Formal Dyotropic Rearrangements in Organometallic Transformations

Abstract

AbstractA thorough understanding of the mechanistic steps that occur in organometallic processes is crucial to the development of new, increasingly sophisticated transformations. This microreview discusses an unusual class of organometallic reactions that occur through formal Type I dyotropic rearrangements, defined as processes involving the interchange of two groups along a stationary scaffold by breaking and reforming two σ bonds in which at least one σ bond is a M–X bond. Examples are subdivided into two categories – stoichiometric and catalytic – and further classified by the number of atoms across which the migrating groups interchange positions. The metal can either serve as the migrating group or function as part of the stationary scaffold. Furthermore, these rearrangements can proceed through a wide variety of different mechanisms that include oxidative insertion/reductive elimination, radical processes, or pathways in which the metal does not change oxidation state.