Organozinc Catalyst on a Phenalenyl Scaffold for Intramolecular Hydroamination of Aminoalkenes

The syntheses and characterization of two organozinc compounds were accomplished by reacting phenalenyl (PLY)-based ligands with ZnMe<sub>2</sub>. Reactions of [HN­(Cy),O-PLY] and [HN­(Cy),N­(Cy)-PLY] ligands with ZnMe<sub>2</sub> led to the formation of the dimeric orange-colored organozinc compound [N­(Cy),O-PLY-ZnMe]<sub>2</sub> (<b>1</b>) and red-colored monomeric organozinc compound [N­(Cy),N­(Cy)-PLY-ZnMe] (<b>2</b>) under evolution of methane. Both <b>1</b> and <b>2</b> were characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction study. The organozinc compound <b>2</b> was tested as a catalyst for intramolecular hydroamination of both unactivated primary and secondary aminoalkenes in the presence of an externally added activator, which generated the zinc-based cation <i>in situ</i>. The catalytic result obtained from the present catalyst <b>2</b> was compared with the catalysts having similar structure from previous studies. The DFT calculation indicates that the stability of the <i>in situ</i> generated cation plays a significant role in the catalytic activity in the hydroamination reaction.