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Synlett 2017; 28(14): 1852-1856
DOI: 10.1055/s-0036-1588432
DOI: 10.1055/s-0036-1588432
letter
Sc(OTf)3-Catalyzed Aza-Friedel–Crafts Reaction of Electron-Rich Arenes with Isatin-Derived Ketimines: Access to 3-Amino-3-Aryl-2-Oxindoles
We 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.Weitere Informationen
Publikationsverlauf
Received: 21. März 2017
Accepted after revision: 30. April 2017
Publikationsdatum:
31. Mai 2017 (online)
![](https://www.thieme-connect.de/media/synlett/201714/lookinside/thumbnails/st-2017-w0202-l_10-1055_s-0036-1588432-1.jpg)
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-oxindolesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588432.
- Supporting Information
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References and Notes
- 1a Peddibhotla S. Curr. Bioact. Compd. 2009; 5: 20
- 1b Badillo JJ. Hanhan NV. Franz AK. Curr. Opin. Drug Discovery Dev. 2010; 13: 758
- 1c Shen K. Liu X. Lin L. Feng X. Chem. Sci. 2012; 3: 327
- 1d Hong L. Wang R. Adv. Synth. Catal. 2013; 355: 1023
- 1e Bergman J. In Advances in Heterocyclic Chemistry . Vol. 117. Scriven EF. V. Ramsden CA. Elsevier; San Diego: 2015: 1
- 1f Kaur M. Singh M. Chadha N. Silakari O. Eur. J. Med. Chem. 2016; 123: 858
- 2a Zhou F. Liu Y.-L. Zhou J. Adv. Synth. Catal. 2010; 352: 1381
- 2b Chauhan P. Chimni SS. Tetrahedron: Asymmetry 2013; 24: 343
- 2c Kaur J. Chimni SS. Mahajan S. Kumar A. RSC Adv. 2015; 5: 52481
- 3a Bernard K. Bogliolo S. Ehrenfeld JB. J. Pharmacol. 2005; 144: 1037
- 3b Shimazaki T. Iijima M. Chaki S. Eur. J. Pharmacol. 2006; 543: 63
- 3c Decaux G. Soupart A. Vassart G. Lancet 2008; 371: 1624
- 3d Oost T. Backfisch G. Bhowmik S. van Gaalen MM. Geneste H. Hornberger W. Lubisch W. Netz A. Unger L. Wernet W. Bioorg. Med. Chem. Lett. 2011; 21: 3828
- 4a Rottmann M. McNamara C. Yeung BS. K. Lee MC. S. Zou B. Russell B. Seitz P. Plouffe DM. Dharia NV. Tan J. Cohen SB. Spencer KR. Gonzalez-Paez G. Lakshiminarayana L. Goh A. Suwanarusk R. Jegla T. Schmitt EK. Beck H.-P. Brun R. Nosten F. Renia L. Dartois V. Keller TH. Fidock DA. Winzeler EA. Diagana TT. Science 2010; 329: 1175
- 4b Yeung BK. S. Zou B. Rottmann M. Lakshminarayana SB. Ang SH. Leong SY. Tan J. Wong J. Keller-Maerki S. Fischli C. Goh A. Schmitt EK. Krastel P. Francotte E. Kuhen K. Plouffe D. Henson K. Wagner T. Winzeler EA. Petersen F. Brun R. Dartois V. Diagana TT. Keller TH. J. Med. Chem. 2010; 53: 5155
- 5a Jia Y.-X. Hillgren JM. Watson EL. Marsden SP. Kündig EP. Chem. Commun. 2008; 4040
- 5b Tolstoy P. Lee SX. Y. Sparr C. Ley SV. Org. Lett. 2012; 14: 4810
- 6a Bui T. Hernández-Torres G. Milite C. Barbas III CF. Org. Lett. 2010; 12: 5696
- 6b Zhou F. Ding M. Liu Y.-L. Wang C.-H. Ji C.-B. Zhang Y.-Y. Zhou J. Adv. Synth. Catal. 2011; 353: 2945
- 6c Yang C. Liu Y. Yang J.-D. Li Y.-H. Li X. Chen J.-P. Org. Lett. 2016; 18: 1036
- 7a Lesma G. Landoni N. Pilati T. Sacchetti A. Silvani A. J. Org. Chem. 2009; 74: 4537
- 7b Jung HH. Buesking AW. Ellman JA. Org. Lett. 2011; 13: 3912
- 7c Peng J. Yan W. Wang D. Li P. Sun Q. Wang R. Chem. Commun. 2012; 48: 8003
- 7d Montesinos-Magraner M. Vila C. Cantón R. Blay G. Fernández I. Muñoz MC. Pedro JR. Angew. Chem. Int. Ed. 2015; 54: 6320
- 7e Montesinos-Magraner M. Vila C. Rendón-Patiño A. Blay G. Fernández I. Muñoz MC. Pedro JR. ACS Catal. 2016; 6: 2689
- 7f He Q. Wu L. Kou X. Butt N. Yang G. Zhang W. Org. Lett. 2016; 18: 288
- 8a Schinzer D. Selectivities in Lewis Acid Promoted Reactions . Kluwer Academic Publishers; Dordrecht: 1989
- 8b Yamamoto H. Lewis Acids in Organic Synthesis . Wiley-VCH; Weinheim: 2000
- 9a Lv H. Tiwari B. Mo J. Xing C. Chi YR. Org. Lett. 2012; 14: 5412
- 9b Chen D. Xu MH. Chem. Commun. 2013; 49: 1327
- 9c Arai T. Matsumura E. Masu H. Org. Lett. 2014; 16: 2768
- 9d BeceÇo C. Chauhan P. Rembiak A. Wang A. Enders D. Adv. Synth. Catal. 2015; 357: 672
- 9e Zhao H. -W. Li B. Pang H.-L. Tian T. Chen X.-Q. Song X.-Q. Meng W. Yang Z. Zhao Y.-D. Liu Y.-Y. Org. Lett. 2016; 18: 848
- 10a Xu J. Mou C. Zhu T. Song B.-A. Chi YR. Org. Lett. 2014; 16: 3272
- 10b Xu J. Yuan S. Miao M. Org. Lett. 2016; 18: 3822
- 10c Xu J. Yuan S. Peng J. Miao M. Chen Z. Ren H. Chem. Commun. 2017; 53: 3430
- 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.
- 12 For a similar product with sulfinyl as the protecting group prepared from Bi(OTf)3-catalyzed aza-Friedel–Crafts reaction of indoles with isatin-derived ketimines, see: Chen J.-P. Chen W.-W. Li Y. Xu M.-H. Org. Biomol. Chem. 2015; 13: 3363
- 13 Marques CS. Burke AJ. Eur. J. Org. Chem. 2016; 806
For a recent review, see ref. 2c; for selected recent examples, see: