We present the synthesis of a B-N analogue of polystyrene, poly(N-methyl-B-vinylazaborine) in high molecular weight (M = 24.9 kDa). Furthermore, it was possible to prepare a copolymer with the C-C analogue. A thorough comparison between the polymers by NMR spectroscopy, TGA, DSC and GPC showed significant differences between these polymers.

The development of a high yielding, both nucleophile and electrophile selective cross-coupling reaction with aromatic rings is presented. The reaction is general with respect to functional groups. Furthermore, the products still contain a boronic ester and a bromide. These two functional groups allow them to be easy-to-prepare, highly complex starting materials for further reactions, avoiding protecting group transformations.

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.