Abstract
<jats:p>Alkoxy radicals are versatile intermediates capable of engaging in diverse reaction pathways, yet the selective exploitation of their reactivity under mild conditions remains a significant challenge. Herein, we expand the synthetic utility of N-oxime-derived bifunctional radical reagents by exploiting two complementary alkoxy radical pathways, β-scission and intramolecular alkene cyclization, in combination with metal-free radical 1,2-carboimination of activated alkenes. Under visible-light irradiation using 5CzBN as an organic photocatalyst, the bifunctional precursors generate alkoxy radicals that undergo substrate-controlled β-scission or cyclization to produce carbon-centered radicals, which are regioselectively trapped by activated alkenes and subsequently coupled with iminyl radicals. This modular strategy provides direct access to remotely iminofunctionalized carbonyl compounds and tetrahydrofurans with broad substrate scope and excellent chemoselectivity, including the latestage functionalization of complex biomolecules and pharmaceuticals. Mechanistic studies support an energy-transfer-initiated radical-chain mechanism</jats:p>