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Synthesis 2012; 44(15): 2374-2384
DOI: 10.1055/s-0032-1316542
paper
© Georg Thieme Verlag Stuttgart · New York

Copper(II)-Mediated Cascade Oxidative C–C Coupling and Aromatization: Synthesis of 3-Hydroxyphenanthridinone Derivatives

Qingzhen Yu
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Nan Zhang
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Yang Tang
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Hang Lu
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Jianhui Huang
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Songqing Wang
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Yunfei Du*
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
,
Kang Zhao*
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, P. R. of China, Fax: +86(22)27404031   Email: duyunfeier@tju.edu.cn   Email: kangzhao@tju.edu.cn
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Further Information

Publication History

Received: 23 March 2012

Accepted after revision: 15 May 2012

Publication Date:
29 June 2012 (online)

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Abstract

A novel copper(II) acetate mediated synthesis of 3-hydroxyphenanthridin-6(5H)-ones from N-(3-oxocyclohex-1-enyl)benzamides was developed. The process is postulated to involve an intramolecular oxidative C(sp2)–C(sp3) bond formation followed by dehydrogenative aromatization.

Key words

copper(II) acetate - phenanthridinone - C–H functionalization - C–C oxidative coupling - dehydrogenative aromatization

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
  • Supporting Information
 

  • References


      • For recent reviews on C–C bond formation, see:
    • 1a Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
    • 1b Liu C, Zhang H, Shi W, Lei A.-W. Chem. Rev. 2011; 111: 1780
      CrossrefPubMed
    • 1c Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
    • 1d Daugulis O, Do H.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
      CrossrefPubMed
    • 1e Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
    • 1f Chen X, Engle KM, Wang D.-H, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
      CrossrefPubMed
    • 1g Ackermann L, Vicente R, Kapdi AR. Angew. Chem. Int. Ed. 2009; 48: 9792
      CrossrefPubMed

      For selected examples on C–C cross-coupling, see:
    • 2a Stuart DR, Fagnou K. Science 2007; 316: 1172
      CrossrefPubMed
    • 2b Li B.-J, Tian S.-L, Fang Z, Shi Z.-J. Angew. Chem. Int. Ed. 2008; 47: 1115
      Crossref
    • 2c Yeung CS, Zhao X.-D, Nadine B, Dong VM. Chem. Sci. 2010; 1: 331
      Crossref
    • 2d Zhao X.-D, Yeung CS, Dong VM. J. Am. Chem. Soc. 2010; 132: 5837
      Crossref
    • 2e Stuart DR, Villemure E, Fagnou K. J. Am. Chem. Soc. 2007; 129: 12072
      CrossrefPubMed
    • 2f Cho SH, Hwang SJ, Chang S. J. Am. Chem. Soc. 2008; 130: 9254
      Crossref
    • 2g Hull KL, Sanford MS. J. Am. Chem. Soc. 2009; 131: 9651
      Crossref
    • 2h Hull KL, Sanford MS. J. Am. Chem. Soc. 2007; 129: 11904
      CrossrefPubMed
    • 2i Dwight TA, Rue NR, Charyk D, Josselyn R, DeBoef B. Org. Lett. 2007; 9: 3137
      CrossrefPubMed
    • 2j Brasche G, Fortanet JG, Buchwald SL. Org. Lett. 2008; 10: 2207
      Crossref
    • 2k Li R, Jiang L, Lu W.-J. Organometallics 2006; 25: 5973
      Crossref
    • 2l Shi Z.-Z, Zhang C, Li S, Pan D.-L, Ding S.-T, Cui Y.-X, Jiao N. Angew. Chem. Int. Ed. 2009; 48: 4572
      CrossrefPubMed
    • 2m Stuart DR, Alsabeh P, Kuhn M, Fagnou K. J. Am. Chem. Soc. 2010; 132: 18326
      Crossref
    • 2n Martinez R, Simon M.-O, Chevalier R, Pautigny C, Genet J.-P, Darses S. J. Am. Chem. Soc. 2009; 131: 7887
      CrossrefPubMed
    • 2o Inoue S, Shiota H, Fukumoto Y, Chatani N. J. Am. Chem. Soc. 2009; 131: 6898

      For selected examples, see:
    • 3a Evano G, Blanchard N, Toumi M. Chem. Rev. 2008; 108: 3054
      CrossrefPubMed
    • 3b He C, Guo S, Huang L, Lei A.-W. J. Am. Chem. Soc. 2010; 132: 8273
      Crossref
    • 3c Do H.-Q, Daugulis O. J. Am. Chem. Soc. 2008; 130: 1128
      Crossref
    • 3d Li Z.-P, Li C.-J. J. Am. Chem. Soc. 2004; 126: 11810
      CrossrefPubMed
    • 3e Li Z.-P, Li C.-J. J. Am. Chem. Soc. 2005; 127: 6968
      CrossrefPubMed
    • 3f Li Z.-P, Li C.-J. J. Am. Chem. Soc. 2005; 127: 3672
      CrossrefPubMed
    • 3g Li Z.-P, Li C.-J. Org. Lett. 2004; 6: 4997
      CrossrefPubMed
    • 3h Kawano T, Yoshizumi T, Hirano K, Satoh T, Miura M. Org. Lett. 2009; 11: 3072
      CrossrefPubMed
    • 3i Yang F.-Z, Xu Z.-Q, Wang Z, Yu Z.-K, Wang R. Chem.–Eur. J. 2011; 17: 6321
    • 3j Wendlandt AE, Suess AM, Stahl SS. Angew. Chem. Int. Ed. 2011; 50: 11062
      CrossrefPubMed
    • 3k Zhang C, Xu Z.-J, Zhang L.-R, Jiao N. Angew. Chem. Int. Ed. 2011; 50: 11088
      CrossrefPubMed
    • 3l Bernini R, Fabrizi G, Sferrazza A, Cacchi S. Angew. Chem. Int. Ed. 2009; 48: 8078
      CrossrefPubMed

      For selected examples, see:
    • 4a Shibasaki M, Kanai M. Chem. Rev. 2008; 108: 2853
      CrossrefPubMed
    • 4b Zhang Y.-H, Li C.-J. Angew. Chem. Int. Ed. 2006; 45: 1949
      Crossref
    • 4c Jia Y.-X, Kündig EP. Angew. Chem. Int. Ed. 2009; 48: 1636
      Crossref
    • 4d Tang B.-X, Song R.-J, Wu C.-Y, Liu Y, Zhou M.-B, Wei W.-T, Deng G.-B, Yin D.-L, Li J.-H. J. Am. Chem. Soc. 2010; 132: 8900
      Crossref
    • 4e Perry A, Taylor RJ. K. Chem. Commun. 2009; 3249
    • 4f Klein JE. M. N, Perry A, Pugh DS, Taylor RJ. K. Org. Lett. 2010; 12: 3446
      Crossref
    • 4g Guru MM, Ali MA, Punniyamurthy T. Org. Lett. 2011; 13: 1194
      CrossrefPubMed
    • 4h Zhang C, Jiao N. J. Am. Chem. Soc. 2010; 132: 28
      CrossrefPubMed
    • 5a Dow RL, Chou TT, Bechle BM, Goddard C, Larson ER. J. Med. Chem. 1994; 37: 2224
      Crossref
    • 5b Kanojia RM, Ohemeng KA, Schwender CF, Barrett JF. Tetrahedron Lett. 1995; 36: 8553
      Crossref

      For selected examples on the synthesis of phenanthridinones by Pd(OAc)2, see:
    • 6a Karthikeyan J, Cheng C.-H. Angew. Chem. Int. Ed. 2011; 50: 9880
      CrossrefPubMed
    • 6b Wang G.-W, Yuan T.-T, Li D.-D. Angew. Chem. Int. Ed. 2011; 50: 1380
      CrossrefPubMed
    • 6c Donati L, Michel S, Tillequin F, Porée F.-H. Org. Lett. 2010; 12: 156
      CrossrefPubMed
    • 6d Furuta T, Kitamura Y, Hashimoto A, Fujii S, Tanaka K, Kan T. Org. Lett. 2007; 9: 183
      CrossrefPubMed
    • 6e Harayama T, Asai M, Miyagoe T, Abe H, Takeuchi Y, Yamaguchi A, Fujii S. Heterocycles 2010; 81: 1881
      Crossref
    • 6f Majumdar KC, Chattopadhyay B, Nath S. Tetrahedron Lett. 2008; 49: 1609
      Crossref
    • 6g Bernini R, Cacchi S, Fabrizi G, Sferrazza A. Synthesis 2008; 729
      Article in Thieme Connect
    • 6h Black DS. C, Keller PA, Kumar N. Tetrahedron 1993; 49: 151
      Crossref
    • 6i For an example on the synthesis of phenanthri-dinones by PIFA, see: Moreno I, Tellitu I, Etayo J, SanMartín R, Dimínguez E. Tetrahedron 2001; 57: 5403
      Crossref
  • 7 Bi W.-Y, Yun X.-L, Fan Y.-F, Qi X.-X, Du Y.-F, Huang J.-H. Synlett 2010; 2899
    Article in Thieme Connect
  • 8 Wang G.-W, Miao C.-B. Green Chem. 2006; 8: 1080
    Crossref

      • For the synthesis of substrate, see:
    • 9a Montalbetti CA. G. N, Falque V. Tetrahedron 2005; 61: 10827
      Crossref
    • 9b Anderson AJ, Nicholson JM, Bakare O, Butcher RJ, Wilson TL, Scott KR. Bioorg. Med. Chem. 2006; 14: 997
      Crossref
    • 9c Zhang W, Pugh G. Tetrahedron 2003; 59: 3009
      Crossref

      For some examples on the use of Cu(OAc)2, see:
    • 10a Würtz S, Rakshit S, Neumann JJ, Dröge T, Glorius F. Angew. Chem. Int. Ed. 2008; 47: 7230
      Crossref
    • 10b Neumann JJ, Rakshit S, Dröge T, Würtz S, Glorius F. Chem.–Eur. J. 2011; 17: 7298
  • 11 We thank one reviewer for suggesting such non-metallic hypervalent iodine oxidants for this cross-coupling and dehydrogenative reaction.
  • 12 In order to further study the substrate scope, we also managed to prepare the substrates containing the bulky isopropyl and tert-butyl groups. However, attempts to prepare such compounds under various condensation conditions were not successful
  • 13 For the previous examples describing such C(sp2)–C(sp2) bond coupling mediated by Pd, see refs. 2c, 6a, and 6h
  • 14 For a previous example involving the Cu(II)-mediated SET process, see ref. 4c
  • 15 Ninomiya BI, Naito T, Kiguchi T. J. Chem. Soc., Perkin Trans. 1 1973; 2257
    Crossref
    • 16a Ueda S, Nagasawa H. J. Org. Chem. 2009; 74: 4272
      CrossrefPubMed
    • 16b Faler CA, Joullié MM. Tetrahedron Lett. 2006; 47: 7229
      Crossref