A variety of Huisgen cyclization or nitrene/carbene alkyne cascade reactions with different types of termination were investigated. Accessible nitrene precursors were assessed, and carbonazidates were found to be the only effective initiators. Solvents, terminal alkynyl substituents, and catalysts can all impact the reaction outcome. Study of the mechanism both computationally (by density functional theory) and experimentally revealed relevant intermediates and plausible reaction pathways.