om400906u_si_001.pdf (783.81 kB)
Organozinc Catalyst on a Phenalenyl Scaffold for Intramolecular Hydroamination of Aminoalkenes
journal contribution
posted on 2013-12-09, 00:00 authored by Arup Mukherjee, Tamal K. Sen, Pradip Kr. Ghorai, Swadhin K. MandalThe
syntheses and characterization of two organozinc compounds were accomplished
by reacting phenalenyl (PLY)-based ligands with ZnMe2.
Reactions of [HN(Cy),O-PLY] and [HN(Cy),N(Cy)-PLY] ligands with ZnMe2 led to the formation of the dimeric orange-colored organozinc
compound [N(Cy),O-PLY-ZnMe]2 (1) and red-colored
monomeric organozinc compound [N(Cy),N(Cy)-PLY-ZnMe] (2) under evolution of methane. Both 1 and 2 were characterized by NMR spectroscopy, elemental analysis, and
single-crystal X-ray diffraction study. The organozinc compound 2 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 in situ. The catalytic result obtained from the present
catalyst 2 was compared with the catalysts having similar
structure from previous studies. The DFT calculation indicates that
the stability of the in situ generated cation plays
a significant role in the catalytic activity in the hydroamination
reaction.