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

Abstract

Oxidation of organic substrates by direct oxygen-atom transfer from transition-metal complexes is of fundamental importance and has been subject to intensive investigation. Highly selective methods for alkene epoxidation and dihydroxylation have been described and are commonly employed in synthesis. By contrast, significantly fewer reagents and protocols are available for the analogous nitrogen-atom-transfer process, despite the enormous potential utility of such methodology. Recent efforts by other groups to develop general olefin amination strategies have led to impressive advances in both metalcatalyzed hydroxyamination and aziridination. Our interest in this area has resulted in the preparation and characterization of novel nitridomanganese complexes which may be activated for nitrogen-atom transfer. Pivotal to the success of this research has been the development of new protocols for the construction of these manganese nitride (Mn≡N) reagents. These systems have proven to be versatile and effective aminating agents with different classes of olefins which include both silyl enol ethers and glycals (eq 1). The following account documents these findings and highlights the unique chemistry of these complexes as nitrogen-atom-transfer reagents.

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