Abstract
Formal [5 + 1] cycloadditions between aryl-substituted vinylcyclopropanes and nitrenoid precursors are reported. The method, which employs Rh(2)(esp)(2) as a catalyst, leads to the highly regioselective formation of substituted tetrahydropyridines. Preliminary mechanistic studies support a stepwise, polar mechanism enabled by the previously observed Lewis acidity of Rh-nitrenoids. Overall, this work expands the application of nitrene-transfer cycloaddition, a relatively underexplored approach to heterocycle synthesis, to the formation of six-membered rings.