, 2,6-dimethylpyridine, or potassium carbonate.

[0018] The above-described photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the additive is elemental iodine.

[0019] The above-described photocatalytic method for synthesizing pyrrole from N-arylglycine and 1,3-enyne is characterized in that the solvent is dimethyl sulfoxide, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0020] Compared with the prior art, the present invention has the following advantages: The present invention innovatively proposes a method for preparing multi-substituted pyrrole compounds using N-arylglycine and 1,3-enyne compounds as substrates. The substrates used are inexpensive and readily available, the operation is simple, the substrate compatibility is good, the yield is high, and it has the potential for industrial production. Detailed Implementation

[0021] The technical solution of the present invention will be further described in detail below through embodiments. Specific implementation methods are as follows:

[0022] Example 1: The preparation method of this example includes the following steps:

[0023] Compound Ia (10 mmol, 1.52 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIa in 79% yield. The reaction equation is as follows:

[0024] Example 2: The preparation method of this example includes the following steps:

[0025] Compound Ib (10 mmol, 1.65 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIb in 82% yield. The reaction equation is as follows:

[0026] Example 3: The preparation method of this example includes the following steps:

[0027] Compound Ic (10 mmol, 1.69 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIc in 70% yield. The reaction equation is as follows:

[0028] Example 4: The preparation method of this example includes the following steps:

[0029] Compound Id (10 mmol, 2.07 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIId in 77% yield. The reaction equation is as follows:

[0030] Example 5: The preparation method of this example includes the following steps:

[0031] Compound Ie (10 mmol, 1.79 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIe in 75% yield. The reaction equation is as follows:

[0032] Example 6: The preparation method of this example includes the following steps:

[0033] Compound Ie (10 mmol, 1.81 mg), compound IIa (5 mmol, 1.02 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIf in 76% yield. The reaction equation is as follows:

[0034] Example 7: The preparation method of this example includes the following steps:

[0035] Compound Ia (10 mmol, 1.52 mg), compound IIb (5 mmol, 1.09 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound III g in 75% yield. The reaction equation is as follows:

[0036] Example 8: The preparation method of this example includes the following steps:

[0037] Compound Ia (10 mmol, 1.52 mg), compound IIc (5 mmol, 1.17 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIh in 75% yield. The reaction equation is as follows:

[0038] Example 9: The preparation method of this example includes the following steps:

[0039] Compound Ia (10 mmol, 1.52 mg), compound IId (5 mmol, 1.36 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIi in 75% yield. The reaction equation is as follows:

[0040] Example 10: The preparation method of this example includes the following steps:

[0041] Compound Id (10 mmol, 1.51 mg), compound IIa (5 mmol, 1.41 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIj in 71% yield. The reaction equation is as follows:

[0042] Example 11: The preparation method of this example includes the following steps:

[0043] Compound Id (10 mmol, 1.51 mg), compound IIa (5 mmol, 1.11 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIk in 71% yield. The reaction equation is as follows:

[0044] Example 12: The preparation method of this example includes the following steps:

[0045] Compound Ia (10 mmol, 1.52 mg), compound IIg (5 mmol, 1.16 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIl in 76% yield. The reaction equation is as follows:

[0046] Example 13: The preparation method of this example includes the following steps:

[0047] Compound Ia (10 mmol, 1.52 mg), compound IIh (5 mmol, 1.09 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIm in 78% yield. The reaction equation is as follows:

[0048] Example 14: The preparation method of this example includes the following steps:

[0049] Compound Ia (10 mmol, 1.52 mg), compound IIh (5 mmol, 1.11 mg), 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile (0.2 mmol, 158 mg), potassium dihydrogen phosphate (10 mmol, 1.74 mg), and dimethyl sulfoxide (5 mL) were added to a 20 mL pressure-resistant tube. The reaction was carried out under blue light at room temperature for 8.0 h, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as the mobile phase to give compound IIIn in 78% yield. The reaction equation is as follows:

[0050] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 1 are as follows:

[0051] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.45(d, J = 7.6 Hz, 2 H), 7.34-7.24(m, 5 H), 7.21-7.08(m, 6 H), 6.90-6.84(m, 3 H), 6.51(d, J = 2.8 Hz, 1 H),4.09(s, 2 H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 140.5, 140.2, 136.9, 128.9,128.5, 128.3, 128.0, 127.9, 127.6, 127.3, 126.5, 125.8, 125.6, 124.6, 122.2,108.9, 30.9. HRMS calcd for C 23 H 19 N [M+H] + 310.1591; found: 310.1590.

[0052] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 2 are as follows:

[0053] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.43(d, J = 7.2 Hz, 2 H), 7.31(t, J= 7.6 Hz, 2 H), 7.20-7.15(m, 3 H), 7.09(dd, J = 6.8 Hz, 3 H), 7.00(d, J = 8.4Hz, 2 H), 6.91(d, J = 6.8 Hz, 2 H), 6.82(d, J = 2.8 Hz, 1 H), 6.49(d, J = 2.8Hz, 1 H), 4.07(s, 2 H), 2.33(s, 3 H); 13C NMR (100 MHz, CDCl3, ppm): δ =140.6, 137.6, 137.2, 137.0, 129.4, 128.4, 128.3, 128.0, 127.8, 127.7, 126.3,125.8, 125.5, 124.3, 122.3, 108.6, 30.9, 21.0. HRMS calcd for C 24 H 21 N [M+H] + 324.1747; found: 324.1762.

[0054] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 3 are as follows:

[0055] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.44(d, J = 7.2 Hz, 2 H), 7.32(t, J= 7.6 Hz, 2 H), 7.23-7.20(m, 2 H), 7.16-7.10(m, 2 H), 7.07-7.03(m, 2 H), 6.95(t, J = 8.4 Hz, 2 H), 6.88(d, J = 7.6 Hz, 2 H), 6.79(d, J = 3.2 Hz, 1 H), 6.49(d, J = 3.2 Hz, 1 H), 4.05(s, 2 H); 13 C NMR (100 MHz, CDCl3, ppm): δ =162.9, 160.5, 140.3, 136.8, 136.2, 128.5, 128.4, 128.3, 128.3, 128.0, 127.9,125.9, 125.8, 124.6, 122.3, 115.8, 115.5, 109.0, 30.9. 19 F NMR (400 MHz, CDCl3) δ= -114.29. HRMS calcd for C 23 H 18 FN [M+H] + 328.1496; found: 328.1492.

[0056] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 4 are as follows:

[0057] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.44(d, J = 8.4 Hz, 2 H), 7.33-7.26(m, 4 H), 7.18-7.11(m, 4 H), 7.04(d, J = 8.8 Hz, 2 H), 6.90(d, J = 8.0 Hz, 2H), 6.84(d, J = 2.8 Hz, 1 H), 6.49(d, J = 3.2 Hz, 1 H), 4.08(s, 2 H), 1.30(s,9 H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 150.4, 140.7, 137.5, 137.0, 128.4,128.2, 128.1, 127.8, 127.8, 126.0, 125.7, 125.5, 124.2, 122.2, 108.7, 34.6,31.4. HRMS calcd for C 27 H 27 N [M+H] + 366.2216; found: 366.2216.

[0058] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 5 are as follows:

[0059] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.51(d, J = 6.4 Hz, 2 H), 7.34(t, J= 6.4 Hz, 2 H), 7.27(t, J = 7.6 Hz, 1 H), 7.22-7.20(m, 2 H), 7.08-7.05(m, 4H), 6.96(d, J = 9.6 Hz, 1 H), 6.76(d, J = 5.6 Hz, 2 H), 6.67(s, 1H), 6.47(s,1 H), 4.03-3.81(m, 2 H), 2.22-2.01(m, 2 H), 0.99(t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3, ppm): δ = 142.2, 140.0, 138.3, 137.2, 128.7, 128.6, 128.5,128.5, 128.4, 128.2, 128.0, 127.9, 125.9, 125.7, 125.5, 123.4, 122.3, 108.3,31.0, 23.3, 14.6. HRMS calcd for C 25 H 23 N [M+H] + 338.1903; found: 338.1903.

[0060] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 6 are as follows:

[0061] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.44(d, J = 7.6 Hz, 2 H), 7.31(t, J= 7.6 Hz, 2 H), 7.20-7.10(m, 4 H), 7.01(d, J = 8.4 Hz, 2 H), 6.90(d, J = 7.2Hz, 2 H), 6.77(d, J = 8.4 Hz, 3 H), 6.48(s, 1 H), 4.05(s, 2 H), 3.77(S, 3 H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 158.8, 140.6, 137.1, 133.1, 128.5, 128.3,128.1, 127.8, 127.8, 125.8, 125.6, 124.1, 122.4, 113.9, 108.5, 55.5, 30.9.HRMS calcd for C 24 H 21 NO [M+H] + 340.1696; found: 340.1694.

[0062] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 7 are as follows:

[0063] 1H NMR (400 MHz, CDCl3, ppm): δ = 7.34(d, J = 7.6 Hz, 3 H), 7.26-7.25(m, 3 H), 7.14(d, J = 7.6 Hz, 6 H), 6.89(d, J = 7.6 Hz, 2 H), 6.83(d, J = 2.8Hz, 1H), 6.48(d, J = 2.8Hz, 1H), 4.08(s, 2H), 2.33(s, 3H); 13 C NMR (100MHz, CDCl3, ppm): δ = 140.6, 135.2, 134.0, 129.2, 128.8, 128.2, 128.0, 127.7,127.4, 127.2, 126.5, 125.7, 122.1, 108.9, 30.9, 21.1. HRMS calcd for C 24 H 21 N[M+H] + 324.1747; found: 324.1763.

[0064] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 8 are as follows:

[0065] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.28(d, J = 8.8 Hz, 2 H), 7.20-7.17(m, 3 H), 7.09-7.02(m, 5 H), 6.81(t, J = 6.4 Hz, 4 H), 6.75(d, J = 2.8 Hz, 1H), 6.38(d, J = 2.8 Hz, 1 H), 3.98(s, 2 H), 3.72(s, 3 H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 157.8, 140.6, 140.2, 129.6, 128.9, 128.9, 128.3, 128.0,127.2, 127.2, 126.5, 125.8, 124.2, 122.0, 113.9, 108.9, 55.3, 30.9. HRMScalcd for C 24 H 21 NO [M+H] +340.1696; found: 340.1694.

[0066] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 9 are as follows:

[0067] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.54(d, J = 7.2 Hz, 3 H), , 7.30-7.29(m, 4 H), 7.18-7.12(m, 5 H), 6.88(dd, J = 12.4 Hz, 3 H), 6.53(d, J = 2.8Hz, 1H), 4.08(s, 2H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 140.0, 129.0,128.4, 127.9, 127.7, 126.5, 126.0, 125.4, 122.7, 108.8, 30.9, 29.7, 14.1. 19 FNMR (400 MHz, CDCl3) δ= -62.21. HRMS calcd for C 24 H 18 F3N [M+H] + 378.1464; found: 378.1473.

[0068] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 10 are as follows:

[0069] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.46-7.41(m, 2 H), 7.34-7.25(m, 6H), 7.21-7.11(m, 6 H), 6.90-6.84(m, 3 H), 6.49(dd, J = 15.2 Hz, 1 H), 4.07(d,J = 16.4 Hz, 2 H); 13C NMR (100 MHz, CDCl3, ppm): δ = 139.4, 130.8, 128.6,128.2, 128.1, 127.7, 127.6, 127.5, 127.3, 127.2, 127.1, 126.8, 126.6, 125.8,125.7, 125.2, 125.0, 124.9, 121.7, 121.5, 108.2, 108.0, 30.2, 30.1. HRMScalcd for C 23 H 18 BrN [M+H] + 388.0696; found: 388.0692.

[0070] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 11 are as follows:

[0071] 1 H NMR (400 MHz, CDCl3, ppm): δ = 7.31-7.27(m, 2 H), 7.20(dd, J = 6.8Hz, 3 H), 7.09-7.02(m, 5 H), 6.92(t, J = 8.4 Hz, 2 H), 6.8(d, J = 7.2 Hz, 2H), 6.76(dd, J = 2.8 Hz, 1 H), 6.37(dd, J = 3.2 Hz, 1 H), 3.97(s, 2 H); 13 CNMR (100 MHz, CDCl3, ppm): δ = 162.5, 160.1, 140.3, 140.1, 133.0, 133.0,129.3, 129.2, 128.9, 128.3, 128.0, 127.5, 127.4, 126.5, 125.9, 123.6, 122.2,115.4, 115.1, 108.9, 30.8. 19 F NMR (400 MHz, CDCl3) δ= -117.67. HRMS calcd forC 23 H 18 FN [M+H] + 328.1496; found: 328.1507.

[0072] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 12 are as follows:

[0073] 1 H NMR (600 MHz, CDCl3, ppm): δ =7.50(d, J = 7.8 Hz, 2 H), 7.38-7.31(m, 5 H), 7.24(t, J = 7.2 Hz, 1 H), 7.17(d, J = 8.4 Hz, 2 H), 7.03(d, J = 6.0Hz, 2 H), 6.89-6.85(m, 3 H), 6.55(s, 1 H), 4.10(s, 2 H), 2.63-2.59(m, 2 H),1.24-1.22(m, 3 H); 13 C NMR (150 MHz, CDCl3, ppm): δ = 141.6, 140.2, 137.7,137.0, 128.8, 128.5, 128.0, 127.9, 127.8, 127.8, 127.3, 126.6, 125.6, 124.4,122.1, 108.9, 30.5, 28.4, 15.6. HRMS calcd for C 25 H 23 N [M+H] + 338.1903; found: 338.1902.

[0074] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 13 are as follows:

[0075] 1 H NMR (600 MHz, CDCl3, ppm): δ = 7.51(d, J = 7.8 Hz, 2 H), 7.38-7.33(m, 5 H), 7.26-7.24(m, 1 H), 7.19(d, J = 6.6 Hz, 2 H), 7.03(d, J = 7.8 Hz, 2H), 6.90(s, 1 H), 6.86(d, J = 6.0 Hz, 2 H), 6.57(s, 1 H), 4.11(s, 2 H), 2.33(s, 3 H); 13C NMR (150 MHz, CDCl3, ppm): δ = 140.2, 137.5, 137.0, 135.2,129.0, 128.9, 128.8, 128.5, 127.9, 127.8, 127.8, 127.3, 126.5, 125.6, 124.4,122.2, 108.9, 30.5, 21.0. HRMS calcd for C 24 H 21 N [M+H] + 324.1747; found: 324.1749.

[0076] The structure, NMR, and high-resolution mass spectrometry data of the product obtained in Example 14 are as follows:

[0077] 1 H NMR (400 MHz, CDCl3, ppm): δ =7.43(d, J = 7.6 Hz, 2 H), 7.35-7.28(m, 6 H), 7.12-7.10(m, 2 H), 6.83-6.79(m, 5 H), 6.49(s, 1 H), 4.05(s, 2H); 13 C NMR (100 MHz, CDCl3, ppm): δ = 162.4, 160.0, 140.1, 136.9, 136.0, 129.4,129.3, 128.9, 128.5, 127.9, 127.5, 127.4, 126.5, 125.8, 124.6, 122.3, 115.1,114.9, 109.0, 30.2. 19 F NMR (400 MHz, CDCl3) δ= -117.63. HRMS calcd for C 23 H 18 FN[M+H] + 328.1496; found: 328.1499. References: 1. Yao, S.; Zhao, X. et al. Visible Light-Driven Direct Access toImine-Containing Azaarene-Substituted Highly Functionalized Pyrroles. Org.Chem. Front. 2023, 10, 4779-4785. 2. Huang, X.; Hu, Y.-Q. et al. Urushiol Derivatives as Biomass-BasedPhotocatalysts for the Transition-Metal-Free Synthesis of 1,2-Amino Alcohols.Green Chem. 2022, 24, 5764-5769. 3. Bhardwaj, V.; Gumber, D. et al. Pyrrole: A Resourceful SmallMolecule in Key Medicinal Hetero-Aromatics. RSC Adv., 2015, 5, 15233-15266. 4. Wu, C.; Wang, W. et al. Programmable Pyrrole-Imidazole Polyamides:A Potent Tool for DNA Targeting. Chin. Chem. Lett. 2018, 29, 1105-1112. 5. Staveness, D.; Bosque, I. et al. Free Radical Chemistry Enabled byVisible Light-Induced Electron Transfer. Acc. Chem. Res. 2016, 49, 2295-2306. 6. Xuan, J.; Zhang, Z.-G. et al. Visible-Light-InducedDecarboxylative functionalization of carboxylic acids and their derivatives.Angew. Chem., Int. Ed. 2015, 54, 15632-15641. 7. Fan, L.; Jia, J. et al. Decarboxylative Aminomethylation of Aryl‐and Vinylsulfonates through Combined Nickel‐ and Photoredox‐Catalyzed Cross‐Coupling. Chem. Eur. J. 2016, 22, 16437-16440. 8. Pan, S.; Jiang, M. et al. Synthesis of 1,2-Amino Alcohols byDecarboxylative Coupling of Amino Acid Derived α-Amino Radicals to CarbonylCompounds via Visible-Light Photocatalyst in Water. Green Chem. 2020, 22,336-341. 9. Liu, Y.; Dong, X. et al. Synthesis of Aziridines by Visible-LightInduced Decarboxylative Cyclization of N-Aryl Glycines and Diazo Compounds.Sci. China Chem. 2016, 59, 199-202. 10. Yang, J.; Song, M. et al. Visible-Light-Promoted DecarboxylativeAddition Cyclization of N-Aryl Glycines and Azobenzenes to Access 1,2,4-Triazolidines. Green Chem., 2021, 23, 5806-5811. 11. Song, T.; Mei, Y. et al. Construction of Bridged Benzazepines viaPhoto‐Induced Dearomatization. Angew. Chem. Int. Ed. 2024, 63, e202314304。

Claims

1. A method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne, comprising the following steps: A compound having general formula I, a compound having general formula II, a catalyst, a base, an additive, and a solvent were added to a pressure-resistant tube. The reaction was carried out under blue light irradiation at room temperature, and the reaction progress was monitored by thin-layer chromatography until the reaction was complete. The mixture was extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate as the mobile phase to obtain compound III. The reaction equation is as follows: In the equation: R 1 For hydrogen atom, methyl, ethyl, tert-butyl, fluorine atom, methoxy; R 2 For hydrogen atom, methyl, ethyl, fluorine atom, bromine atom, trifluoromethyl, methoxy; R 3 It consists of hydrogen atoms, methyl groups, and ethyl groups.

2. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The molar ratio of compounds with general formula I, compounds with general formula II, and catalysts is 2.0~3.0 : 1 : 0.

4.

3. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The wavelength of the reaction light is blue light (455-465nm).

4. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The reaction temperature is 18-25℃.

5. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The photocatalyst is 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, 2,4,6-tris(diphenylamino)-3,5-difluorobenzylonitrile, or 10-phenylphenthiazine.

6. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The base is dipotassium hydrogen phosphate, 2,6-dimethylpyridine, or potassium carbonate.

7. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The additive is elemental iodine.

8. The method for photocatalytic synthesis of pyrrole from N-arylglycine and 1,3-enyne according to claim 1, characterized in that: The solvent is dimethyl sulfoxide, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide.

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