Nitridomanganese(V) Complexes:  Design, Preparation, and Use as Nitrogen Atom-Transfer Reagents

Abstract

Oxidation of organic substrates by direct oxygen-atom
\ntransfer from transition-metal complexes is of fundamental
\nimportance and has been subject to intensive investigation.
\nHighly selective methods for alkene epoxidation
\nand dihydroxylation have been described and are commonly
\nemployed in synthesis. By contrast, significantly fewer reagents and protocols are available for the analogous
\nnitrogen-atom-transfer process, despite the enormous
\npotential utility of such methodology. Recent efforts by other groups to develop general olefin amination
\nstrategies have led to impressive advances in both metalcatalyzed hydroxyamination and aziridination. Our
\ninterest in this area has resulted in the preparation and
\ncharacterization of novel nitridomanganese complexes
\nwhich may be activated for nitrogen-atom transfer. Pivotal
\nto the success of this research has been the development
\nof new protocols for the construction of these
\nmanganese nitride (Mn≡N) reagents. These systems have
\nproven to be versatile and effective aminating agents with
\ndifferent classes of olefins which include both silyl enol
\nethers and glycals (eq 1). The following account documents
\nthese findings and highlights the unique chemistry
\nof these complexes as nitrogen-atom-transfer reagents.