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.
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