Hydrozirconation and Its Applications

Abstract

Next to hydroboration and hydrostannylation, hydrozirconation is among the few general methods available for the stoichiometric conversion of readily available alkenes and alkynes into stable, strongly nucleophilic synthetic intermediates. More significantly, the sterically shielded carbon–zirconium bond of organozirconocenes can participate in transmetalation schemes that link zirconium chemistry with many other elements in the periodic table, in particular with the highly functional group tolerant late transition metals. The in situ conversion of alkenes and alkynes into chain-extended synthetic building blocks by sequential hydrozirconation and further metal-catalyzed or metal-mediated condensations with electrophiles is thus characterized by experimental convenience and considerable strategic flexibility. In addition, the number of synthetic protocols that use organozirconocenes directly for intra- or intermolecular carbon–carbon and carbon–heteroatom bond formations is steadily increasing. As an extension of our comprehensive treatment of the topic in 1996, this review concentrates on the developments in hydrozirconation and its applications in synthesis from 1996 through mid-2002.