Strained, three-membered rings were found to undergo oxidative addition to the previously reported [iPrNDI]Ni2(C6H6) complex [NDI = napthyridine-diimine). Activation of the C-N bond of 1-tosyl-2-vinylaziridine generates a dinickel metallacyclic product. Based on this reactivity, the [iPrNDI]Ni2(C6H6) complex was shown to be a highly active catalyst for rearranging vinylcyclopropanes to cyclopentenes. Notably, 2-phenyl-1-vinylcyclopropane undergoes regioselective activation at the less hindered C–C bond in contrast to the non-catalytic 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.

Dinuclear pathways for the activation of strained three-membered rings

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.