Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides

Anna Pintus, Luca Rocchigiani, Julio Fernandez-Cestau, Peter H.M. Budzelaar, Manfred Bochmann

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Abstract

The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer-sphere mechanism to cleanly form trans-insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio- and stereospecific for the formation of Z-vinyl isomers, with Z/E ratios of >99:1 in most cases.
Original languageEnglish
Pages (from-to)12321–12324
Number of pages4
JournalAngewandte Chemie International Edition
Volume55
Issue number40
Early online date4 Sep 2016
DOIs
Publication statusPublished - 26 Sep 2016

Keywords

  • alkynes
  • density functional calculations
  • gold
  • insertion
  • reaction mechanisms

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