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Synlett 2017; 28(14): 1852-1856
DOI: 10.1055/s-0036-1588432
letter
© Georg Thieme Verlag Stuttgart · New York

Sc(OTf)3-Catalyzed Aza-Friedel–Crafts Reaction of Electron-Rich Arenes with Isatin-Derived Ketimines: Access to 3-Amino-3-Aryl-2-Oxindoles

Hongjie Gao
a   College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   eMail: xuxsh1970@126.com
,
Xiangsheng Xu*
a   College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   eMail: xuxsh1970@126.com
,
Jianfeng Xu  *
b   Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. of China   eMail: jfxu@zstu.edu.cn
› InstitutsangabenWe gratefully acknowledge the National Natural Science Foundation of China (Grant No. 21602203), the Natural Science Foundation of Zhejiang Province (Grant No. LQ16B020001), and the Natural Science Foundation of Zhejiang Sci-Tech University (Grant No. 15062018-Y) for financial support.
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Publikationsverlauf

Received: 21. März 2017

Accepted after revision: 30. April 2017

Publikationsdatum:
31. Mai 2017 (online)

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Abstract

A Sc(OTf)3-catalyzed aza-Friedel–Crafts reaction of electron-rich arenes with isatin-derived ketimines is disclosed, providing biologically interesting 3-amino-3-aryl-2-oxindoles in moderate to good yields with broad substrate scope. This reaction can be easily scaled up, and the Boc protecting group could be readily removed under mild reaction conditions to afford the free amine.

Key words

Lewis acids - aza-Friedel–Crafts - electron-rich arenes - isatin-derived ketimines - 3-amino-3-aryl-2-oxindoles

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588432.
  • Supporting Information
 

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  • 11 General Procedure for the Catalytic Synthesis of Products 3 To a dry 4 mL vial equipped with a magnetic stir bar, were added electron-rich arene 1 (0.15 mmol), isatin-derived ketamine 2 (0.1 mmol), 4 Å MS (100 mg, powder), Sc(OTf)3 (0.01 mmol), and anhydrous MeCN (1 mL). The tube was sealed with a septum, and the reaction mixture was stirred at r.t. for another 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and the residue was subjected to column chromatography using hexane–EtOAc = 4:1 as eluent to afford the desired product 3. tert-Butyl-[1-benzyl-2-oxo-3-(2,4,6-trimethoxyphenyl)indolin-3-yl]carbamate (3a) 41.4 mg, 82% yield, white solid, mp 164–165 °C. 1H NMR (500 MHz, CDCl3): δ = 7.52 (d, J = 7.5 Hz, 2 H), 7.36 (d, J = 7 Hz, 1 H), 7.32 (t, J = 7.5 Hz, 2 H), 7.26 (t, J = 6.5 Hz, 1 H), 7.09 (t, J = 7.5 Hz, 1 H), 6.87 (t, J = 7.5 Hz, 1 H), 6.65 (d, J = 7.5 Hz, 1 H), 6.13 (s, 2 H), 5.07 (br, 2 H), 3.73 (s, 3 H), 3.63 (br, 6 H), 1.31 (br, 9 H). 13C NMR (125 MHz, CDCl3): δ = 176.6, 160.5, 159.0, 153.6, 143.9, 136.8, 131.4, 128.4, 128.3, 127.7, 127.1, 123.4, 122.0, 108.7, 108.4, 93.1, 79.2, 62.6, 56.3, 55.2, 44.6, 28.3. ESI-HRMS: m/z calcd for C29H32N2O6Na+: 527.2158; found: 527.2167.
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