Intramolecular Aromatic Amination through Iron-Mediated Nitrene Transfer

摘要

Much attention has been concentrated on metal-catalyzed atom and group transfers to organic molecules as a strategy for carbon-heteroatom bond formation in synthetic organic chemistry. Similar to isolobal epoxidation reactions, nitrene (that is, RN=) transfer to olefins (that is, aziridination) can be catalyzed by metalloporphyrins, iron corroles, as well as low-coordinate copper complexes and salts. Nitrene insertions to give aliphatic C-H bond animations have also been effected by metalloporphyrins or cytochrome P450. In contrast, metal-catalyzed arene amination is practically unknown, even though free organonitrenes will readily add to aromatics. Substoichiometric and unselective naphthalene amination by an uncharacterized adduct of iron(II) chloride and chloramine-T has been reported, along with a handful of possibly analogous organometallic ligand transformations.