A differentially protected diboron bearing the naphthalene-1,8-diaminato group Oil one of the two boron atoms undergoes highly regioselective diboration with terminal alkynes in the presence of Pt or Ir catalysts. giving 1-alkene-1,2-diboronic, acid derivatives in which the less reactive B(dan) group is located at the terminal position. The products undergo selective Suzuki-Miyaura coupling With aryl bromides at the internal boronyl group, leading to the formation of 2,2-substituted alkenylboronic acid derivatives.