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)

Biographical Sketches

Pranab Haldar was born in Midnapur, India. He received his M.Sc. (Chemistry) degree in 2001 from Banaras Hindu University (India). He is currently working on his Ph.D. thesis under the supervision of Prof. J. K. Ray at Indian Institute of Technology (Kharagpur), India. He received ‘Young Scientist’ award of the Indian Chemical ­Society in 2002. His research interests focus on synthesis of bioactive N-aryl-γ-lactam derivatives and pyrroles and development of environmentally benign methodologies for the synthesis of aza­heterocycles.

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.

Abstracts

(A) Rh(II)-catalyzed regioselective intramolecular and regiospecific intermolecular CH insertion into aliphatic and aromatic C-H bonds is a very powerful methodology for the synthesis of a ­diverse range of organic compounds. [7]

(B) Rh2(OAc)4 is a very useful catalyst for two-component­cycloaddition as well as three-component 1,3-dipolar cycloaddition reactions. [8]

(C) On treatment with catalytic rhodium(II) acetate, cyclic diazo­amides and diazoamines furnished the corresponding cyclic ­enamides and Z enamines, repectively. [9]

(D) Allylic and benzylic alcohols were oxidized to the corresponding carbonyl compounds using tert-butyl hydroperoxide in ­stoichiometric amounts and Rh2(OAc)4 as catalyst (1 mol%) in dichloromethane at ambient temperature. [10]

(E) Intramolecular 1,2-insertions into C-C bonds by Rh(II) ­carbenoids have been used for the synthesis of substituted dienes. [11]

(F) Rh(II) carbenoids react with amines, alcohols or thiols to yield the product of a formal intra- or intermolecular X-H bond (X = N/O/S) insertion via the formation of an ylide intermediate. [12]

(G) Rh(II) carbenoids react readily with lone pairs giving the ­corresponding ylides, which are valuable intermediates, capable of undergoing a broad range of synthetically useful transformations. [13]

(H) Rh2(OAc)4 is an effective catalyst for the intra- and inter­molecular cyclopropanation reactions through the decomposition of diazocarbonyl compounds. [14]

(I) Du Bois et al. reported the Rh(II)-catalyzed oxidative cyclization of sulfamate and carbamate esters. [15]

    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 

    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