Deep Electroreductive Chemistry: Harnessing Carbon- and Silicon-Based Reactive Intermediates in Organic Synthesis

A tutorial on asymmetric electrocatalysis

“…While these cations are electrochemically inert, they may or may not interact with the homogenous reactants as Lewis acids. 47,48 Alternatively, recent advances have shown that homogenous sacrificial reductants can be employed in lieu of sacrificial metal anodes, in combination with an inert electrode such as carbon and platinum. 49 The most common sacrificial reductants are amines (e.g., triethylamine and diisopropylethylamine) and phosphines (e.g., triphenylphosphine).…”

Electrocatalytic oxidative C–H cycloamination towards tricyclic [1,2,4]triazolo-[3,4-i]purine nucleosides mediated by bromide ions

“…Initially, the anodic oxidation of the bromide anion resulted in the formation of molecular bromine, which reacted with 1a to afford the active N–Br species A . Then, nitrogen-centered radical B was generated either by a single electron transfer (SET) procedure on the cathode surface 21 or homolytic cleavage of the N–Br bond. 20 a Intermediate B was easily converted to its radical resonance structure C , which subsequently underwent direct intramolecular cyclization leading to radical intermediate D .…”

Electrochemically Driven Deoxygenative Borylation of Alcohols and Carbonyl Compounds

“…Reductive electrochemistry has emerged in recent years as a powerful tool for the activation of strong bonds . In previous work (Scheme A, upper), we showed that at a sufficiently reducing potential, an alkyl halide ( A ) can undergo a sequence of electron transfer–chemical reaction–electron transfer (ECE) processes that results in cleavage of the C–X bond to form a carbanion intermediate ( F ) .…”