Nucleophile-Selective Cross-Coupling Reactions with Vinyl and Alkynyl Bromides on a Dinucleophilic Aromatic Substrate

A nucleophile-selective cross-coupling reaction on an aromatic compound bearing two metal groups, Bpin and SnMe₃, has been developed. Previously, only aryl bromides and iodides could be used as electrophilic components, but in this work, the scope could be extended to vinyl and alkynyl bromides as electrophiles. This means that the roles typical in Sonogashira couplings or Heck reactions of the aromatic ring as the dielectrophile coupling to vinyl and alkynyl metal species are reversed, which presents a new tool for organic synthesis. The first nucleophilic site to react is the stannyl group, and subsequently, a Suzuki-Miyaura cross-coupling reaction can take place on the same molecule.