Electrochemical Synthesis of Nitroaromatic Ketones

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

“…From a practical point of view, these electrochemical S N Ar reactions are usually carried out under potentiostatic conditions, based on first oxidation peak of in situ generated Meisenheimer complexes. Gallardo showed that cyanide (Figure 25B), 393,394 alkyl metal reagents (Figure 25D) (e.g., alkyl lithium or Grignard), 395,396 organophosphorous nucleophiles (Figure 25E), 397 and amines (Figure 25F) 398,394 could serve as nucleophiles in both S N X and S N H processes, while enolates 399 and tetraalkylborate salts 396 have been used as nucleophiles in S N H reactions (Figure 25C). Conversely, σ H -complexes between nitroarenes and alkoxides, 394 thiolates, 394 or fluoride 394 tend to undergo one-electron electrochemical oxidation, extruding the heteroatom nucleophile to regenerate the parent arene.…”

Electrochemical Synthesis of Alkyl Nitroaromatic Compounds

“…The oxidation step of the σ-complex remains to be solved, since the use of chemical oxidants represents a significant environmental hazard when scaling-up the reactions. Our previous work has demonstrated that the electrochemical oxidation of σ-complexes leads to substitution products. For cyanation, amination, and reaction with enolate anions, fair to good yields were obtained in what can be considered a “green” process.…”

Dakin—West Synthesis of β‐Aryl Ketones.

“…Phenyl-2-propanone, 1,3-diphenyl-2-propanone, 4-phenyl-2-butanone, 1,5-diphenyl-3-pentanone, 1-(4-methoxyphenyl)-2-propanone, 1,3-bis(4-methoxyphenyl)-2-propanone, 3-phenyl-2-pentanone, 1-(4-nitrophenyl)-2-propanone and 1,3-bis(4-nitrophenyl)-2-propanone have been previously characterized. [1][2][3][4][5]…”