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Synlett 2009(20): 3355-3359  
DOI: 10.1055/s-0029-1218373
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Ruthenium-Catalyzed Regioselective Reactions of Nitriles and 1,3-Dicarbonyl Compounds with Terminal Alkynes [¹]

Shun-Ichi Murahashi*a,b, Takeshi Naotaa, Yoshinori Nakanoa
a Department of Chemistry, Graduate School of Engineering Science, Osaka University, 1-3, Machikaneyama, Toyonaka, Osaka 560-8531, Japan
b Department of Applied Chemistry, Faculty of Engineering, Okayama University of Science, 1-1 Ridai-cho, Okayama 700-0005, Japan
Fax: +81(86)2564292; e-Mail: murahashi@high.ous.ac.jp;
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Publication History

Received 23 September 2009
Publication Date:
18 November 2009 (online)

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Abstract

RuH2(PPh3)4-catalyzed reaction of nitriles with terminal alkynes proceeds highly efficiently under neutral conditions to give the corresponding Michael adducts. Furthermore, 1,3-dicarbonyl compounds react with terminal alkynes at the α-position to afford the exo-methylene compounds with high regioselectivity under neutral conditions. The regioselectivity depends upon the change of substrates. The precise mechanism is presented.

Key words

ruthenium catalyst - regioselective addition - nitriles - 1,3-dicarbonyl compounds - alkynes

1

Presented at the 40th Symposium on Organometallic Chemistry, 1995, Osaka, Japan.

    References and Notes

  • 2a Murahashi S.-I. In Handbook of C-H Transformation   Vol. 2:  Dyker G. Wiley-VCH; Weinheim: 2005.  p.319 
    Google Scholar
  • 2b Murahashi S.-I. Takaya H. Acc. Chem. Res.  2000,  33:  225 
    Google Scholar
  • 2c Murahashi S.-I. Naota T. Bull. Chem. Soc. Jpn.  1996,  69:  1805 
    Google Scholar
  • 3a Naota T. Taki T. Mizuno M. Murahasi S.-I. J. Am. Chem. Soc.  1989,  111:  5954 
    Google Scholar
  • 3b Murahashi S.-I. Naota T. Taki H. Mizuno M. Takaya H. Komiya S. Mizuho Y. Oyasato N. Hiraoka M. Hirano H. Fukuoka A.
    J. Am. Chem. Soc.  1995,  117:  12436 
    Google Scholar
  • 3c Takaya H. Murahashi S.-I. Synlett  2001,  991 
    Google Scholar
  • 3d Takaya H. Naota T. Murahashi S.-I. J. Am. Chem. Soc.  1998,  120:  4244 
    Google Scholar
  • 3e Takaya H. Yoshida K. Isozaki K. Terai H. Murahshi S.-I. Angew. Chem. Int. Ed.  2003,  42:  3302 
    Google Scholar
  • 4 Takaya H. Kojima S. Murahashi S.-I. Org. Lett.  2001,  3:  421 
    CrossrefGoogle Scholar
  • 5 Guo Y. Zhao X. Zhang D. Murahashi S.-I. Angew. Chem. Int. Ed.  2009,  48:  2047 
    CrossrefGoogle Scholar
  • 6 Takaya H. Ito M. Murahashi S.-I. J. Am. Chem. Soc.  2009,  131:  10824 
    CrossrefGoogle Scholar
  • 7a Nakamura M. Endo K. Nakamura E. J. Am. Chem. Soc.  2003,  125:  13002 
    Google Scholar
  • 7b Endo T. Hatakeyama T. Nakamura M. Nakamura E. J. Am. Chem. Soc.  2007,  129:  5264 
    Google Scholar
  • 7c Tsuji H. Yamagata K. Itoh Y. Endo K. Nakamura M. Nakamura E. Angew. Chem. Int. Ed.  2007,  46:  8060 
    Google Scholar
  • 7d Kaneda K. Motokura K. Nakagiri N. Mizugaki T. Jitsukawa K. Green Chem.  2008,  10:  1231 
    Google Scholar
  • 8a Kennedy-Smith JJ. Staben ST. Toste FD. J. Am. Chem. Soc.  2004,  126:  4626 
    Google Scholar
  • 8b Corley BK. Toste FD. J. Am. Chem. Soc.  2005,  127:  17168 
    Google Scholar
  • 9a Kuninobu T. Kanata A. Takai K. Org. Lett.  2005,  7:  4823 
    Google Scholar
  • 9b Kuninobu Y. Kawata A. Takai K. Org. Lett.  2008,  10:  1219 
    Google Scholar
  • 9c Kuninobu Y. Kawata A. Nishi M. Salprima YS. Chen M. Takai K. Chem. Asian J.  2009,  4:  1424 
    Google Scholar
  • 9d Zhao W.-G. Hua R. Tetrahedron  2007,  63:  11803 
    Google Scholar
  • 10 Guo Q. Zheng BF. Li J.-H. Org. Lett.  2005,  7:  2185 
    CrossrefGoogle Scholar
  • 11a Naota T. Tannna A. Murahashi S.-I. J. Am. Chem. Soc.  2000,  122:  2960 
    Google Scholar
  • 11b Naota T. Tannna A. Kamuro S. Murahashi S.-I. J. Am. Chem. Soc.  2002,  124:  6842 
    Google Scholar
  • 11c Naota T. Tannna S. Kamuro S. Hieda M. Ogata K. Murahashi S.-I. Takaya H. Chem. Eur. J.  2008,  14:  2482 
    Google Scholar
1

Presented at the 40th Symposium on Organometallic Chemistry, 1995, Osaka, Japan.