Synthetic applications of Pd(II)-catalyzed C-H carboxylation and mechanistic insights: Expedient routes to anthranilic acids, oxazolinones, and quinazolinones

Ramesh Giri, Jonathan K. Lam, Jin Quan Yu

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247 Scopus citations

Abstract

A Pd(II)-catalyzed reaction protocol for the carboxylation of ortho-C-H bonds in anilides to form N-acyl anthranilic acids has been developed. This reaction procedure provides a novel and efficient strategy for the rapid assembly of biologically and pharmaceutically significant molecules, such as benzoxazinones and quinazolinones, from simple anilides without installing and removing an external directing group. The reaction conditions are also amenable to the carboxylation of N-phenyl pyrrolidinones. A monomeric palladacycle containing p-toluenesulfonate as an anionic ligand has been characterized by X-ray crystallography, and the crucial role of p-toluenesulfonic acid in the activation of C-H bonds in the presence of carbon monoxide is discussed. Identification of two key intermediates, a mixed anhydride and benzoxazinone formed by reductive elimination from organometallic Ar(CO)Pd(II)-OTs species, provides mechanistic evidence for a dual-reaction pathway.

Original languageEnglish (US)
Pages (from-to)686-693
Number of pages8
JournalJournal of the American Chemical Society
Volume132
Issue number2
DOIs
Publication statusPublished - Jan 20 2010

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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