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Synlett 2014; 25(14): 2009-2012
DOI: 10.1055/s-0034-1378354
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Oxidative Electrophilic Carbofunctionalization of Acrylamides for the Synthesis of Oxindoles

Xueqin Li
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Jian Xu
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Pengbo Zhang
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Yuzhen Gao
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Ju Wu
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Guo Tang*
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Yufen Zhao
a   Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
b   Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 05 April 2014

Accepted after revision: 27 May 2014

Publication Date:
28 July 2014 (online)

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Abstract

A novel and efficient copper-catalyzed tandem oxidative cyclization of arylacrylamides with diaryliodonium salts is reported. This reaction provides a novel approach for the synthesis of oxindoles and various functional groups were well tolerated.

Key words

copper-catalyzed - acrylamides - diphenyliodonium ­triflate - oxindoles - electrophilic arylation

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References and Notes


      • For some selected examples, see:
    • 1a Singhand GS, Desta ZY. Chem. Rev. 2012; 112: 6104
      Crossref
    • 1b Marti C, Carreira EM. Eur. J. Org. Chem. 2003; 2209
    • 1c Ball-Jones NR, Badillo JJ, Franz AK. Org. Biomol. Chem. 2012; 10: 5165
      CrossrefPubMed
    • 1d Trost BM, Brennan MK. Synthesis 2009; 3003
      Article in Thieme Connect
    • 1e Jiang T, Kuhen KL, Wolff K, Yin H, Bieza K, Caldwell J, Bursulaya B, Tuntland T, Zhang K, Karanewsky D, He Y. Bioorg. Med. Chem. Lett. 2006; 16: 2109
      CrossrefPubMed
    • 1f Kitamura H, Kato A, Esaki T. Eur. J. Pharmacol. 2001; 418: 225
      Crossref

      For some selected examples, see:
    • 3a Jia Y.-X, Kndig EP. Angew. Chem. Int. Ed. 2009; 48: 1636
      Crossref
    • 3b Wu T, Mu X, Liu G. Angew. Chem. Int. Ed. 2011; 50: 12578
      Crossref
    • 3c Broggini G, Barbera V, Beccalli EM, Borsini E, Galli S, Lanza G, Zecchi G. Adv. Synth. Catal. 2012; 354: 159
      Crossref
    • 3d Perry A, Taylor RJ. K. Chem. Commun. 2009; 3249
    • 3e An G, Zhou W, Zhang G, Sun H, Han J, Pan Y. Org. Lett. 2010; 12: 4
      Crossref

      For the difunctionalization of alkenes leading to oxindoles through a radical process, see:
    • 4a Wei WT, Zhou MB, Fan JH, Liu W, Song RJ, Liu Y, Hu M, Xie P, Li J.-H. Angew. Chem. Int. Ed. 2013; 52: 3638
      CrossrefPubMed
    • 4b Li YM, Sun M, Wang HL, Tian Q.-P, Yang SD. Angew. Chem. Int. Ed. 2013; 52: 3972
      Crossref
    • 4c Xie J, Xu P, Li H, Xue Q, Jin H, Cheng Y, Zhu C. Chem. Commun. 2013; 49: 5672
      CrossrefPubMed
    • 4d Matcha K, Narayan R, Antonchick AP. Angew. Chem. Int. Ed. 2013; 52: 7985
      CrossrefPubMed
    • 4e Zhou MB, Song RJ, Ouyang XH, Liu Y, Wei WT, Deng G.-B, Li JH. Chem. Sci. 2013; 4: 2690
      Crossref
    • 4f Li XQ, Xu XS, Hu P, Xiao XQ, Zhou C. J. Org. Chem. 2013; 78: 7343
      CrossrefPubMed
    • 4g Li Y.-M, Wei XH, Li XA, Yang SD. Chem. Commun. 2013; 49: 11701
      CrossrefPubMed
    • 4h Majumdar KC, Karunakar GV, Sinha B. Synthesis 2012; 44: 2475
      Article in Thieme Connect
    • 4i Zhang J.-L, Liu Y, Song R.-J, Jiang G.-F, Li J.-H. Synlett 2014; 25: 1031
      Article in Thieme Connect
    • 5a Merritt EA, Olofsson B. Angew. Chem. Int. Ed. 2009; 48: 9052
    • 5b Zhou B, Hou W, Yang Y, Feng H, Li YC. Org. Lett. 2014; 16: 1322
      CrossrefPubMed
    • 5c Vaddula BR, Saha A, Leazer J, Varma RS. Green Chem. 2012; 14: 2133
      Crossref
    • 5d Kang SK, Yoon SK, Kim YM. Org. Lett. 2001; 3: 2697
      CrossrefPubMed
    • 5e Jalalian N, Ishikawa EE, Silva LF, Olofsson B. Org. Lett. 2011; 13: 1552
      Crossref
    • 5f Petersen TB, Khan R, Olofsson B. Org. Lett. 2011; 13: 3462
      Crossref
    • 5g Umierski N, Manolikakes G. Org. Lett. 2013; 15: 188
      CrossrefPubMed
    • 5h Kraszkiewicz L, Skulski L. Synthesis 2008; 2373
      Article in Thieme Connect
    • 5i Xu J, Zhang PB, Gao YZ, Chen YY, Tang G, Zhao YF. J. Org. Chem. 2013; 78: 8176
    • 5j Phipps RJ, Grimster NP, Gaunt MJ. J. Am. Chem. Soc. 2008; 130: 8172
    • 5k Allen AE, MacMillan DW. C. J. Am. Chem. Soc. 2011; 133: 4260
      CrossrefPubMed
    • 5l Liu YX, Xue D, Wang JD, Zhao CJ, Zou QZ, Wang C, Xiao J. Synlett 2013; 24: 507
      Article in Thieme Connect
    • 5m During the preparation of our manuscript, similar research was reported: Zhou B, Hou W, Yang Y, Feng H, Li YC. Org. Lett. 2014; 16: 1322
      CrossrefPubMed
  • 6 Phipps RJ, Gaunt MJ. Science 2009; 323: 1593
    CrossrefPubMed
    • 7a Walkinshaw AJ, Xu W, Suero MG, Gaunt MJ. J. Am. Chem. Soc. 2013; 135: 12532
      CrossrefPubMed
    • 7b Suero MG, Bayle ED, Collins BS. L, Gaunt MJ. J. Am. Chem. Soc. 2013; 135: 5332
      CrossrefPubMed
  • 8 Cahard E, Bremeyer N, Gaunt MJ. Angew. Chem. Int. Ed. 2013; 52: 9284
    CrossrefPubMed
  • 10 Typical Procedure: An oven-dried 10-mL Schlenk tube containing CuCl (4.5 mg, 15 mol%), N-arylacrylamide 1a (90.3 mg, 0.3 mmol), and diphenyliodonium triflate (2a; 154.8 mg, 0.36 mmol) was evacuated and purged with nitrogen three times. DTBP (68.8 mg, 0.36 mmol) in freshly distilled CH2Cl2 (2.0 mL) was added to the system at r.t. The reaction mixture was heated with stirring at 60 °C for 24 h. The reaction mixture was allowed to cool to ambient temperature, and then transferred to a round-bottom flask. Silica gel (3.0 g) was added, and the solvent was removed under reduced pressure to afford a free-flowing powder. This powder was then dry-loaded onto a silica gel column and purified by flash chromatography using petroleum ether–EtOAc (20:1) as the eluent to give the product 3a. Yield: 75 mg (81%). MS (ESI): m/z = 274.0 [M + Na]+. 1H NMR (400 MHz, CDCl3): δ = 7.03–7.18 (m, 6 H), 6.83–6.85 (m, 2 H), 6.62 (d, J = 7.7 Hz, 1 H), 3.12 (d, J = 13.0 Hz, 1 H), 3.01 (d, J = 13.0 Hz, 1 H), 2.98 (s, 3 H), 1.47 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 179.9, 142.9, 136.0, 132.9, 129.7, 127.6, 126.3, 123.2, 121.9, 107.6, 50.0, 44.4, 26.7, 22.6.