Download PDF
Synlett 2010(3): 419-422  
DOI: 10.1055/s-0029-1218555
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes with Arylamines

Alethea N. Duncan, Ross A. Widenhoefer*
French Family Science Center, Duke University, Durham, NC 27708, USA
Fax: +1(919)660-1605; e-Mail: rwidenho@chem.duke.edu;
Further Information

Publication History

Received 21 August 2009
Publication Date:
07 January 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A mixture of [P(t-Bu)2-o-biphenyl]AuCl and AgOTf catalyzes the intermolecular hydroamination of monosubstituted and 1,1- and 1,3-disubstituted allenes with primary and secondary aryl­amines.

Key words

allylations - allenes - amines - homogenous catalysis - ­regioselectivity

    References and Notes

  • For recent reviews of catalytic hydroamination, see:
  • 1a Müller TE. Hultzsch KC. Yus M. Foubelo F. Tada M. Chem. Rev.  2008,  108:  3795 
    Google Scholar
  • 1b Widenhoefer RA. Han X. Eur. J. Org. Chem.  2006,  4555 
    Google Scholar
  • 1c Pohlki F. Doye S. Chem. Soc. Rev.  2003,  32:  104 
    Google Scholar
  • 1d Hong S. Marks TJ. Acc. Chem. Res.  2004,  37:  673 
    Google Scholar
  • For recent examples of the intramolecular hydroamination of allenes, see:
  • 2a Volz F. Krause N. Org. Biomol. Chem.  2007,  5:  1519 
    Google Scholar
  • 2b Morita N. Krause N. Eur. J. Org. Chem.  2006,  4634 
    Google Scholar
  • 2c Morita N. Krause N. Org. Lett.  2004,  6:  4121 
    Google Scholar
  • 2d Hoover JM. Petersen JR. Pikul JH. Johnson AR. Organometallics  2004,  23:  4614 
    Google Scholar
  • 2e Zhang Z. Bender CF. Widenhoefer RA. Org. Lett.  2007,  9:  2887 
    Google Scholar
  • 2f LaLonde RL. Sherry BD. Kang EJ. Toste FD. J. Am. Chem. Soc.  2007,  129:  2452 
    Google Scholar
  • 2g Lee PH. Kim H. Lee K. Kim M. Noh K. Kim H. Seomoon D. Angew. Chem. Int. Ed.  2005,  44:  1840 
    Google Scholar
  • 2h Patil NT. Lutete LM. Nishina N. Yamamoto Y. Tetrahedron Lett.  2006,  47:  4749 
    Google Scholar
  • 2i Zhang Z. Bender CF. Widenhoefer RA. J. Am. Chem. Soc.  2007,  129:  14148 
    Google Scholar
  • 3 Zhang Z. Liu C. Kinder RE. Han X. Qian H. Widenhoefer RA. J. Am. Chem. Soc.  2006,  128:  9066 
    CrossrefGoogle Scholar
  • 4 Walsh PJ. Baranger AM. Bergman RG. J. Am. Chem. Soc.  1992,  114:  1708 
    Google Scholar
  • 5a Johnson JS. Bergman RG. J. Am. Chem. Soc.  2001,  123:  2923 
    Google Scholar
  • 5b Ayinla RO. Schafer LL. Inorg. Chim. Acta  2006,  359:  3097 
    Google Scholar
  • 6 Al-Masum M. Meguro M. Yamamoto Y. Tetrahedron Lett.  1997,  38:  6071 
    Google Scholar
  • 7 Besson L. Gore J. Cazes B. Tetrahedron Lett.  1995,  36:  3857 
    Google Scholar
  • 8 Nishina N. Yamamoto Y. Angew. Chem. Int. Ed.  2006,  45:  3314 
    CrossrefGoogle Scholar
  • 9 Nishina N. Yamamoto Y. Synlett  2007,  1767 
    Article in Thieme ConnectGoogle Scholar
  • 10 Lavallo V. Frey GD. Donnadieu B. Soleilhavoup M. Bertrand G. Angew. Chem. Int. Ed.  2008,  47:  5224 
    Google Scholar
  • 11 Kinder RE. Zhang Z. Widenhoefer RA. Org. Lett.  2008,  10:  3157 
    Google Scholar
  • 12 Zeng X. Soleilhavoup M. Bertrand G. Org. Lett.  2009,  11:  3166 
    Google Scholar
  • 13a Lavallo V. Frey GD. Kousar S. Donnadieu B. Bertrand G. Proc. Natl. Acad. Sci. U.S.A.  2007,  104:  13569 
    Google Scholar
  • 13b Frey GD. Dewhurst RD. Kousar S. Donnadieu B. Bertrand G. J. Organomet. Chem.  2008,  693:  1674 
    Google Scholar
  • 15 Zhang Z. Widenhoefer RA. Org. Lett.  2008,  10:  2079 
    Google Scholar
14

Experimental Procedure and Spectroscopic Data for the Gold(I)-Catalyzed Hydroamination of 1 with o -Bromo-aniline (Table 2, entry 2): Dioxane (0.50 mL) was added to a mixture of o-bromoaniline (39 mg, 0.23 mmol), (3)AuCl (6.2 mg, 1.1 × 10-² mmol), and AgOTf (2.8 mg, 1.1 × 10-² mmol) and the resulting suspension was stirred for 10 min at r.t. 3-Methyl-1,2-butadiene (1; 29 mg, 0.43 mmol) was added via syringe and the resulting mixture was stirred at 45 ˚C for 24 h. Column chromatography of the reaction mixture (SiO2; hexanes-EtOAc, 15:1) gave N-(3-methyl-2-butenyl)-o-bromoaniline (48 mg, 87%) as a pale yellow oil. ¹H NMR (400 MHz, CDCl3): δ = 7.41 (dd, J = 1.5, 8.5 Hz, 1 H), 7.17 (dd, J = 1.5, 7.8 Hz, 1 H), 6.62 (dd, J = 1.0, 8.3 Hz, 1 H), 6.55 (dt, J = 1.5, 7.5 Hz, 1 H), 5.31-5.35 (m, 1 H), 4.23 (br s, 1 H), 3.72 (d, J = 6.8 Hz, 2 H), 1.76 (d, J = 1.0 Hz, 3 H), 1.72 (s, 3 H). ¹³C{¹H} NMR (100 MHz, CDCl3): δ = 145.1, 136.1, 132.3, 128.4, 121.1, 117.5, 111.4, 109.7, 41.9, 25.7, 18.1. HRMS: m/z [M+] calcd for C11H14BrN: 239.0310; found: 239.0313.