A highly selective C�H amination reaction under iron catalysis will be presented. This novel method, which employs an inexpensive, non-toxic [Fe(III)Pc] catalyst (typically used as an industrial dye), displays a strong preference for allylic C�H amination over aziridination and all other C�H bond types (i.e. allylic > benzylic > ethereal > 3� > 2� >> 1�), with the highest chemoselectivities reported to date for nitrene-based C�H aminations. Moreover, in polyolefinic substrates, site selectivities can be controlled by the electronic and steric character of the allylic C�H bond. Although this reaction is shown to proceed via a stepwise mechanism, the stereoretentive nature of C�H amination for 3� aliphatic C�H bonds suggests a very rapid radical rebound step.

Iron-catalyzed intramolecular allylic C-H amination

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.