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Synlett 2023; 34(05): 457-464
DOI: 10.1055/a-1938-9550
DOI: 10.1055/a-1938-9550
cluster
Special Edition Thieme Chemistry Journals Awardees 2022
Visible-Light-Promoted Metal-Free 3-Arylation of 2-Aryl-2H-indazoles with Triarylsulfonium Salts
We acknowledge the financial support from the Hunan Provincial Natural Science Foundation of China (2021JJ40432), and the National Natural Science Foundation of China (21971224, 22171249).
Abstract
An efficient approach for the photosynthesis of various arylated 2-aryl-2H-indazoles (38 examples) in moderate to good yields (up to 87% yield) under mild conditions was developed by employing 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as an inexpensive photocatalyst. This protocol features wide substrate scope, good functional group tolerance, and operational simplicity. In addition, the strategy was successfully applied to the late-stage modification of drug molecules, and the meaningful introduction of complex drugs to the skeleton of 2H-Indazole was achieved for the first time.
Key words
visible light - radical - metal-free - arylation - 2-aryl-2H-indazoles - triarylsulfonium saltsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1938-9550.
- Supporting Information
Publication History
Received: 09 August 2022
Accepted after revision: 08 September 2022
Accepted Manuscript online:
08 September 2022
Article published online:
17 October 2022
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- 21 General Experimental Procedures for the Desired Product 3 The mixture of 2-aryl-2H-indazole (0.2 mmol), aryl sulfonium salt (0.3 mmol, 1.5 equiv.), DMAP (0.4 mmol, 2.0 equiv.), 4CzIPN (5 mol%), and MeCN (2.0 mL) were sequentially added in a 25 mL reaction vessel. Then the reaction vessel was exposed to 10 W blue LED irradiation at room temperature under N2 atmosphere for 12 h. After reaction, the solvent was evaporated under vacuum, and all the crude products were purified by silica gel chromatography (petroleum ether/ethyl acetate = 30/1) as eluting solvent to give the desired products. Methyl 2-[2-Fluoro-4′-(2-phenyl-2H-indazol-3-yl)-(1,1′-biphenyl)-4-yl]propanoate (3r) White solid (56.7 mg, 63%); mp 142.5–143.2 °C. 1H NMR (400 MHz, chloroform-d): δ = 7.83 (dd, J = 16.3, 8.6 Hz, 2 H), 7.65–7.57 (m, 2 H), 7.55–7.49 (m, 2 H), 7.49–7.33 (m, 7 H), 7.23–7.13 (m, 3 H), 3.80 (q, J = 7.2 Hz, 1 H), 3.73 (s, 3 H), 1.57 (d, J = 7.2 Hz, 3 H). 13C NMR (101 MHz, chloroform-d): δ = 174.4, 161.0, 149.1, 142.3 (d, J = 7.7 Hz), 140.2, 135.4, 135.0, 130.6 (d, J = 3.8 Hz), 129.7, 129.2 (d, J = 3.3 Hz), 129.1, 128.4, 127.1, 127.0, 126.8, 126.1, 123.7 (d, J = 3.4 Hz), 122.7, 121.8, 120.5, 117.8, 115.4 (d, J = 23.7 Hz), 52.3, 44.9, 18.4. 19F NMR (376 MHz, chloroform-d): δ = –117.19. HRMS (ESI-TOF): m/z [M + H]+ calcd for C29H24N2O2: 451.1816; found: 451.1821. 2-Phenyl-3-(4-{4-[2-(pyridin-2-yloxy)propoxy]phenoxy}phenyl)-2H-indazole (3s)White solid (72.9 mg, 71%); mp 171.1–172.3 °C. 1H NMR (400 MHz, chloroform-d): δ = 8.21–8.16 (m, 1 H), 7.82 (d, J = 8.8 Hz, 1 H), 7.73 (d, J = 8.5 Hz, 1 H), 7.62–7.57 (m, 1 H), 7.53–7.22 (m, 8 H), 7.16 (ddd, J = 8.4, 6.6, 0.7 Hz, 1 H), 7.08–7.02 (m, 2 H), 7.01–6.93 (m, 4 H), 6.91–6.86 (m, 1 H), 6.77 (d, J = 8.3 Hz, 1 H), 5.65–5.58 (m, 1 H), 4.23 (dd, J = 9.9, 5.3 Hz, 1 H), 4.11 (dd, J = 9.8, 4.8 Hz, 1 H), 1.52 (d, J = 6.4 Hz, 3 H). 13C NMR (101 MHz, chloroform-d): δ = 163.1, 158.9, 155.7, 149.2, 149.0, 146.8, 140.3, 138.7, 135.1, 131.0, 129.0, 128.3, 127.0, 126.0, 123.7, 122.4, 121.6, 121.4, 120.5, 117.7, 117.3, 116.8, 115.9, 111.7, 71.0, 69.2, 17.0. HRMS (ESI-TOF): m/z [M + H]+ calcd for C33H28N3O3: 514.2125; found: 514.2136.
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