Isomerization of Terminal Epoxides by a [Pd–H] Catalyst: A Combined Experimental and Theoretical Mechanistic Study

An
unusual palladium hydride complex has been shown to be a competent
catalyst in the isomerization of a variety of terminal and internal
epoxides. The reaction displayed broad scope and synthetic utility.
Experimental and theoretical evidence are provided for an unprecedented
hydride mechanism characterized by two distinct enantio-determining
steps. These results hold promise for the development of an enantioselective
variant of the reaction.