Inspired by the reaction chemistry of heme-based enzymes, we have generated a new class of semi-porphyrin (dipyrromethene) supported iron complexes capable of C-H bond functionalization via nitrene, oxo, and carbene transfer. Our progress with iron-mediated, C-H bond amination catalysis will be highlighted. Reaction of aryl and alkyl organoazides with ferrous dipyrromethene complexes results in rapid azide decomposition and formation of a reactive Fe(III) imido radical intermediate. In the presence of benzylic, allylic and aliphatic C�H bonds, the nitrene functionality is catalytically transferred from the Fe(III) intermediate to substrate via an intermolecular H-atom abstraction/radical rebound pathway. Utilizing this same chemistry in an intramolecular cyclization reaction, we can access a wide range of N-heterocycles from linear alkyl azides. Reaction of the dipyrromethene iron complex with linear azides terminated with benzyl, allyl, or alkyl groups generates phenyl, vinyl, or alkyl substituted N-heterocycles. The reaction is amenable to the formation of a wide variety of substituted azetidines, pyrrolidines, piperidines, and oxazolidines.

N-heterocycle synthesis via iron-catalyzed C-H bond amination

245th National Meeting (2013)

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