Interrogating Pd(II) anion metathesis using a bifunctional chemical probe: a transmetalation switch

John J. Molloy, Ciaran P. Seath, Matthew J. West, Calum McLaughlin, Neal J. Fazakerley, Alan R. Kennedy, David J. Nelson, Allan J. B. Watson

Research output: Contribution to journalLetter

21 Citations (Scopus)
13 Downloads (Pure)

Abstract

Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.
Original languageEnglish
Pages (from-to)126-130
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number1
Early online date22 Dec 2017
DOIs
Publication statusPublished - 10 Jan 2018

Keywords

  • cross-coupling
  • control
  • transmetalation switch

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