Regio- and Diastereoselective Synthesis of α-Cyanoamines by Anodic Oxidation of 6-Membered α-Silylamines

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

“…The α-cyanation of cyclic amines can be accomplished in numerous ways either via one-electron or two-electron redox chemistries or via HAT processes as summarized in Scheme . Early electrochemical methods focus on cation pool or direct oxidation approaches. − Onomura reported an undivided cell electrolysis method using TMSCN, MeSO 3 H, and graphite carbon (GRC) electrodes at 0 °C (method A1) . The acid was essential for the generation of product and was proposed to control the equilibrium between HCN and CN – in addition to suppressing enamine formation from the proposed iminium intermediate.…”

Electrochemical strategies for C–H functionalization and C–N bond formation

“…50 This concept relies on the inherent properties of the electroauxiliaries to lower the oxidation potential of the substrate, thereby facilitating and providing enhanced control of the anodic oxidation of the substrate. The electroauxiliaries employed in Shono-type oxidations have typically been silylbased, [199][200][201][202][203][204][205][206][207][208][209][210][211][212][213] although 2,4,6-trimethoxyphenyl 214 and sulfurbased [215][216][217] electroauxiliaries have also been employed.…”

Modern Strategies in Electroorganic Synthesis

“…Cyanide anion is also effective as a nucleophile in electroauxiliary-assisted electrochemical oxidation of nitrogen-containing compounds. For example, the anodic oxidation of cyclic α-silyl amines in the presence of sodium cyanide gives rise to effective cyanation under mild conditions (Scheme ) . The control of the reaction pathway by the silyl group is demonstrated by the fact that methoxylation occurs selectively in the cyclohexane ring.…”