37689-18-2Relevant academic research and scientific papers
Dinuclear Pathways for the Activation of Strained Three-Membered Rings
Rounds, Heather R.,Zeller, Matthias,Uyeda, Christopher
, p. 545 - 550 (2018/03/08)
Dinuclear, strain-induced ring-opening reactions of vinylaziridines and vinylcyclopropanes are described. The previously reported [NDI]Ni2(C6H6) complex (NDI = naphthyridine-diimine) reacts with N-tosyl-2-vinylaziridine via C-N oxidative addition to generate a dinickel metallacyclic product. On the basis of this stoichiometric reactivity, the [NDI]Ni2(C6H6) complex is shown to be a highly active catalyst for the rearrangement of vinylcyclopropane to cyclopentene. Notably, 2-phenyl-1-vinylcyclopropane undergoes regioselective activation at the less hindered C-C bond in contrast to the noncatalytic thermal rearrangement. DFT calculations provide insight into the ability of the Ni-Ni bond to stabilize key intermediates and transition states along the catalytic pathway.
