Multicomponent Oxyalkylation of Styrenes Enabled by Hydrogen‐Bond‐Assisted Photoinduced Electron Transfer

Herein, we disclose a strategy for the activation of N‐(acyloxy)phthalimides towards photoinduced electron transfer through hydrogen bonding. This activation mode enables efficient access to C(sp3)‐centered radicals upon decarboxylation from bench‐stable and readily available substrates. Moreover, we demonstrate that the formed alkyl radicals can be successfully employed in a novel redox‐neutral method for constructing sp3−sp3 bonds across styrene moieties that gives straightforward access to complex alcohol and ether scaffolds. OH, I see: An efficient strategy to activate N‐(acyloxy)phthalimides towards direct photoinduced electron transfer with photoexcited catalysts was developed. This strategy enables efficient visible‐light‐mediated formation of alkyl radicals that can be used to achieve the challenging oxyalkylation of styrenes under mild redox‐neutral conditions.