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Synthesis 2009(4): 681-686  
DOI: 10.1055/s-0028-1083286
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© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Catalyzed Cross-Couplings of Unsaturated Halides Bearing Relatively Acidic Hydrogen Atoms with Organozinc Reagents

Zhibing Donga,b, Georg Manolikakesa, Jinshan Lib, Paul Knochel*a
a Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, Haus F, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: paul.knochel@cup.uni-muenchen.de;
b State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
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Publication History

Received 4 August 2008
Publication Date:
19 December 2008 (online)

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Abstract

A wide range of polyfunctional aryl, heteroaryl, alkyl, and benzylic zinc reagents were coupled with unsaturated aryl halides bearing an acidic NH or OH proton, using palladium(II) acetate (1 mol%), and S-Phos (2 mol%) as catalyst without the need of protecting groups.

Key words

palladium catalysis - cross-coupling - functionalized zinc reagents - polyfunctional biaryls

    References

  • 1a Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 1b Tsuji J. Transition Metal Reagents and Catalysis: Innovations in Organic Synthesis   Wiley; Chichester: 1995. 
    Google Scholar
  • 1c Transition Metals for Organic Synthesis   2nd ed.:  Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 2a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
    Google Scholar
  • 2b Littke AF. Fu GC. Angew. Chem. Int. Ed.  1998,  37:  3387 
    Google Scholar
  • 2c Wolfe JP. Buchwald SL. Angew. Chem. Int. Ed.  1999,  38:  2413 
    Google Scholar
  • 2d Zapf A. Ehrentraut A. Beller M. Angew. Chem. Int. Ed.  2000,  39:  4153 
    Google Scholar
  • 2e Molander GA. Biolatto B. J. Org. Chem.  2003,  68:  4302 
    Google Scholar
  • 3a Handy ST. Zhang Y. Bregman H. J. Org. Chem.  2004,  69:  2362 
    Google Scholar
  • 3b Chaumeil H. Signorella S. Le Drian C. Tetrahedron  2000,  56:  9655 
    Google Scholar
  • 3c Wanatabe T. Miyaura N. Suzuki A. Synlett  1992,  207 
    Google Scholar
  • 4a Negishi E. Valente LF. Kobayashi M. J. Am. Chem. Soc.  1980,  102:  3298 
    Google Scholar
  • 4b Negishi E. Acc. Chem. Res.  1982,  15:  340 
    Google Scholar
  • 4c Zeng X. Quian M. Hu Q. Negishi E. Angew. Chem. Int. Ed.  2004,  43:  2259 
    Google Scholar
  • For selected examples from our group, see:
  • 5a Sase S. Jaric M. Metzger A. Malakhov V. Knochel P. J. Org. Chem.  2008,  73:  7380 
    Google Scholar
  • 5b Gavryushin A. Kofink C. Manolikakes G. Knochel P. Org. Lett.  2005,  7:  4871 
    Google Scholar
  • 6 Manolikakes G. Schade MA. Muñoz Hernandez C. Mayr H. Knochel P. Org. Lett.  2008,  10:  2765 
    CrossrefGoogle Scholar
  • 7a Altman RA. Buchwald SL. Nature Protocols  2007,  2:  3115 
    Google Scholar
  • 7b Barder TE. Buchwald SL. J. Am. Chem. Soc.  2007,  129:  5096 
    Google Scholar
  • 7c Milne JE. Buchwald SL. J. Am. Chem. Soc.  2004,  126:  13028 
    Google Scholar
  • 7d Barder TE. Walker SD. Martinelli JR. Buchwald SL. J. Am. Chem. Soc.  2005,  127:  4685 
    Google Scholar
  • 8 Krasovskiy A. Malakhov V. Gavryushin A. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  6040 
    CrossrefGoogle Scholar
  • 10 For the possible use of thioarylaminyls as spin source or building block for organic magnets, see: Magnetic Properties of Organic Materials   Lathi PM. Marcel Dekker; New York: 1999. 
    Google Scholar
  • 11 Metzger A. Schade MA. Knochel P. Org. Lett.  2008,  10:  1107 
    CrossrefGoogle Scholar
  • 13 Krasovskiy A. Knochel P. Synthesis  2006,  890 
    Article in Thieme ConnectGoogle Scholar
9

Typical pK a values (in DMSO) for anilines range between 20-30; for a comprehensive compilation of pK a data see http://www.chem.wisc.edu/areas/reich/pkatable/index.htm and references cited therein.

12

Our experiments indicate a relative kinetic basicity of zinc reagents: arylzinc halide > alkylzinc halide > benzylic zinc halide. For further experimental details, see ref. 7.