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Scientific article
English

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

Published inChemistry, vol. 18, no. 21, p. 6626-6631
Publication date2012
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.

Keywords
  • Carbenoids
  • Diazo compounds
  • Medium-ring compounds
  • Rhodium
  • Ylides
Citation (ISO format)
BALLESTEROS GARRIDO, Rafael et al. Medium-Sized Rings versus Macrocycles through Rhodium-Catalyzed Ring-Expansion Reactions of Cyclic Acetals. In: Chemistry, 2012, vol. 18, n° 21, p. 6626–6631. doi: 10.1002/chem.201103870
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Article (Published version)
accessLevelRestricted
Identifiers
ISSN of the journal0947-6539
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Technical informations

Creation05/15/2012 9:48:00 AM
First validation05/15/2012 9:48:00 AM
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