Iron-Catalyzed Cross-Electrophile Coupling of Inert C-O Bonds with Alkyl Bromides

An example of iron-catalyzed cross-electrophile couplingof inert C-O bonds with alkyl bromides via aniron/B_(2)pin_(2) catalytic system has been developed.Aryl and heteroaryl carbamates can smoothly undergothis transformation under mild conditions, deliveringthe alkylated products with good efficiency.This protocol exhibits good functional group compatibilityand enables the late-stage functionalizationof biorelevant compounds, thus providingexcellent opportunities for applications in medicinalchemistry. Control experiments and computationalstudies reveal that a high spin Fe(I/II/III) catalyticmechanism might be involved in this reactionthrough single electron transfer to activate alkylbromides, oxidative addition of aryl carbamates, andreductive elimination to form Csp^(2)-Csp^(3) bonds.