Bromonium ion induced transannular oxonium ion formation-fragmentation in model obtusallene systems and structural reassignment of obtusallenes V-VII

J Org Chem. 2009 Mar 6;74(5):1835-41. doi: 10.1021/jo8026577.

Abstract

Ring-closing metathesis was used to construct the strained 11-membered ring of obtusallenes II (and IV). Bromonium ion induced transannular oxonium ion formation-fragmentation gave the macrocyclic carbon skeleton of obtusallene VII with a bromine atom at C-13, in line with a previously published hypothesis. An additional brominated [5.5.1]bicyclotridecane adduct that must arise from a bromonium ion induced transannular oxonium ion formation-fragmentation could also be isolated, suggesting that this adduct represents the core of an as yet undiscovered natural product. An authentic sample of obtusallene V was studied by NMR spectroscopy, and the position of the halogens at C-7 and C-13 was reassigned on the basis of a (13)C NMR chlorine induced isotopic shift. This revised structure was subsequently confirmed by X-ray crystallography. These findings allow us to confidently conclude that the structures of obtusallenes VII and VI should also be reassigned.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bromine / chemistry*
  • Cyclization
  • Ethers, Cyclic / chemical synthesis
  • Ethers, Cyclic / chemistry*
  • Ions / chemistry
  • Models, Molecular
  • Molecular Conformation
  • Oxygen / chemistry*
  • Stereoisomerism

Substances

  • Ethers, Cyclic
  • Ions
  • obtusallene
  • Oxygen
  • Bromine