Selectivity switch in the synthesis of vinylgold(I) intermediates

A. Stephen K Hashmi, Andreas M. Schuster, Sylvain Gaillard, Luigi Cavallo, Albert Poater, Steven P. Nolan

Research output: Contribution to journalArticlepeer-review

101 Scopus citations

Abstract

An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.
Original languageEnglish (US)
Pages (from-to)6328-6337
Number of pages10
JournalOrganometallics
Volume30
Issue number22
DOIs
StatePublished - Nov 28 2011

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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