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Synlett 2022; 33(19): 1938-1942
DOI: 10.1055/a-1937-9244
letter

Free-Radical-Involved Trifluoromethylthiolation Cyclization of Alkenes To Access SCF3-Substituted Indolo[2,1-a]isoquinolines

Yang Li
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
,
Lijun Li∗
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
,
Qinqin Yan
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
,
Yingming Ren
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
,
Xuan Li
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
,
Zhong-Quan Liu∗
b   State Key Laboratory Cultivation Base for TCM Quality and Efficacy, College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing, Jiangsu, 210023, P. R. of China
,
Zejiang Li  ∗
a   Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002, P. R. of China
› InstitutsangabenThis project is supported by the National Natural Science Foundation of China (21702044, 21971116), the Natural Science Foundation of Hebei Province (B2020201014, B2022201059), the Science and ­Technology Project of Department of Education of Hebei Province (QN2019063), and the Research Innovation Team of College of Chemistry and Environmental Science of Hebei University (hxkytd-py2102).
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Abstract

Free-radical-promoted tandem trifluoromethylthiolation of alkenes with AgSCF3, which provides an efficient protocol for the construction of SCF3-modified indolo[2,1-a]isoquinolines with moderate to good yields. A series of scaled-up experiments, other substrate transformations, and radical inhibition experiments were operated to verify the merit of this reaction system.

Key words

trifluoromethylthiolation - tandem cyclization - alkenes - AgSCF3 - indolo[2,1-a]isoquinolines

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1937-9244.
  • Supporting Information


Publikationsverlauf

Eingereicht: 15. August 2022

Angenommen nach Revision: 06. September 2022

Accepted Manuscript online:
06. September 2022

Artikel online veröffentlicht:
14. Oktober 2022

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  • 18 Typical Procedure for the Synthesis of 5-Methyl-5-{[(trifluoromethyl)thio]methyl}indolo[2,1-a]isoquinolin-6(5H)-one A mixture of 2-methyl-1-(2-phenyl-1H-indol-1-yl)prop-2-en-1-one (1 equiv., 0.1 mmol), AgSCF3 (2 equiv., 0.2 mmol), Na2S2O8 (3 equiv., 0.3 mmol), HMPA (0.6 equiv., 0.06 mmol), and CH3CN (3 mL) was stirred at 80 °C for 12 h under N2. When it was finished, the mixture was condensed under vacuum and purified by column chromatography (petroleum ether/ethyl acetate = 20/1) to access a white solid, 28.9 mg, with an 80% yield. 1H NMR (400 MHz, CDCl3): δ = 8.57 (d, J = 8.0 Hz, 1 H), 7.88 (dd, J = 5.6, 3.2 Hz, 1 H), 7.61 (d, J = 7.6 Hz, 1 H), 7.44–7.34 (m, 5 H), 7.07 (s, 1 H), 3.94 (d, J = 12.4 Hz, 1 H), 3.56 (d, J = 12.4 Hz, 1 H), 1.79 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 170.5, 135.3, 135.2, 134.8, 130.6, 130.3 (q, J = 304.6 Hz), 129.2, 128.3, 126.2, 125.6, 125.0, 124.9, 124.0, 120.6, 116.8, 103.9, 48.6, 39.8, 29.00. 19F NMR (565 MHz, CDCl3): δ = –41.15 (s, 3 F). HRMS (ESI): m/z calcd for C19H15F3NOS [M + H]+: 362.0821; found: 362.0825