Zirconocene-Mediated Selective C–C Bond Cleavage of Strained Carbocycles: Scope and Mechanism

International audienceSeveral approaches using organozirconocene species for the remote cleavage of strained three-membered ring carbocycles such as w-ene polysubstituted cyclopropanes, alkylidenecyclopropanes, w-ene spiro[2.2]pentanes and wene cyclopropyl methyl ethers, into stereodefined organometallic intermediates were successfully developed to access highly stereoenriched scaffolds in good yields. Two acyclic stereocenters including a quaternary carbon stereogenic carbon atom were easily obtained with very high diastereoselectivities. DFT calculations and isotopic labeling experiments were performed to delineate the origin of the observed stereoselectivities