Synlett 2011(8): 1121-1124  
DOI: 10.1055/s-0030-1259937
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Aerobic Oxidation of Cyclic Amines to Lactams Catalyzed by PVP-Stabilized Nanogold

Patcharee Preedasuriyachaia,b, Warinthorn Chavasiric, Hidehiro Sakurai*b,d,e
a Program in Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
b Department of Functional Molecular Science, The Graduate University for Advanced Studies, Myodaiji, Okazaki 444-8787, Japan
c Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
d Research Center for Molecular Scale Nanoscience, Institute for Molecular Science, Myodaiji, Okazaki 444-8787, Japan
Fax: +81(564)595527; e-Mail: hsakurai@ims.ac.jp;
e PRESTO, Japan Science and Technology Agency, Tokyo 102-0075, Japan
Further Information

Publication History

Received 15 January 2011
Publication Date:
07 April 2011 (online)

Abstract

Gold nanoclusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) are active and selective catalysts under aerobic conditions for oxidation of cyclic secondary amines at the α-position of the nitrogen atom. The catalyst accelerates the formation of the imines by oxidation of the amines in aqueous solvent to afford the corresponding lactams.

    References and Notes

  • 1a Bäckvall J.-E. In Modern Oxidation Methods   Bäckvall J.-E. Wiley-VCH; Weinheim: 2004.  p.193 
  • 1b Murahashi S.-I. Komiya N. In Ruthenium in Organic Synthesis   Murahashi S.-I. Wiley-VCH; Weinheim: 2004.  p.53 
  • 1c Pina CD. Falletta E. Rossi M. Top. Catal.  2007,  44:  325 
  • 2a Ochiai M. Kajishima D. Sueda T. Tetrahedron Lett.  1999,  40:  5541 
  • 2b Huang W.-J. Singh OV. Chen C.-H. Chiou S.-Y. Lee S.-S. Helv. Chim. Acta  2002,  85:  1069 
  • 2c Sueda T. Kajishima D. Goto S. J. Org. Chem.  2002,  68:  3307 
  • 3 Venkov AP. Statkova-Abeghe SM. Tetrahedron  1996,  52:  1451 
  • 4 Mohamed MA. Yamada K.-I. Tomioka K. Tetrahedron Lett.  2009,  50:  3436 
  • 5a Tamaru Y. Yamada Y. Yoshida Z. Synthesis  1983,  474 
  • 5b Noata T. Murahashi S.-i. Synlett  1991,  693 
  • 5c Tillack A. Rudloff I. Beller M. Eur. J. Org. Chem.  2001,  523 
  • 5d Yoo W.-J. Li C.-J. J. Am. Chem. Soc.  2006,  128:  13064 
  • 6 Nakagawa K. Onoue H. Minami K. Chem. Commun.  1996,  17 
  • 7 An G.-i. Kim M. Kim JY. Rhee H. Tetrahedron Lett.  2003,  44:  2183 
  • 8 Ekoue-Kovi K. Wolf C. Org. Lett.  2007,  9:  3429 
  • 9 Gao J. Wang G.-W. J. Org. Chem.  2008,  73:  2955 
  • 10 Punniyamurthy T. Velusamy S. Iqbal J. Chem. Rev.  2005,  105:  2329 
  • 11 Mizuno N. Yamaguchi K. Catal. Today  2008,  132:  18 
  • 12 Kodama S. Yoshida J. Nomoto A. Ueta Y. Yano S. Ueshima M. Ogawa A. Tetrahedron Lett.  2010,  51:  2450 
  • 13 Maeda Y. Nishimura T. Uemura S. Bull. Chem. Soc. Jpn.  2003,  76:  2399 
  • 14 Wang J.-R. Fu Y. Zhang B.-B. Cui X. Liu L. Guo Q.-X. Tetrahedron Lett.  2006,  47:  8293 
  • 15a Zhu B. Angelici RJ. Chem. Commun.  2007,  2157 
  • 15b Angelici RJ. J. Organomet. Chem.  2008,  693:  847 
  • 15c Zhu B. Lazar M. Trewyn BG. Angelici RJ.
    J. Catal.  2008,  260: 
  • 15d Grirrane A. Corma A. Garcia H. Science  2008,  322:  1661 
  • 15e So M.-H. Liu Y. Ho C.-M. Che C.-M. Chem. Asian J.  2009,  4:  1551 
  • 15f Aschwanden L. Mallat T. Krumeich F. Baiker A. J. Mol. Catal. A: Chem.  2009,  309:  57 
  • 15g Grirrane A. Corma A. Garcia H. J. Catal.  2009,  264:  138 
  • 15h Aschwanden L. Panella B. Rossbach P. Keller B. Baiker A. ChemCatChem  2009,  1:  111 
  • 15i Aschwanden L. Mallat T. Maciejewski M. Krumeich F. Baiker A. ChemCatChem  2010,  2:  666 
  • 15j Zhou Y. Angelici RJ. Woo LK. Catal. Lett.  2010,  137: 
  • 16a Tsunoyama H. Sakurai H. Ichikuni N. Negishi Y. Tsukuda T. Langmuir  2004,  20:  11293 
  • 16b Sakurai H. Tsunoyama H. Tsukuda T. J. Organomet. Chem.  2007,  692:  368 
  • 17a Tsunoyama H. Sakurai H. Negishi Y. Tsukuda T.
    J. Am. Chem. Soc.  2005,  127:  9374 
  • 17b Tsunoyama H. Sakurai H. Tsukuda T. Chem. Phys. Lett.  2006,  429:  528 
  • 17c Tsunoyama H. Tsukuda T. Sakurai H. Chem. Lett.  2007,  36:  212 
  • 17d Chaki NK. Tsunoyama H. Negishi Y. Sakurai H. Tsukuda T. J. Phys. Chem. C  2007,  111:  4885 
  • 17e Kanaoka S. Yagi N. Fukuyama Y. Aoshima S. Tsunoyama H. Tsukuda T. Sakurai H. J. Am. Chem. Soc.  2007,  129:  12060 
  • 17f Tsunoyama H. Ichikuni N. Sakurai H. Tsukuda T. J. Am. Chem. Soc.  2009,  127:  7086 
  • 18 Sakurai H. Tsunoyama H. Tsukuda T. Trans. Mater. Res. Soc. Jpn.  2006,  31 521:  8 
  • 19a Kamiya I. Tsunoyama H. Tsukuda T. Sakurai H. Chem. Lett.  2007,  36:  646 
  • 19b Kitahara H. Kamiya I. Sakurai H. Chem. Lett.  2009,  38:  908 
  • 19c Kitahara H. Sakurai H. Chem. Lett.  2010,  39:  46 
  • 20 Preedasuriyachai P. Kitahara H. Sakurai H. Chem. Lett.  2010,  39:  1174 
  • 21 Zhou W. Zhang L. Jiao N. Tetrahedron  2009,  65:  1982 
22

Typical Procedure for the Oxidation of 1a Catalyzed by Au:PVP under NaOH/H 2 O-EtOH Conditions
A test tube (ϕ = 30 mm) was placed with 1a (13.3 mg, 0.10 mmol), NaOH (8 mg, 0.20 mmol), and EtOH (5 mL). The aq solution of Au:PVP (1 mM, 10 mL = 10 atom%) was added, and the reaction mixture was stirred vigorously (1300 rpm) at 27 ˚C or 50 ˚C for 24 h. The reaction mixture was extracted with EtOAc (3 × 10 mL), and then washed the organic layers with brine, dried over Na2SO4, and concen-trated in vacuo. The crude products were separated by preparative TLC.