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DOI: 10.1055/s-2005-922755
Dirhodium Tetraacetate: An Effective Catalyst in Organic Synthesis
Publication History
Publication Date:
28 November 2005 (online)
Biographical Sketches
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] |
- 1
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4a
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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