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. 2006 Dec 8;71(25):9253-60.
doi: 10.1021/jo061411m.

Perspective on dirhodium carboxamidates as catalysts

Michael P Doyle  1
Affiliations

Perspective on dirhodium carboxamidates as catalysts

Michael P Doyle. J Org Chem. .

Abstract

Dirhodium compounds are emerging as highly efficient catalysts for diverse reactions, and those with carboxamidate ligands have the broadest applications. The unique features of these compounds are their structural rigidity, ease of ligand exchange, open diaxial sites for coordination with Lewis bases, and their low oxidation potential. As consequences of this, dirhodium carboxamidates are efficient and effective catalysts for metal carbene reactions, Lewis acid-catalyzed processes, and chemical oxidations. With chiral carboxamidate ligands these dirhodium compounds show exceptional enantiocontrol for intramolecular cyclopropanation and carbon-hydrogen insertion reactions of diazoacetates, and they are also highly efficient and selective for hetero-Diels-Alder reactions. Their limitations lie in their moderate reactivities for metal carbene generation and Lewis acid catalysis and in the cost of the precious metal rhodium.

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Figures

SCHEME 1
SCHEME 1
Some metal catalyzed reactions of diazocarbonyl compounds
SCHEME 2
SCHEME 2
Nitrogen-hydrogen insertion in the Merck synthesis of thienamycin
FIGURE 1
FIGURE 1
Generalized structure for (cis-2,2) dirhodium carboxamidates; (cis-2,2) refers to the atomic distribution of N and O on rhodium.
SCHEME 3
SCHEME 3
Chiral dirhodium(II) carboxamidate
FIGURE 2
FIGURE 2
Structure of Rh2(5R-MEPY)4, MEPY = methyl 2-oxapyrrolidine-5R-carboxylate: (a) and (b) are common representations, (c) is the x-ray structure with axially-coordinated acetonitrile molecules.
SCHEME 4
SCHEME 4
Attachment of a dirhodium carboxamidate to a polymer backbone (polystyrene-polyethylene glycol and Merrifield resins)
SCHEME 5
SCHEME 5
Oxidation potentials for dirhodium(II) compounds
FIGURE 3
FIGURE 3
Ring size versus %ee for reactions of with catalysts CuPF6/bis-oxazoline (1) and Rh2(4S-IBAZ)4.
SCHEME 6
SCHEME 6
Synthesis of S-(+)-imperanene via a carbon-hydrogen insertion reaction
SCHEME 7
SCHEME 7
Diastereoselectivity from match/mismatch of catalyst and substrate configurations in carbon-hydrogen insertion reactions
SCHEME 8
SCHEME 8
Dirhodium(II) catalysts for asymmetric oxonium ylide formation/[2,3]-sigmatropic rearrangement
SCHEME 9
SCHEME 9
Contrast between catalysts in regioselective cyclopropanation of farnesyl diazoacetate
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See this image and copyright information in PMC

References

    1. Cotton FA, DeBoer BG, LaPrade MD, Pipal JR, Ucko DA. J. Am. Chem. Soc. 1970;92:2926.
    2. Felthouse TR. Prog. Inorg. Chem. 1982;29:73.
    3. Boyar EB, Robinson SD. Coord. Chem. Rev. 1983;50:109.
    4. Ren T. Coord. Chem. Rev. 1998;175:43.
    1. Paulissenen R, Reimlinger H, Hayez E, Hubert AJ, Teyssie P. Tetrahedron Lett. 1973:2233.
    1. Doyle MP, McKervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds. Wiley; New York: 1998.

    1. Early contributions to Rh2(OAc)4–catalyzed C-H insertion reactions: Wenkert E, Davis LL, Mylari BL, Solomon MF, da Silva RR, Shulman S, Warnet RJ, Ceccherelli P, Curini M, Pellicciari R. J. Org. Chem. 1982;47:3242. Taber DF, Petty EH. J. Org. Chem. 1982;47:4808. Taber DF, Ruckle RE., Jr. J. Am. Chem. Soc. 1986;108:7686. Adams J, Frenette R. Tetrahedron Lett. 1987;28:4773. Stork G, Nakatani K. Tetrahedron Lett. 1988;29:2283. Doyle MP, Taunton J, Pho HQ. Tetrahedron Lett. 1989;30:5397.

    1. Early contributions to Rh2(OAc)4-catalyzed ylide formation: Gillespie RJ, Murray-Rust J, Murray-Rust P, Porter AEA. J. Chem. Soc., Chem. Commun. 1978;83 Doyle MP, Tamblyn WH, Bagheri V. J. Org. Chem. 1981;46:5094. Doyle MP, Griffin JH, Chinn MS, van Leusen D. J. Org. Chem. 1984;49:1917. Pirrung MC, Werner JA. J. Am. Chem. Soc. 1986;108:6060. Roskamp EJ, Johnson CR. J. Am. Chem. Soc. 1986;108:6060.

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