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Synlett 2019; 30(16): 1909-1913
DOI: 10.1055/s-0039-1690193
letter
© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Radical Methylation of Activated Alkenes with tert-Butanol as the Methyl Source

Zhengbao Xu∗
a   Institute of Biomedical Research, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China   Email: 1208241003@qq.com   Email: shen@sdut.edu.cn   Email: jhf@sdut.edu.cn
c   Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Zibo Key Laboratory of New Drug Development of Neurodegenerative Diseases, School of Life Sciences, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China
,
Rui Jia
b   Zibo Meteorological Bureau, Zibo, 255000, Shandong, P. R. of China
,
Zhiwei Ma
c   Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Zibo Key Laboratory of New Drug Development of Neurodegenerative Diseases, School of Life Sciences, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China
,
Shouhao Cao
c   Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Zibo Key Laboratory of New Drug Development of Neurodegenerative Diseases, School of Life Sciences, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China
,
Liang Shen∗
a   Institute of Biomedical Research, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China   Email: 1208241003@qq.com   Email: shen@sdut.edu.cn   Email: jhf@sdut.edu.cn
c   Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Zibo Key Laboratory of New Drug Development of Neurodegenerative Diseases, School of Life Sciences, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China
,
Hongfang Ji∗
a   Institute of Biomedical Research, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China   Email: 1208241003@qq.com   Email: shen@sdut.edu.cn   Email: jhf@sdut.edu.cn
c   Shandong Provincial Research Center for Bioinformatic Engineering and Technique, Zibo Key Laboratory of New Drug Development of Neurodegenerative Diseases, School of Life Sciences, Shandong University of Technology, Zibo, 255000, Shandong, P. R. of China
› Author AffiliationsThis work was supported by the Shandong Provincial Natural Science Foundation (Grant No. ZR2018MH010), Shandong Provincial Key Research and Development Program (Grant No. 2018GSF121001), and the Talent Program of Zibo.
Further Information

Publication History

Received: 03 July 2019

Accepted after revision: 13 August 2019

Publication Date:
27 August 2019 (online)

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◊ These authors contributed equally to this work.

Abstract

A free-radical-initiated methylation/addition/cyclization of N-arylacrylamides and a methylation/addition/elimination of quinines have been developed in which t-BuOH is used as a methyl source. These reactions provide effective and selective methods for the synthesis of various methylated oxindoles and quinones in moderate to good yields.

Key words

methylation - oxinidoles - quinones - arylacrylamides - quinones - cascade reaction

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690193.
  • Supporting Information

Primary Data

    for this article are available online at https://doi.org/10.1055/s-0039-1690193 and can be cited using the following DOI: 10.4125/pd0106th.
  • Primary Data
 

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  • 20 3-Ethyl-1,3-dimethyl-1,3-dihydro-2H-indol-2-one (1); Typical Procedure A mixture of N-methyl-N-phenylmethacrylamide (1 equiv, 0.2 mmol), Fe(acac)3 (2 mol%, 0.004 mmol), PIFA (2 equiv, 0.4 mmol), and t-BuOH (2 mL) was refluxed at 120 °C for 9 h. When the reaction was complete, the mixture was concentrated under vacuum and the residue was purified by flash column chromatography (silica gel) to give a colorless liquid; yield: 78%. 1H NMR (400 MHz, CDCl3): δ = 7.26 (t, J = 7.6 Hz, 1 H), 7.16 (d, J = 7.2 Hz, 1 H), 7.07 (t, J = 7.6 Hz, 1 H), 6.85 (d, J = 7.6 Hz, 1 H), 3.21 (s, 3 H), 1.97–1.88 (m, 1 H), 1.81–1.72 (m, 1 H), 1.34 (s, 3 H), 0.57 (t, J = 7.6 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 181.2, 143.2, 133.8, 127.6, 122.6, 122.4, 108.0, 49.1, 31.3, 26.1, 23.2, 8.7. MS (EI): m/z (%) = 189 (51.4), 160 (100.0). 2-Chloro-3-methylnaphthoquinone (19); Typical Procedure A mixture of 2-chloronaphthoquinone (1 equiv, 0.2 mmol), Fe(acac)3 (2 mol%, 0.004 mmol), PIFA (2 equiv, 0.4 mmol), and t-BuOH (2 mL) was refluxed at 120 °C for 5 h. When the reaction was complete, the mixture was concentrated under vacuum and the residue was purified by flash column chromatography (silica gel) to give a yellow solid; yield: 71%. 1H NMR (400 MHz, CDCl3): δ = 8.13–8.07 (m, 2 H), 7.74–7.72 (m, 2 H), 2.32 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 182.5, 177.4, 144.8, 143.2, 134.1, 133.8, 131.5, 131.2, 127.1, 126.9, 14.4. MS (EI): m/z (%) = 208 (4.1), 206 (13.3), 171 (100.0).