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Medium-Sized Rings versus Macrocycles through Rhodium-Catalyzed Ring-Expansion Reactions of Cyclic Acetals

Authors

  • Dr. Rafael Ballesteros-Garrido,

    1. Département de Chimie Organique, Université de Genève quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215
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  • Dr. Diane Rix,

    1. Département de Chimie Organique, Université de Genève quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215
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  • Dr. Céline Besnard,

    1. Laboratoire de Cristallographie, Université de Genève quai Ernest Ansermet 24, 1211 Geneva 4 (Switzerland)
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  • Prof. Jérôme Lacour

    Corresponding author
    1. Département de Chimie Organique, Université de Genève quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215
    • Département de Chimie Organique, Université de Genève quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215
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Abstract

α-Diazo β-ketoesters and diketones react with cyclic acetals under RhII catalysis to yield unprecedented polyoxygenated 8- and 9-membered rings in one pot. The reactions occur under mild conditions with yields up to 90 %. A perfect regioselectivity is obtained, which can be rationalized through a mechanistic hypothesis that considers 1) the formation of an oxonium ylide, 2) its transformation into an unsaturated acyclic oxocarbenium electrophilic intermediate, and 3) an intramolecular nucleophilic attack in a direct application of Baldwin’s rules.

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