Strategic Leverage of β-OH Elimination for Catalytic Assembly of Alkylidenecyclopropanes

We report the transition-metal-catalyzed synthesis of ACP from readily available cyclopropenyl α-carbon alcohols and their O-alkyl ethers via a catalytic addition–elimination strategy. The Rh-catalyzed arylation (alkenylation) and Ni-catalyzed borylation and silylation proceed via OH (OR)-directed addition with subsequent OH (OR) elimination events to deliver various functionalized ACPs (FACPs) with broad functional group compatibility and good to high yields. The products serve as a synthetic linchpin for more elaborate scaffolds such as cyclopropyl alcohol, skipped halogenated diene, 2H-naphthalene, indene, etc., significantly expanding the accessibility and synthetic utility of ACPs.