Ligand‐Controlled Regiodivergence in Nickel‐Catalyzed Vinylcyclopropane Rearrangement
Keiichi Irifune, Ken Yamazaki, Takayuki Nakamuro, Masahiro Murakami, Tomoya Miura
Abstract
Abstract A ligand‐controlled regiodivergence in Ni‐catalyzed rearrangement of vinylcyclopropanes to 1,4‐ or 1,5‐disubstituted cyclopentenes is reported. The 1,4‐ or 1,5‐disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six‐membered η 1 ‐allyl intermediate.
Topics & Concepts
CyclopenteneLigand (biochemistry)Catalytic cycleCatalysisChemistrySelectivityNickelMedicinal chemistryCombinatorial chemistryStereochemistryOrganic chemistryReceptorBiochemistryCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsCatalytic Alkyne Reactions