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
› Institutsangaben
This 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.
Weitere Informationen

Publikationsverlauf

Received: 04. Januar 2020

Accepted after revision: 13. Februar 2020

Publikationsdatum:
03. März 2020 (online)


‡ 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.

Supporting Information

 
  • References


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

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

      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
    • 3b Yoo EJ, Ma S, Mei T.-S, Chan KS. L, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 7652
    • 3c Sun K, Li Y, Xiong T, Zhang J, Zhang Q. J. Am. Chem. Soc. 2011; 133: 1694
    • 3d Ng K.-H, Chan AS. C, Yu W.-Y. J. Am. Chem. Soc. 2010; 132: 12862

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

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

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

    • Selected reviews:
    • 9a Ujwaldev SM, Harry NA, Divakar MA, Anilkumar G. Catal. Sci. Technol. 2018; 8: 5983
    • 9b Kommagalla Y, Chatani N. Coord. Chem. Rev. 2017; 350: 117
    • 9c Moselage M, Li J, Ackermann L. ACS Catal. 2016; 6: 498
    • 9d Gao K, Yoshikai N. Acc. Chem. Res. 2014; 47: 1208
    • 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
    • 10b Cheng H, Hernández JG, Bolm C. Adv. Synth. Catal. 2018; 360: 1800
    • 10c Wang F, Jin L, Kong L, Li X. Org. Lett. 2017; 19: 1812
    • 10d Mei R, Loup J, Ackermann L. ACS Catal. 2016; 6: 793
    • 10e Wang F, Wang H, Wang Q, Yu S, Li X. Org. Lett. 2016; 18: 1306
    • 10f Liang Y, Liang Y.-F, Tang C, Yuan Y, Jiao N. Chem. Eur. J. 2015; 21: 16395
    • 10g Park J, Chang S. Angew. Chem. Int. Ed. 2015; 54: 14103
    • 10h Patel P, Chang S. ACS Catal. 2015; 5: 853
    • 10i Sun B, Yoshino T, Matsunaga S, Kanai M. Chem. Commun. 2015; 51: 4659
    • 10j Sun B, Yoshino T, Matsunaga S, Kanai M. Adv. Synth. Catal. 2014; 356: 1491
  • 11 Barsu N, Rahman MA, Sen M, Sundararaju B. Chem. Eur. J. 2016; 22: 9135
  • 12 Tan PW, Mak AM, Sullivan MB, Dixon DJ, Seayad J. Angew. Chem. Int. Ed. 2017; 56: 16550
  • 13 Fukagawa S, Kato Y, Tanaka R, Kojima M, Yoshino T, Matsunaga S. Angew. Chem. Int. Ed. 2019; 58: 1153
    • 14a Ren J, Pi C, Wu Y, Cui X. Org. Lett. 2019; 21: 4067
    • 14b Jin H, Tian B, Song X, Xie J, Rudolph M, Rominger F, Hashmi AS. K. Angew. Chem. Int. Ed. 2016; 55: 12688
    • 14c Han S.-J, Vogt F, May JA, Krishnan S, Gatti M, Virgil SC, Stoltz BM. J. Org. Chem. 2015; 80: 528
    • 14d Chauhan J, Fletcher S. Tetrahedron Lett. 2012; 53: 4951
    • 14e Domene C, Jenneskens LW, Fowler PW. Tetrahedron Lett. 2005; 46: 4077
    • 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
    • 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
    • 15b Li J, Knochel P. Angew. Chem. Int. Ed. 2018; 57: 11436
    • 15c Zhang Z, Han S, Tang M, Ackermann L, Li J. Org. Lett. 2017; 19: 3315
    • 15d Li J, Tang M, Zang L, Zhang X, Zhang Z, Ackermann L. Org. Lett. 2016; 18: 2742
  • 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
  • 17 Li L, Wang H, Yu S, Yang X, Li X. Org. Lett. 2016; 18: 3662
  • 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
  • 19 Avalos M, Babiano R, Duran CJ, Jimenez JL, Palacios JC. Tetrahedron Lett. 1994; 35: 477
  • 20 Levesque P, Fournier P.-A. J. Org. Chem. 2010; 75: 7033
  • 21 Avalos M, Babiano R, Duran CJ, Jimenez JL, Palacios JC. Tetrahedron Lett. 1994; 35: 477
  • 22 Levesque P, Fournier P.-A. J. Org. Chem. 2010; 75: 7033