Download PDF
Synthesis 2019; 51(16): 3085-3090
DOI: 10.1055/s-0037-1611521
paper
© Georg Thieme Verlag Stuttgart · New York

Iron-Promoted Construction of Indoles via Intramolecular Oxidative C–N Coupling of 2-Alkenylanilines Using Persulfate

Menglan Wang
a   State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   Email: qawu@zjut.edu.cn
b   State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China   Email: yhli@licp.cas.cn
,
Yudong Li
b   State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China   Email: yhli@licp.cas.cn
,
Qing-An Wu*
a   State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   Email: qawu@zjut.edu.cn
,
Shuping Luo
a   State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. of China   Email: qawu@zjut.edu.cn
,
Yuehui Li*
b   State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China   Email: yhli@licp.cas.cn
› Author AffiliationsThe authors acknowledge financial support of this work by the National Natural Science Foundation of China (21633013, 21101109, 21602228) and Natural Science Foundation of Jiangsu Province (BK20160394).
Further Information

Publication History

Received: 15 February 2019

Accepted after revision: 01 April 2019

Publication Date:
30 April 2019 (online)

    Permissions and Reprints All articles of this category


Abstract

Indole scaffold synthesis relies primarily on oxidative C–H amination of N-protected alkenylanilines for C–N intramolecular cyclization reactions. Herein, for the first time, without N-protection, various readily prepared 2-alkenylanilines were transformed into the desired indole products in good yields by using K2S2O8 as oxidant in the presence of catalytic amounts of FeF2. The K2S2O8/FeF2 system offers a direct and benign synthetic route to 3-arylindoles and it is applicable to a wide range of substituted indoles including drug intermediates.

Key words

indoles - C–N coupling - 2-alkenylanilines - oxidative amination - iron catalysis - 3-arylindoles - unprotected anilines

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611521.
  • Supporting Information
 

  • References

    • 1a Cacchi S, Fabrizi G. Chem. Rev. 2011; 111: PR215
      PubMed
    • 1b Kochanowska-Karamyan AJ, Hamann MT. Chem. Rev. 2010; 110: 4489
      CrossrefPubMed
    • 2a Rosenbaum C, Röhrs S, Müller O, Waldmann H. J. Med. Chem. 2005; 48: 1179
      CrossrefPubMed
    • 2b Morin D, Zini R, Urien S, Tillement JP. J. Pharmacol. Exp. Ther. 1989; 249: 288
      PubMed
    • 2c Pedras MS. C, Hossain M. Bioorg. Med. Chem. 2007; 15: 5981
      CrossrefPubMed
    • 2d Richardson TI, Clarke CA, Yu KL, Yee YK, Bleisch TJ, Lopez JE, Jones SA, Hughes NE, Muehl BS, Lugar CW, Moore TL, Shetler PK, Zink RW, Osborne JJ, Montrose-Rafizadeh C, Patel N, Geiser AG, Galvin RJ. S, Dodge JA. ACS Med. Chem. Lett. 2011; 2: 148
      CrossrefPubMed
    • 2e Mésangeau C, Amata E, Alsharif W, Seminerio MJ, Robson MJ, Matsumoto RR, Poupaert JH, McCurdy CR. Eur. J. Med. Chem. 2011; 46: 5154
      CrossrefPubMed
    • 2f Youn SW, Ko TY, Jang YH. Angew. Chem. Int. 2017; 56: 6636
      CrossrefPubMed
    • 3a Inman M, Moody CJ. Chem. Sci. 2013; 4: 29
      Crossref
    • 3b Vicente R. Org. Biomol. Chem. 2011; 9: 6469
      CrossrefPubMed
    • 3c Youn SW, Ko TY. Asian J. Org. Chem. 2018; 7: 1467
      Crossref
    • 3d Taylor RD, Maccoss M, Lawson AD. G. J. Med. Chem. 2014; 57: 5845
      CrossrefPubMed
    • 4a Fischer E, Jourdan F. Ber. Dtsch. Chem. Ges. 1883; 16: 2241
      Crossref
    • 4b Bischler A, Brion H. Ber. Dtsch. Chem. Ges. 1892; 25: 2860
      Crossref
    • 4c Gassman PG, Grurtzmacher G, van Bergen TJ. J. Am. Chem. Soc. 1974; 96: 5512
      Crossref
  • 5 Zhao CY, Li K, Pang Y, Li JQ, Liang C, Su GF, Mo DL. Adv. Synth. Catal. 2018; 360: 1919
    Crossref
  • 6 Jang YH, Youn SW. Org. Lett. 2014; 16: 3720
    CrossrefPubMed
  • 7 Ma AL, Li YL, Li J, Deng J. RSC Adv. 2016; 6: 35764
    Crossref
    • 8a Cacchi S, Fabrizi G, Goggiamani A. Adv. Synth. Catal. 2006; 348: 1301
      Crossref
    • 8b Álvarez R, Martínez C, Madich Y, Denis JG, Aurrecoechea JM, de Lera ÁR. Chem. Eur. J. 2010; 16: 12746
      CrossrefPubMed
    • 8c Han XL, Lu XY. Org. Lett. 2010; 12: 3336
      CrossrefPubMed
    • 9a Cajaraville A, López S, Varela JA, Saá C. Org. Lett. 2013; 15: 4576
      CrossrefPubMed
    • 9b Cai S. j, Lin SY, Yi XL, Xi CJ. J. Org. Chem. 2017; 82: 512
      CrossrefPubMed
    • 9c Sharma U, Kancherla R, Naveen T, Agasti S, Maiti D. Angew. Chem. Int. Ed. 2014; 53: 11895
      CrossrefPubMed
    • 9d Liu Y, Yao B, Deng CL, Tang RY, Zhang XG, Li JH. Org. Lett. 2011; 13: 1126
      CrossrefPubMed
  • 10 Youn SW, Lee SR. Org. Biomol. Chem. 2015; 13: 4652
    CrossrefPubMed
  • 11 Yang R, Yu JT, Sun S, Zheng QH, Cheng J. Tetrahedron Lett. 2017; 58: 445
    Crossref
    • 12a Mao XR, Wu YZ, Jiang XX, Liu XH, Cheng YX, Zhu C. RSC Adv. 2012; 2: 6733
      Crossref
    • 12b Jadhav SD, Singh A. Org. Lett. 2017; 19: 5673
      CrossrefPubMed
    • 12c Gao P, Wang J, Bai ZJ, Fan MJ, Yang DS, Guan ZH. Org. Lett. 2018; 20: 3627
      CrossrefPubMed
    • 13a Laha JK, Tummalapalli KS. S, Gupta A. Org. Lett. 2014; 16: 4392
      CrossrefPubMed
    • 13b Mandal S, Bera T, Dubey G, Saha J, Laha JK. ACS Catal. 2018; 8: 5085
      Crossref
    • 13c Bauer I, Knölker HJ. Chem. Rev. 2015; 115: 3170
      CrossrefPubMed
    • 13d Bernoud E, Ouli P, Guillot R, Mellah M, Hannedouche J. Angew. Chem. Int. Ed. 2014; 53: 4930
      CrossrefPubMed
    • 14a Jang SS, Youn SW. Org. Biomol. Chem. 2016; 14: 2200
      CrossrefPubMed
    • 14b Gao P, Wang J, Bai ZJ, Shen L, Yan YY, Yang DS, Fan MJ, Guan ZH. Org. Lett. 2016; 18: 6074
      CrossrefPubMed
  • 15 Elangovan S, Neumann J, Sortais JB, Junge K, Darcel C, Bellere M. Nat. Commun. 2016; 7: 12641
    CrossrefPubMed
  • 16 Choi I, Chung H, Park JW, Chung YK. Org. Lett. 2016; 18: 5508
    CrossrefPubMed
  • 17 Modha SG, Greaney MF. J. Am. Chem. Soc. 2015; 137: 1416
    CrossrefPubMed
  • 18 Chen SP, Liao YF, Zhao F, Qi HR, Liu SW, Deng GJ. Org. Lett. 2014; 16: 1618
    CrossrefPubMed
  • 19 Yamaguchi M, Suzuki K, Sato Y, Manabe K. Org. Lett. 2017; 19: 5388
    CrossrefPubMed
  • 20 Chen YX, Guo SB, Li KN, Qu JP, Yuan H, Hua QR, Chen BH. Adv. Synth. Catal. 2013; 355: 711
    Crossref
  • 21 Zhang JZ, Yin ZW, Leonard P, Wu J, Sioson K, Liu C, Lapo R, Zheng SP. Angew. Chem. Int. Ed. 2013; 52: 1753
    CrossrefPubMed
  • 22 Bering L, Paulussen FM, Antonchick AP. Org. Lett. 2018; 20: 1978
    CrossrefPubMed
  • 23 Ackermann L, Kaspara LT, Gschrei CJ. Chem. Commun. 2004; 2824
    PubMed
  • 24 Zhou Q, Zhang ZK, Zhou YJ, Li SC, Zhang Y, Wang JB. J. Org. Chem. 2017; 82: 48
    CrossrefPubMed
  • 25 Krüll J, Hubert A, Nebel N, Prante O, Heinrich MR. Chem. Eur. J. 2017; 23: 16174
    CrossrefPubMed