Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.

Original languageEnglish
Pages (from-to)1582-1586
Number of pages5
JournalTetrahedron Letters
Volume60
Issue number24
DOIs
StatePublished - 13 Jun 2019

    Research areas

  • Kinetic control, Metal carbene species, Oxonium ylides, Quantum chemical calculations, Stevens rearrangement, [1,4]-Alkyl shift, α-Diazocarbonyl compounds, alpha-Diazocarbonyl compounds, CATALYSIS, INSERTION, RING EXPANSION, DECOMPOSITION, REARRANGEMENTS, OXETANES, HETEROCYCLES, CARBENES, DERIVATIVES, MACROCYCLIZATION

    Scopus subject areas

  • Drug Discovery
  • Biochemistry
  • Organic Chemistry

ID: 41855948