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 <i>O</i>-alkyl ethers <i>via</i> a catalytic addition-elimination strategy. The Rh-catalyzed arylation (alkenylation) and Ni-catalyzed borylation and silylation proceed <i>via</i> 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, 2<i>H</i>-naphthalene, indene, etc., significantly expanding the accessibility and synthetic utility of ACPs.