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Synlett 2023; 34(05): 457-464
DOI: 10.1055/a-1938-9550
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Special Edition Thieme Chemistry Journals Awardees 2022

Visible-Light-Promoted Metal-Free 3-Arylation of 2-Aryl-2H-­indazoles with Triarylsulfonium Salts

Anzai Shi
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
,
Panjie Xiang
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
,
Yanxuan Wu
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
,
Chang Ge
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
,
Yan Liu
c   Henan International Joint Laboratory of Rare Earth Composite Material, College of Materials Engineering, Henan University of Engineering, Zhengzhou 451191, P. R. of China
,
Kai Sun∗
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
b   College of Chemistry & Materials Engineering, Huaihua University, Huaihua 418008, P. R. of China
,
Bing Yu∗
a   Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R. of China
› Author AffiliationsWe acknowledge the financial support from the Hunan Provincial Natural Science Foundation of China (2021JJ40432), and the National Natural Science Foundation of China (21971224, 22171249).
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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 salts

Supporting 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

© 2022. Thieme. All rights reserved

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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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