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We report a novel example of electro‐mediated photoredox catalysis (e‐PRC) in the reductive cleavage of C(sp3)−O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E‐selective and can be made Z‐selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide‐type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity‐determining C(sp3)−O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch‐type reductions. [ABSTRACT FROM AUTHOR]

Keywords: electrophotocatalysis; hydrogen atom transfer; photoelectrochemistry; photoredox catalysis; preassembly EN electrophotocatalysis hydrogen atom transfer photoelectrochemistry photoredox catalysis preassembly 1 1 1 03/11/22 20220314 NES 220314 B Molecular photoelectrochemistry b , allowing access to a broader window of single electron transfer chemistry in a greener way, is a rapidly expanding toolbox for synthesis and selective functionalizations of complex molecules. Inside Cover: Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability (Angew. Electrophotocatalysis, hydrogen atom transfer, photoelectrochemistry, photoredox catalysis, preassembly. [Extracted from the article]