Highly selective catalyst-dependent competitive 1,2-C→C, -O→C, and -N→C migrations from β-methylene-β-silyloxy-β-amido-α-diazoacetates

J Am Chem Soc. 2013 Jan 30;135(4):1244-7. doi: 10.1021/ja311392m. Epub 2013 Jan 17.

Abstract

Transition-metal catalysts direct 1,2-C→C, -O→C, and -N→C migrations from β-methylene-β-silyloxy-β-amido-α-diazoacetates with high selectivity. The key to achieving this unique display of differential selectivities relies on steric and stereoelectronic control by their catalytically generated metal carbenes.

Publication types

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

MeSH terms

  • Azo Compounds / chemistry*
  • Catalysis
  • Cyclization
  • Heterocyclic Compounds / chemical synthesis*
  • Heterocyclic Compounds / chemistry
  • Methane / analogs & derivatives*
  • Methane / chemistry
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Siloxanes / chemistry*

Substances

  • Azo Compounds
  • Heterocyclic Compounds
  • Organometallic Compounds
  • Siloxanes
  • carbene
  • Methane