Highly selective intramolecular carbene insertion into primary C-H bond of α-diazoacetamides mediated by a (p-cymene)ruthenium(II) carboxylate complex

J Am Chem Soc. 2012 May 9;134(18):7588-91. doi: 10.1021/ja3006989. Epub 2012 Apr 24.

Abstract

Complex [(p-cymene)Ru(η(1)-O(2)CCF(3))(2)(OH(2))] mediated transformation of α-diazoacetamides ArCH(2)N(C(CH(3))(3))C(O)CHN(2) to result in carbene insertion into the primary C-H bond exclusively, with the γ-lactam products being isolated in up to 98% yield. This unexpected reaction is striking in view of the presence of usually more reactive sites such as secondary C-H bonds in the substrates. DFT calculations based on proposed Ru-carbene species provide insight into this unique selectivity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetamides / chemistry*
  • Azo Compounds / chemistry*
  • Carboxylic Acids / chemistry*
  • Coordination Complexes / chemistry
  • Cymenes
  • Methane / analogs & derivatives*
  • Methane / chemistry
  • Models, Molecular
  • Monoterpenes / chemistry*
  • Ruthenium / chemistry*

Substances

  • Acetamides
  • Azo Compounds
  • Carboxylic Acids
  • Coordination Complexes
  • Cymenes
  • Monoterpenes
  • 4-cymene
  • carbene
  • Ruthenium
  • Methane