Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans: scope and mechanism

J Org Chem. 2015 May 15;80(10):5196-209. doi: 10.1021/acs.joc.5b00604. Epub 2015 May 6.

Abstract

A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by (13)C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond of the cyclopropane to form a platinacyclobutane intermediate. To our knowledge, this is the first alkoxy-substituted platinacyclobutane that has been observed spectroscopically. The scope and a proposed mechanism of this new Pt-catalyzed transformation are described.

Publication types

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

MeSH terms

  • Carbon Radioisotopes / chemistry*
  • Catalysis
  • Cyclopropanes / chemistry*
  • Furans / chemical synthesis*
  • Furans / chemistry
  • Oxidation-Reduction
  • Platinum Compounds / chemical synthesis*
  • Platinum Compounds / chemistry*
  • Spiro Compounds / chemistry*

Substances

  • Carbon Radioisotopes
  • Cyclopropanes
  • Furans
  • Platinum Compounds
  • Spiro Compounds
  • cyclopropane