Anodic Oxidation of Aliphatic and Aromatic Amides, Bisamides and Related Derivatives

The current comprehensive review covers four main parts, of which some are presented in the form of a personal account. 1. Anodic oxidation of a) N‐alkyl and N,N‐diallyl carbonyl moieties, b) Azacycloalkyl amides and the effect of ring‐size on the outcome, c) Lactams, d) Sulfonamides, and e) The effect of a substituent R attached to carbonyl (N−CO−R) or sulfonamides (N−SO 2 R) on their oxidation potentials. 2. Anodic oxidation of aromatic amides, in particular of type Ph 2 CHCONHAr, lacking hydrogen(s) at the α‐position to nitrogen. They undergo three types of bond‐cleavage, yielding a variety of fragmentation products. 3. a) Anodic oxidation of symmetrical bisamides of type ZCONH(CH 2 ) n NHCOZ (Z=Me, Ph, Ar; n=2–4) under constant current electrolysis, in methanol. For n=3, 4 they afford mostly mono‐ and dimethoxylation products. For n=2 they undergo ′CH 2 −CH 2 ′ bond cleavage to yield fragmentation products. b) Anodic oxidation of symmetrical bisamides of type ArCONH(CH 2 ) 2 NHCOAr under controlled potential electrolysis, in acetonitrile, leads to gem ‐unsymmetrical bisamides of type ArCONHCH 2 NHCOMe as the major product, in fair yields. 4. Utilization of the anodic process in organic synthesis to form C−C bonds by both intra‐ and inetr molecular processes; as well as C−O and C−N bonds for generating heterocycles.