Research Progress on the Carbonylation of Methylenecyclopropanes

Small‐ring compounds have garnered significant attention in organic synthesis due to their high reactivity. Methylenecyclopropane (MCP), a unique C ₃ ‐synthon combining a highly strained three‐membered ring with a terminal alkene, undergoes controllable ring‐opening and efficient transformation under transition metal catalysis. Carbonylation reactions, characterized by high atom economy and excellent functional group compatibility, represent a core methodology for constructing carbonyl compounds. Combining MCP with carbonylation reactions leverages the synergistic advantages of strained‐ring opening and alkene difunctionalization, enabling one‐step formation of multiple bonds, precise site‐selective control, and efficient construction of complex fused‐ring and medium‐ring skeletons. This review summarizes the advancements in transition‐metal‐catalyzed carbonylation of MCPs, including asymmetric carbonylation, selective CC bond cleavage carbonylation, ring‐opening carbonylative cyclization, and strain‐driven cycloadditions. It details catalytic systems based on Rh, Pd, Cu, Mn, Ru (both single‐metal and bimetallic cooperative systems) and their ring‐opening mechanisms. Key developments in asymmetric hydroformylation, borylcarbonylation, dialkoxycarbonylation, and tandem cyclization are highlighted.