Synthesis 2010(13): 2313-2318  
DOI: 10.1055/s-0029-1220008
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Preparation of Heterocyclic Amines via a Copper(I)-Mediated Oxidative Cross-Coupling of Organozinc Reagents with Lithium Amides

Cora Dunst, Marcel Kienle, Paul Knochel*
Ludwig-Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: [email protected];
Further Information

Publication History

Received 14 April 2010
Publication Date:
20 May 2010 (online)

Abstract

Functionalized heteroaromatic amines are readily prepared by the oxidative coupling of polyfunctional zinc amidocuprates using PhI(OAc)2 as oxidant. Various sensitive heterocyclic organometallics undergo this oxidative cross-coupling reaction furnishing aminated heteroaromatics. A high functional group tolerance and relative insensibility to steric hindrance characterize this general amination reaction. A practical procedure for the preparation of protected primary and secondary as well as tertiary heteroaryl amines is described.

    References

  • 1a Czarnik AW. Acc. Chem. Res.  1996,  29:  112 
  • 1b Law KY. Chem. Rev.  1993,  93:  44 
  • 1c MacDiarmid AG. Synth. Met.  1997,  84:  27 
  • 1d Gospodinova N. Terlemezyan L. Prog. Polym. Sci.  1998,  23:  1443 
  • 2a Metzger JV. Thiazole and its Derivatives   Wiley; New York: 1979. and references cited therein
  • 2b Koike K. Jia Z. Nikaido T. Liu Y. Zhao Y. Guo D. Org. Lett.  1999,  1:  197 
  • 2c Walcynski K. Guryn R. Zuiderveld OP. Timmermann H. Farmaco  1999,  54:  684 
  • 2d Law KY. Chem. Rev.  1993,  93:  449 
  • For selected reviews, see:
  • 3a Surry DS. Buchwald SL. Angew. Chem. Int. Ed.  2008,  47:  6338 
  • 3b Hartwig JF. Acc. Chem. Res.  2008,  41:  1534 
  • For recent reports, see:
  • 3c Shekhar S. Ryberg P. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  3584 
  • 3d Strieter ER. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  925 
  • 3e Surry DS. Buchwald SL. J. Am. Chem. Soc.  2007,  129:  10354 
  • 3f Fors BP. Watson DA. Biscoe MR. Buchwald SL. J. Am. Chem. Soc.  2008,  130:  13552 
  • 3g Fors BP. Davis NR. Buchwald SL. J. Am. Chem. Soc.  2009,  131:  5766 
  • 3h Schulz T. Torborg C. Enthaler S. Schäffner B. Dumrath A. Spannenberg A. Neumann H. Börner A. Beller M. Chem. Eur. J.  2009,  15:  4528 
  • 4 Yamamoto H. Maruoka K. J. Org. Chem.  1980,  45:  2739 
  • 5a Casarini A. Dembech P. Lazzari D. Marini E. Reginato G. Ricci A. Seconi G. J. Org. Chem.  1993,  58:  5620 
  • 5b Alberti A. Canè F. Dembech P. Lazzari D. Ricci A. Seconi G. J. Org. Chem.  1996,  61:  1677 
  • 5c Canè F. Brancaleoni D. Dembech P. Ricci A. Seconi G. Synthesis  1997,  545 
  • 5d Bernardi P. Dembech P. Fabbri G. Ricci A. Seconi G. J. Org. Chem.  1999,  64:  641 
  • 6a del Amo V. Dubbaka SR. Krasovskiy A. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  7838 
  • 6b Kienle M. Dubbaka SR. del Amo V. Knochel P. Synthesis  2007,  1272 
  • 7 Arzel E. Rocca P. Marsais F. Quéguiner G. Tetrahedron Lett.  1998,  39:  6465 
  • 8 For an excellent overview of hypervalent iodine compounds, see: Zhdankin VV. Stang PJ. Chem. Rev.  2008,  108:  5299 
  • 9 Kienle M. Dunst C. Knochel P. Org. Lett.  2009,  11:  5158 ; highlighted in Synfacts 2010, 213 and Angew. Chem. Int. Ed. 2010, 49, 2282
  • 10a Wunderlich SH. Knochel P. Angew. Chem. Int. Ed.  2007,  46:  7685 
  • 10b Wunderlich SH. Knochel P. Chem. Commun.  2008,  6387 
  • 11 Krasovskiy A. Krasovskaya V. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  2958 
  • 12 Piller FM. Metzger A. Schade MA. Haag BA. Gavryushin A. Knochel P. Chem. Eur. J.  2009,  15:  7192 
  • 13a Krasovskiy A. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  3333 
  • 13b Krasovskiy A. Straub B. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  159 
  • 14a Egi M. Liebeskind LS. Org. Lett.  2003,  5:  801 
  • 14b Metzger A. Melzig L. Despotopoulou C. Knochel P. Org. Lett.  2009,  11:  4228 
  • 14c Melzig L. Metzger A. Knochel P. J. Org. Chem.  2010,  75:  2131 
  • 15 Lin H.-S. Paquette LA. Synth. Commun.  1994,  24:  2503 
  • 16 Krasovskiy A. Knochel P. Synthesis  2006,  890 
  • 17 Hammett LP. Walden GH. Edmonds SM. J. Am. Chem. Soc.  1934,  56:  1092 
  • 18 For the use of i-Bu2AlH, see: Tilstan U. Weinmann H. Org. Process Res. Dev.  2002,  6:  906