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Issue 14, 2012
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Enantioselective, transition metal catalyzed cycloisomerizations

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This review illustrates enantioselective transition-metal promoted skeletal rearrangements of polyunsaturated substrates possessing olefin, alkyne or allene functions. These processes are classified according to the number of carbon atoms involved in the cyclization, from (1C+1C) to (2C+2C+2C) or (2C+5C) cyclizations. Thus, for instance, (1C+1C) processes are typified notably by Alder-ene type reactions taking place mainly under palladium and rhodium catalysis, in the presence of chiral phosphorus ligands. Also, rhodium, platinum, and gold promoted insertions of unsaturated carbon–carbon bonds into C–H bonds belong to this class. For each class of reactions or substrate type the best ligand–metal pairs are highlighted. Unfortunately, unlike other transition metal promoted reactions, the mechanisms of chiral induction and stereochemical pathways have not been established so far in any of these reactions. In only a few instances, qualitative heuristic models have been tentatively proposed. Although the available stereochemical information is systematically given here, the paper focuses mainly on synthetic aspects of enantioselective cycloisomerizations.

Graphical abstract: Enantioselective, transition metal catalyzed cycloisomerizations

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The article was received on 20 Jan 2012 and first published on 06 Jun 2012

Article type: Critical Review
DOI: 10.1039/C2CS35020C
Chem. Soc. Rev., 2012,41, 4884-4908

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    Enantioselective, transition metal catalyzed cycloisomerizations

    A. Marinetti, H. Jullien and A. Voituriez, Chem. Soc. Rev., 2012, 41, 4884
    DOI: 10.1039/C2CS35020C

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