Download PDF
Synthesis 2020; 52(24): 3881-3890
DOI: 10.1055/s-0039-1690087
paper
© Georg Thieme Verlag Stuttgart · New York

Electrophilic Amination with Anthranils through Thioamide-Assisted Cobalt(III)-Catalyzed C(sp3)–H Activation

Lei Liu ‡
a   School of Pharmaceutical Sciences, Jiangnan University, Lihu Road 1800, 214122 Wuxi, Jiangsu, P. R. of China   Email: jjackli@jiangnan.edu.cn
,
Zhao Zhang ‡
a   School of Pharmaceutical Sciences, Jiangnan University, Lihu Road 1800, 214122 Wuxi, Jiangsu, P. R. of China   Email: jjackli@jiangnan.edu.cn
,
Yucheng Wang ‡
a   School of Pharmaceutical Sciences, Jiangnan University, Lihu Road 1800, 214122 Wuxi, Jiangsu, P. R. of China   Email: jjackli@jiangnan.edu.cn
,
Yan Zhang
a   School of Pharmaceutical Sciences, Jiangnan University, Lihu Road 1800, 214122 Wuxi, Jiangsu, P. R. of China   Email: jjackli@jiangnan.edu.cn
,
Jie Li  ∗
a   School of Pharmaceutical Sciences, Jiangnan University, Lihu Road 1800, 214122 Wuxi, Jiangsu, P. R. of China   Email: jjackli@jiangnan.edu.cn
b   Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Ren-Ai Road 199, 215123 Suzhou, Jiangsu, P. R. of China
› Author AffiliationsThis work was supported by the National Natural Science Foundation of China (Grant No. 21602083) and the Natural Science Foundation of Jiangsu Province (Grant No. BK20160160). We also thank the Fundamental Research Funds for the Central Universities (JUSRP51703A) and Soochow University.
Further Information

Publication History

Received: 04 January 2020

Accepted after revision: 13 February 2020

Publication Date:
03 March 2020 (online)

    Permissions and Reprints All articles of this category


‡ These authors contributed equally to this work.

Abstract

Cobalt(III)-catalyzed electrophilic amination of inert C(sp3)–H bonds of weakly coordinating thioamides with readily accessible anthranil derivatives was accomplished under mild conditions, with good functional group tolerance, thus providing various amino aldehydes and amino ketones. Moreover, our protocol with the versatile [Cp*Co(MeCN)3][SbF6]2 features excellent atom-economy and oxidant-free conditions, and allows facile late-stage functionalization.

Key words

C(sp3)–H activation - electrophilic amination - cobalt(III) catalysis­ - anthranils - thioamides

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690087.
  • Supporting Information
 

  • References


      • Recent reviews on C–H aminations:
    • 1a Park Y, Kim Y, Chang S. Chem. Rev. 2017; 117: 9247
      CrossrefPubMed
    • 1b Vitaku E, Smith DT, Njardarson JT. J. Med. Chem. 2014; 57: 10257 ; and references cited therein
      CrossrefPubMed

      Selected reviews:
    • 2a Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
      CrossrefPubMed
    • 2b Ma W, Gandeepan P, Li J, Ackermann L. Org. Chem. Front. 2017; 4: 1435
      Crossref
    • 2c Trost BM. Science 1991; 254: 1471
      CrossrefPubMed

      Representative examples for Pd:
    • 3a Zhu D, Yang G, He J, Chu L, Chen G, Gong W, Chen K, Eastgate MD, Yu J.-Q. Angew. Chem. Int. Ed. 2015; 54: 2497
      CrossrefPubMed
    • 3b Yoo EJ, Ma S, Mei T.-S, Chan KS. L, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 7652
      CrossrefPubMed
    • 3c Sun K, Li Y, Xiong T, Zhang J, Zhang Q. J. Am. Chem. Soc. 2011; 133: 1694
      CrossrefPubMed
    • 3d Ng K.-H, Chan AS. C, Yu W.-Y. J. Am. Chem. Soc. 2010; 132: 12862
      CrossrefPubMed

      Representative examples for Rh:
    • 4a Shi H, Dixon DJ. Chem. Sci. 2019; 10: 3733
      CrossrefPubMed
    • 4b Wang M, Kong L, Wang F, Li X. Adv. Synth. Catal. 2017; 359: 4411
      CrossrefPubMed
    • 4c Hu X.-H, Yang X.-F, Loh T.-P. ACS Catal. 2016; 6: 5930
      Crossref
    • 4d Wippich J, Truchan N, Bach T. Adv. Synth. Catal. 2016; 358: 2083
      Crossref
    • 4e Ali MA, Yao X, Li G, Lu H. Org. Lett. 2016; 18: 1386
      CrossrefPubMed
    • 4f Yu S, Tang G, Li Y, Zhou X, Lan Y, Li X. Angew. Chem. Int. Ed. 2016; 55: 8696
      CrossrefPubMed
    • 4g Zou M, Liu J, Tang C, Jiao N. Org. Lett. 2016; 18: 3030
      CrossrefPubMed
    • 4h Park SH, Kwak J, Shin K, Ryu J, Park Y, Chang S. J. Am. Chem. Soc. 2014; 136: 2492
      CrossrefPubMed
    • 4i Zhou B, Du J, Yang Y, Feng H, Li Y. Org. Lett. 2013; 15: 6302
      CrossrefPubMed
    • 4j Tang R.-J, Luo C.-P, Yang L, Li C.-J. Adv. Synth. Catal. 2013; 355: 869
      Crossref
    • 4k Yu S, Wan B, Li X. Org. Lett. 2013; 15: 3706
      CrossrefPubMed
    • 4l Yu D.-G, Suri M, Glorius F. J. Am. Chem. Soc. 2013; 135: 8802
      CrossrefPubMed
    • 4m Grohmann C, Wang H, Glorius F. Org. Lett. 2013; 15: 3014
      CrossrefPubMed
    • 4n Kim JY, Park SH, Ryu J, Cho SH, Kim SH, Chang S. J. Am. Chem. Soc. 2012; 134: 9110
      CrossrefPubMed
    • 4o Ng K.-H, Zhou Z, Yu W.-Y. Org. Lett. 2012; 14: 272 ; and references cited therein
      CrossrefPubMed

      Representative examples for Ir:
    • 5a Lanke V, Prabhu KR. Chem. Commun. 2017; 53: 5117
      CrossrefPubMed
    • 5b Kim H, Park G, Park J, Chang S. ACS Catal. 2016; 6: 5922
      Crossref
    • 5c Zhang T, Hu X, Wang Z, Yang T, Sun H, Li G, Lu H. Chem. Eur. J. 2016; 22: 2920
      CrossrefPubMed
    • 5d Zhang T, Wang Z, Hu X, Yu M, Deng T, Li G, Lu H. J. Org. Chem. 2016; 81: 4898
      CrossrefPubMed
    • 5e Pan C, Jin N, Zhang H, Han J, Zhu C. J. Org. Chem. 2014; 79: 9427
      CrossrefPubMed

      Representative examples for Ru:
    • 6a Raghuvanshi K, Zell D, Rauch K, Ackermann L. ACS Catal. 2016; 6: 3172
      Crossref
    • 6b Wang X, Zhang C, Li J, Jiang C, Su F, Zhan Z, Hai L, Chen Z, Wu Y. RSC Adv. 2016; 6: 68929
      Crossref
    • 6c Pan C, Abdukader A, Han J, Cheng Y, Zhu C. Chem. Eur. J. 2014; 20: 3606
      CrossrefPubMed
    • 6d Shin K, Ryu J, Chang S. Org. Lett. 2014; 16: 2022
      CrossrefPubMed
    • 6e Shin Y. J. Org. Chem. 2014; 79: 9262
      CrossrefPubMed
    • 6f Thirunavukkarasu VS, Raghuvanshi K, Ackermann L. Org. Lett. 2013; 15: 3286
      CrossrefPubMed
    • 6g Zheng QZ, Liang YF, Qin C, Jiao N. Chem. Commun. 2013; 49: 5654
      CrossrefPubMed
    • 7a Hendrick CE, Bitting KJ, Cho S, Wang Q. J. Am. Chem. Soc. 2017; 139: 11622
      CrossrefPubMed
    • 7b Peng J, Xie Z, Chen M, Wang J, Zhu Q. Org. Lett. 2014; 16: 4702
      CrossrefPubMed
  • 8 Ding Y, Zhang S.-Y, Chen Y.-C, Fan S.-X, Tian J.-S, Loh T.-P. Org. Lett. 2019; 21: 2736
    CrossrefPubMed

      • Selected reviews:
    • 9a Ujwaldev SM, Harry NA, Divakar MA, Anilkumar G. Catal. Sci. Technol. 2018; 8: 5983
      Crossref
    • 9b Kommagalla Y, Chatani N. Coord. Chem. Rev. 2017; 350: 117
      Crossref
    • 9c Moselage M, Li J, Ackermann L. ACS Catal. 2016; 6: 498
      Crossref
    • 9d Gao K, Yoshikai N. Acc. Chem. Res. 2014; 47: 1208
      CrossrefPubMed
    • 9e Kulkarni A, Daugulis O. Synthesis 2009; 4087 ; and references cited therein

      Representative examples:
    • 10a Wang S.-B, Gu Q, You S.-L. J. Catal. 2018; 361: 393
      Crossref
    • 10b Cheng H, Hernández JG, Bolm C. Adv. Synth. Catal. 2018; 360: 1800
      Crossref
    • 10c Wang F, Jin L, Kong L, Li X. Org. Lett. 2017; 19: 1812
      CrossrefPubMed
    • 10d Mei R, Loup J, Ackermann L. ACS Catal. 2016; 6: 793
      Crossref
    • 10e Wang F, Wang H, Wang Q, Yu S, Li X. Org. Lett. 2016; 18: 1306
      CrossrefPubMed
    • 10f Liang Y, Liang Y.-F, Tang C, Yuan Y, Jiao N. Chem. Eur. J. 2015; 21: 16395
      CrossrefPubMed
    • 10g Park J, Chang S. Angew. Chem. Int. Ed. 2015; 54: 14103
      CrossrefPubMed
    • 10h Patel P, Chang S. ACS Catal. 2015; 5: 853
      Crossref
    • 10i Sun B, Yoshino T, Matsunaga S, Kanai M. Chem. Commun. 2015; 51: 4659
      CrossrefPubMed
    • 10j Sun B, Yoshino T, Matsunaga S, Kanai M. Adv. Synth. Catal. 2014; 356: 1491
      Crossref
  • 11 Barsu N, Rahman MA, Sen M, Sundararaju B. Chem. Eur. J. 2016; 22: 9135
    CrossrefPubMed
  • 12 Tan PW, Mak AM, Sullivan MB, Dixon DJ, Seayad J. Angew. Chem. Int. Ed. 2017; 56: 16550
    CrossrefPubMed
  • 13 Fukagawa S, Kato Y, Tanaka R, Kojima M, Yoshino T, Matsunaga S. Angew. Chem. Int. Ed. 2019; 58: 1153
    CrossrefPubMed
    • 14a Ren J, Pi C, Wu Y, Cui X. Org. Lett. 2019; 21: 4067
      CrossrefPubMed
    • 14b Jin H, Tian B, Song X, Xie J, Rudolph M, Rominger F, Hashmi AS. K. Angew. Chem. Int. Ed. 2016; 55: 12688
      CrossrefPubMed
    • 14c Han S.-J, Vogt F, May JA, Krishnan S, Gatti M, Virgil SC, Stoltz BM. J. Org. Chem. 2015; 80: 528
      CrossrefPubMed
    • 14d Chauhan J, Fletcher S. Tetrahedron Lett. 2012; 53: 4951
      Crossref
    • 14e Domene C, Jenneskens LW, Fowler PW. Tetrahedron Lett. 2005; 46: 4077
      Crossref
    • 14f Matos MA. R, Miranda MS, Morais VM. F, Liebman JF. Eur. J. Org. Chem. 2004; 3340
    • 14g Sharma S, Srivastava VK, Kumar A. Eur. J. Med. Chem. 2002; 37: 689
      CrossrefPubMed
    • 14h Wünsch K.-H, Boulton AJ. Adv. Heterocycl. Chem. 1967; 8: 277

      Recent examples:
    • 15a Han S, Liu S, Liu L, Ackermann L, Li J. Org. Lett. 2019; 21: 5387
      CrossrefPubMed
    • 15b Li J, Knochel P. Angew. Chem. Int. Ed. 2018; 57: 11436
      CrossrefPubMed
    • 15c Zhang Z, Han S, Tang M, Ackermann L, Li J. Org. Lett. 2017; 19: 3315
      CrossrefPubMed
    • 15d Li J, Tang M, Zang L, Zhang X, Zhang Z, Ackermann L. Org. Lett. 2016; 18: 2742
      CrossrefPubMed
  • 16 Li J, Tan E, Keller N, Chen Y.-H, Zehetmaier PM, Jakowetz AC, Bein T, Knochel P. J. Am. Chem. Soc. 2019; 141: 98
    CrossrefPubMed
  • 17 Li L, Wang H, Yu S, Yang X, Li X. Org. Lett. 2016; 18: 3662
    CrossrefPubMed
  • 18 During the preparation of our manuscript, a similar cobalt(III)-catalyzed C(sp3)–H amination with anthranils was published; see: Liu R.-H, Shan Q.-C, Hu X.-H, Loh T.-P. Chem. Commun. 2019; 55: 5519
    CrossrefPubMed
  • 19 Avalos M, Babiano R, Duran CJ, Jimenez JL, Palacios JC. Tetrahedron Lett. 1994; 35: 477
    Crossref
  • 20 Levesque P, Fournier P.-A. J. Org. Chem. 2010; 75: 7033
    CrossrefPubMed
  • 21 Avalos M, Babiano R, Duran CJ, Jimenez JL, Palacios JC. Tetrahedron Lett. 1994; 35: 477
    Crossref
  • 22 Levesque P, Fournier P.-A. J. Org. Chem. 2010; 75: 7033
    CrossrefPubMed