Propargyltrimethylsilanes as allene equivalents in transition metal-catalyzed [5 + 2] cycloadditions

Org Lett. 2014 Jun 6;16(11):2923-5. doi: 10.1021/ol501114q. Epub 2014 May 12.

Abstract

Conventional allenes have not been effective π-reactive 2-carbon components in many intermolecular cycloadditions including metal-catalyzed [5 + 2] cycloadditions. We report herein that rhodium-catalyzed [5 + 2] cycloadditions of propargyltrimethylsilanes and vinylcyclopropanes provide, after in situ protodesilylation, a highly efficient route to formal allene cycloadducts. Propargyltrimethylsilanes function as safe, easily handled synthetic equivalents of gaseous allenes and hard-to-access monosubstituted allenes. In this one-flask procedure, they provide cycloadducts of what is formally addition to the more sterically encumbered allene double bond.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkadienes / chemistry*
  • Catalysis
  • Cycloaddition Reaction
  • Molecular Structure
  • Rhodium / chemistry*
  • Stereoisomerism
  • Transition Elements / chemistry*
  • Trimethylsilyl Compounds / chemical synthesis*
  • Trimethylsilyl Compounds / chemistry*

Substances

  • Alkadienes
  • Transition Elements
  • Trimethylsilyl Compounds
  • propadiene
  • Rhodium