Electrochemical Carboxylation of Several Organic Halides in Supercritical Carbon Dioxide

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

“…The use of NaOMe as a base leads to the formation of the corresponding epoxide. Use of 18 O-labeled DMSO leads to the formation of the corresponding 18 O-labeled epoxide. Because 18 O-labeled DMSO can be easily synthesized from 18 O-labeled water, the transformation serves as a useful method for obtaining 18 Olabeled epoxides, which can be utilized for various mechanistic and biological studies.…”

“…Use of 18 O-labeled DMSO leads to the formation of the corresponding 18 O-labeled epoxide. Because 18 O-labeled DMSO can be easily synthesized from 18 O-labeled water, the transformation serves as a useful method for obtaining 18 Olabeled epoxides, which can be utilized for various mechanistic and biological studies. Schubert and co-workers reported that the electrochemical oxidation of naphthalene in Bu 4 NPF 6 /CH 2 Cl 2 at −45 °C in an undivided cell afforded red-violet needles with an approximate composition of (C 10 H 8 ) 2 PF 6 .…”

“…(1) New reaction media: It is well-known that reaction media such as solvents and supporting electrolytes play important roles in organic electrochemistry, because solvation and the behavior of ions often play major roles in electron-transfer processes in solution. Recently, ionic liquids , and supercritical fluids − have been used as new reaction media, and they can be employed as solvents for electrolysis as well. Solid-supported electrolytes − and mediators , have also been developed.…”

Electrochemical Fixation of Carbon Dioxide

“…Supercritical carbon dioxide (scCO 2 ) has significant potential as an environmentally benign solvent to replace the hazardous organic solvents, as carbon dioxide is abundant, economical, Scheme 10.14 Magnesium-promoted carboxylation of ethyl cinnamates and nontoxic and can be recovered and reused after the reaction. The use of scCO 2 to electrochemical carboxylation has been studied, and a novel method for electrochemical carboxylation in scCO 2 by the use of small amount of acetonitrile (5-10 to 155 mL of scCO 2 ) as a cosolvent has been developed [82]. No current flows in pure supercritical carbon dioxide due to its poor conductivity.…”

“…Fixation of carbon dioxide to aromatic compounds successfully takes place in scCO 2 . Electrochemical reduction of aromatic halides 43 in scCO 2 containing a small amount of acetonitrile with a platinum plate cathode and a magnesium anode results in efficient fixation of carbon dioxide to give aryl carboxylic acids such as 44a-c in high yields [82,83] (Scheme 10.15).…”