Visible-Light-Induced Hydrogen Atom Transfer En Route to Exocylic Alkenylation of Cyclic Ethers Enabled by Electron Donor–Acceptor Complex

An electron donor-acceptor (EDA)-triggered hydrogen atom transfer (HAT) process is developed for the efficient generation of an α-alkoxy radical from cyclic ethers to synthesize exocyclic alkenylated ethers with exclusive E-selectivity. A judiciously chosen donor-acceptor pair (DABCO and maleimide) serves as the desired HAT reagent under visible light irradiation without using any photocatalyst or peroxide. A wide variety of substrates were explored to demonstrate the diverse applicability and practical viability of this cross-dehydrogenative transformation. Detailed mechanistic studies revealed a radical reaction pathway under the oxidative environment.