Synlett 2005(20): 3169-3170  
DOI: 10.1055/s-2005-922755
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

Dirhodium Tetraacetate: An Effective Catalyst in Organic Synthesis

Pranab Haldar*
Department of Chemistry, Indian Institute of Technology, ­Kharagpur 721302, India
e-Mail: pranab@chemist.com;
Further Information

Publication History

Publication Date:
28 November 2005 (online)

Introduction

Unlike free carbenes, Rh(II)-catalyzed carbenoids often undergo highly regio- and stereoselective intra- and intermolecular insertion into a sigma bond. Although many transition-metal complexes afford carbenoids, only those of Rh(II) have shown general applicability due to their higher selectivity. The pioneering development of Rh(II) acetate by Teyssie and co-workers [1] has resulted in highly chemo-, regio- and stereoselective reactions of α-diazocarbonyl compounds via a variety of reactivity modes. Subsequently, an extensive library of successful transformations rapidly evolved, ranging from Rh(II)-catalyzed OH [2] and NH [3] insertion to cyclopropanation of olefins [4] and aromatic systems. [5]

Rh(II)-catalyzed reactions can often be performed in the presence of water. Because of the high partition of Rh2(OAc)4 in the water phase, the catalyst can be effectively reused, [6] permitting the development of a more environmentally benign process. Dirhodium tetraacetate is conveniently prepared by refluxing RhCl3·3H2O and sodium acetate/acetic acid in ethanol and is now also commercially available. The Rh2(OAc)4 core has approximately D 4h symmetry, with the Lewis base adducts H2O in 1 coordinating to the sites trans to the Rh-Rh bond.

    References

  • 1 Paulissenen R. Reimlinger H. Hayez E. Hubert AJ. Teyssie P. Tetrahedron Lett.  1973,  14:  2233 
  • 2 McKervey MA. Ratananukul P. Tetrahedron Lett.  1982,  23:  2509 
  • 3 Paulissenen R. Reimlinger H. Hayez E. Hubert AJ. Teyssie P. Tetrahedron Lett.  1974,  15:  607 
  • 4a Hubert AJ. Feron A. Warin R. Teyssie P. Tetrahedron Lett.  1976,  17:  1317 
  • 4b Anciaux AJ. Hubert AJ. Noels AF. Petiniot N. Teyssie P. J. Org. Chem.  1980,  45:  695 
  • 5a Anciaux AJ. Demonceau A. Hubert AJ. Noels AF. Petiniot N. Teyssie P. J. Chem. Soc., Chem. Commun.  1980,  765 
  • 5b Anciaux AJ. Demonceau A. Hubert AJ. Noels AF. Warin R. Teyssie P. J. Org. Chem.  1981,  46:  873 
  • 6 Candeias NR. Gois PMP. Afonoso CAM. Chem. Commun.  2005,  391 
  • 7a Padwa A. Dean DC. Osterhout MH. Precedo L. Semones MA. J. Org. Chem.  1994,  59:  5347 
  • 7b Wang P. Adams J. J. Am. Chem. Soc.  1994,  116:  3296 
  • 7c Padwa A. Kassir JM. Semones MA. Weingarten MD. J. Org. Chem.  1995,  60:  53 
  • 7d Sawada T. Fuerest DE. Wood JL. Tetrahedron Lett.  2003,  44:  4919 
  • 7e Yoon CH. Flanigan DL. Chong B.-D. Jung KW. J. Org. Chem.  2002,  67:  6582 
  • 7f Haldar P. Kar GK. Ray JK. Tetrahedron Lett.  2003,  44:  7433 
  • 8a Padwa A. Zhi L. J. Am. Chem. Soc.  1990,  112:  2037 
  • 8b Pirrung MC. Lee YR. J. Chem. Soc., Chem. Commun.  1995,  673 
  • 8c Muthusamy S. Gunanathan C. Nethaji M. J. Org. Chem.  2004,  69:  5631 
  • 9 Muthusamy S. Gunanathan C. Babu SA. Synthesis  2002,  471 
  • 10 Moody CJ. Palmer FN. Tetrahedron Lett.  2002,  43:  139 
  • 11a Baird MS. Hussain HH. Tetrahedron  1987,  43:  215 
  • 11b Nagao K. Chiba M. Kim SW. Synthesis  1983,  197 
  • 12a Fehn S. Burger K. Tetrahedron: Asymmetry  1997,  8:  2001 
  • 12b Moyer MP. Feldman PL. Rapoprt H. J. Org. Chem.  1985,  50:  5223 
  • 12c Ferris L. Haigh D. Moody CJ. J. Chem. Soc., Perkin Trans. 1  1996,  2885 
  • 12d Williams RM. Lee BH. Miller MM. Anderson OP. J. Am. Chem. Soc.  1989,  111:  1073 
  • 13a West FG. Naidu BN. Tester RW. J. Org. Chem.  1994,  59:  6892 
  • 13b Kim G. Kang S. Keum G. Tetrahedron Lett.  1994,  35:  3747 
  • 14a Shi GQ. Cai WL. J. Chem. Soc., Perkin Trans. 1  1996,  2337 
  • 14b Adams J. Frenette R. Belley M. Chibante F. Springer JP. J. Am. Chem. Soc.  1987,  109:  5432 
  • 14c Padwa A. Chiacchio U. Fairfax DJ. Kassir JM. Litrico A. Semones MA. Xu SL. J. Org. Chem.  1993,  58:  6429 
  • 15a Espino CG. Bois JD. Angew. Chem. Int. Ed.  2001,  40:  598 
  • 15b Espino CG. When PM. Chow J. Bois JD. J. Am. Chem. Soc.  2001,  123:  6935 
  • 15c Fleming JJ. Fiori KW. Bois JD. J. Am. Chem. Soc.  2003,  125:  2028