Photoredox catalysis (PRC) and synthetic organic electrochemistry (SOE) are often considered competing technologies in organic synthesis. Their fusion has been largely overlooked. We review state‐of‐the‐art synthetic organic photoelectrochemistry, grouping examples into three categories: 1) electrochemically mediated photoredox catalysis (e‐PRC), 2) decoupled photoelectrochemistry (dPEC), and 3) interfacial photoelectrochemistry (iPEC). Such synergies prove beneficial not only for synthetic “greenness” and chemical selectivity, but also in the accumulation of energy for accessing super‐oxidizing or ‐reducing single electron transfer (SET) agents. Opportunities and challenges in this emerging and exciting field are discussed.

Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of dithianes, and SRN1 reactions. Direct electron transfer would imply that alkali metal alkoxides are willing partners in these electron transfer reactions, but the literature reports provide little or no experimental evidence for this. This paper examines each of these classes of reaction in turn, and contests the roles proposed for KOtBu; instead, it provides new mechanistic information that in each case supports the in situ formation of organic electron donors. We go on to show that direct electron transfer from KOtBu can however occur in appropriate cases, where the electron acceptor has a reduction potential near the oxidation potential of KOtBu, and the example that we use is CBr4. In this case, computational results support electrochemical data in backing a direct electron transfer reaction.

Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of the visible photon (>4.0 V vs. SCE) in anti-Kasha photo(electro)chemical super-oxidations of arenes.

We report a simple one-pot protocol that affords functionalization of N-CH groups in N-methyl-N,N-dialkylamines with high selectivity over N-CHR or N-CHR groups. The radical cation DABCO, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C-H abstraction from N-CH groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH groups. Chemoselectivity, scalability, and recyclability of reagents are demonstrated, and a mechanistic proposal is corroborated by computational and experimental results. The utility of the transformation is demonstrated in the late-stage site-selective functionalization of natural products and pharmaceuticals, allowing rapid derivatization for investigation of structure-activity relationships.