Orthogonal Pd- and Cu-based catalyst systems for C- and N-arylation of oxindoles

J Am Chem Soc. 2008 Jul 23;130(29):9613-20. doi: 10.1021/ja803179s. Epub 2008 Jun 28.

Abstract

In the cross-coupling reactions of unprotected oxindoles with aryl halides, Pd- and Cu-based catalyst systems displayed orthogonal chemoselectivity. A Pd-dialkylbiarylphosphine-based catalyst system chemoselectively arylated oxindole at the 3 position, while arylation occurred exclusively at the nitrogen using a Cu-diamine-based catalyst system. Computational examination of the relevant L1Pd(Ar)(oxindolate) and diamine-Cu(oxindolate) species was performed to gain mechanistic insight into the controlling features of the observed chemoselectivity.

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

  • Benzene Derivatives / chemical synthesis
  • Benzene Derivatives / chemistry*
  • Catalysis
  • Copper / chemistry*
  • Hydrocarbons, Halogenated / chemistry
  • Indoles / chemical synthesis
  • Indoles / chemistry*
  • Ligands
  • Organometallic Compounds / chemistry
  • Oxindoles
  • Palladium / chemistry*
  • Pyrrolidinones / chemical synthesis
  • Pyrrolidinones / chemistry
  • Thermodynamics

Substances

  • Benzene Derivatives
  • Hydrocarbons, Halogenated
  • Indoles
  • Ligands
  • Organometallic Compounds
  • Oxindoles
  • Pyrrolidinones
  • 2-oxindole
  • Palladium
  • Copper