The mechanism of carboxylative cyclization of propargylamine by N-heterocyclic carbene complexes of Au(I).

Jack V. Davis, Mohan M. Gamage, Oswaldo Guio, Tahani A.C.A. Bayrakdar, Steven P. Nolan, Manuel Temprado, Burjor Captain, Carl D. Hoff

Research output: Contribution to journalArticlepeer-review

Abstract

The complex [Au(IPr)(2-oxazolidinone)] (1 = IKa) was prepared from reaction of [Au(IPr)Cl] (2), K2CO3, and propargyl amine (PPA). Kinetic studies have been performed for acid cleavage of 1 to yield the oxazolidinone product and an [Au(IPr)(X)] adduct. The fastest rates of cleavage were found to occur for the hydrogen chloride salt of PPA (PPA-HCl) and for the CO2 adduct of PPA, PPA-CO2 = the carbamic acid (CA). This transformation was studied as a function of [CA], pressure of CO2 as well as temperature. Detailed computational studies support the formation of a key intermediate and are also in agreement with a rapid carbonylation/decarbonylation reaction. The computed reactions mechanisms for addition of PPA-HCl and CA are also presented as well as the crystal structure of 1.

Original languageEnglish (US)
Article number121583
JournalJournal of Organometallic Chemistry
Volume934
DOIs
StatePublished - Feb 15 2021

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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