Electrochemical radical–polar crossover diesterification of alkenes with carboxylic acids

Abstract

An electrochemical method for the direct synthesis of 1,2-diester derivatives from abundant and readily available olefins and carboxylic acids is described. The method is applicable to a variety of aromatic/aliphatic...

Electrochemical remote C(sp3)–H thiocyanation

“…Based on control experiments and previous reports, 16b a possible radical-polar crossover mechanism is shown in Scheme 6. 20 The sulfonamide 1 is first deprotonated by the hexafluoroisopropanol anion, followed by anodic oxidation to produce N-radical 40, which undergoes 1,5-HAT to furnish the translocated C-radical 41. The thiocyano radical trapping process is precluded, as the free energy barrier is higher (26.9 kcal mol −1 ).…”

Electrochemically enabled (3+2) cycloaddition of unbiased alkenes and β-dicarbonyls

“…Recently, radical polar crossover reactions have gained significant attention for multiple bond-forming reactions. 29,30 Anodic oxidation of 1,3-dicarbonyl in the presence of alkene to synthesize dihydrofurans was reported in 1968 by Scha ¨fer and coworkers under constant potential electrolysis (Scheme 1). 31 Later, in 1986, Yoshida/Isoe and their coworkers reported the synthesis of dihydrofuran derivatives under constant current electrolysis conditions using an operationally simple two-electrode setup with improved yields.…”

“…Recently, radical polar crossover reactions have gained significant attention for multiple bond-forming reactions. 29,30…”

Direct alkylation of quinoxalinones with electron-deficient alkenes enabled by a sequential paired electrolysis

“…9 Initially, the electroreduction of quinoxalinones I would give radical ion IV by applying a sufficiently reducing potential. 10 The radical addition of IV to alkenes followed by protonation would afford carbon-centered radical V, which undergoes reductive radical-polar crossover 11 and subsequent protonation to generate intermediate VI. Finally, the consecutive two-electron oxidation followed by deprotonation would realize the C-3 alkylation.…”