Abstract
Directed hydrogen atom transfer to alkenes is described. The process is catalyzed by iron complexes and allows for the site-selective hydrofunctionalization of polyenols. Experimental data suggest that coordination of the hydroxy group to the iron hydride intermediate plays an important role in preferential engagement of the allylic alcohol motif and provides a new basis for selectivity in radical hydrofunctionalization events. As a proof of concept, β- and γ-amino alcohols are prepared from the corresponding polyenols in a selective manner.