Zirconocene Complexes of Imines: General Synthesis, Structure, Reactivity, and in Situ Generation To Prepare Geometrically Pure Allylic Amines

Article abstract of DOI:10.1021/ja00194a052

A general method for the preparation of zirconocene complexes of imines has been developed.The X-ray crystal structure of the (trimethylsilyl)benzaldimine complex 2b shows that these complexes should be viewed as metallaaziridenes due to significant ?-donation from the zirconium center to the ?^* orbitals of the coordinated imine.These complexes undergo a number of chemo-, regio-, and diastereoselective coupling reactions with unsaturated organic compounds to cleanly form metallacyclic compounds.In situ generation of the complexes followed by coupling with alkynes and hydrolysis affords a general route to geometrically pure allylic amines.