One-Pot Vicinal and Geminal Double Carboalkoxylation with N-Carboalkoxy-imidazole by Electroreduction of Aromatic Vinyl and Imine Derivatives

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

“…658,659 An analogous geminal double carboalkoxylation of imine derivatives has been achieved in a similar fashion. 659 In the reduction of styrenes, the styrenyl radical anion could also react with phenyl diesters where the nucleophilic terminal carbon could add into a carbonyl. The resulting homoenolate was found to undergo cyclization to eventually afford cyclopropyl spirolactones after the loss of a phenol (Figure 40G, right).…”

“…Nishiguchi and co-workers reported the reductive carboxyalkylation of activated olefins such as styrenes or Michael acceptors using magnesium as the reductant. , Alternatively, the same group demonstrated that the electron-deficient olefins can be reduced cathodically to the radical anions whereupon reactions with two equivalents of acyl chlorides/acid anhydrides or N -acylimidazoles (Figure G, left) afford vicinal bis -acylation products after subsequent reductions. , An analogous geminal double carboalkoxylation of imine derivatives has been achieved in a similar fashion . In the reduction of styrenes, the styrenyl radical anion could also react with phenyl diesters where the nucleophilic terminal carbon could add into a carbonyl.…”

Modern Strategies in Electroorganic Synthesis

“…Recent progress in sacrificial Mg electrode technology includes the synthesis of polysilanes with ordered sequences and silylene−germylene copolymers using Mg electrodes developed by Kashimura, Ishifune, and co-workers. Double C-acylation and C-carboxylation of olefins using Zn electrodes developed by Nishiguchi, Maekawa, and co-workers are also interesting. It is also noteworthy that sacrificial sulfur−graphite electrodes containing reactive polysulfide anions have been developed and used in electroorganic synthesis …”

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

“…[227a,258] It has also been demonstrated that geminal double carboxylation of imine derivatives occurs. [258] In reducing styrene, the phenyl radical anion converts the nucleophilic terminal carbon into a carbonyl radical. Cyclopropyl spirolactone was discovered to be formed from cyclized homoenolates after the loss of a phenol.…”

“…[ 257 ] The same group also reported cathode‐reducing electron‐deficient olefins to radical anions by adding two equivalents of acyl chloride/acid anhydride or N‐acyl imidazole after radical anions are reduced to vicinal bis‐acylation products. [ 227 , 258 ]…”