Shono‐Type Oxidation for Functionalization of N‐Heterocycles

• Published in: Chemical record Vol. 21; no. 9; pp. 2239 - 2253
• Main Authors: Yamamoto, Kosuke, Kuriyama, Masami, Onomura, Osamu
• Format: Journal Article
• Language: English
• Published: United States Wiley Subscription Services, Inc 01.09.2021
• Subjects: Acetals; Amines; Amino acids; Bioactive compounds; Biological activity; Chirality; Electrochemical oxidation; Electrochemistry; Enantiomers; Halogen mediators; N,O-Acetals; Natural products; Nitrogen; Nitrogen heterocycles; Organic chemistry; Oxidation; Synthesis; N,O-Acetals; Electrochemistry; Oxidation; Nitrogen heterocycles; Halogen mediators
• ISSN: 1527-8999; 1528-0691; 1528-0691
• DOI: 10.1002/tcr.202100031

The development of facile synthetic methods for stereodefined aliphatic cyclic amines is an important research field in synthetic organic chemistry since such scaffolds constitute a variety of natural products and biologically active compounds. N‐Acyl cyclic N,O‐acetals which prepared by electrochemical oxidation of the corresponding cyclic amines have proven to be useful and versatile precursors for the synthesis of such skeletons. In this Personal Account, we introduce our efforts toward the development of synthetic strategies for the diastereo‐ and/or enantioselective synthesis of cyclic amines by using electrochemically prepared cyclic N,O‐acetals. In addition, the investigation of the “memory of chirality” in the electrooxidative methoxylation of N‐acyl amino acid derivatives, the strategy for the synthesis of chiral azabicyclic compounds by utilizing electrochemical oxidation, and halogen cation‐mediated synthesis of nitrogen‐containing heterocycles are also described. This Personal Account describes the synthetic strategies for stereodefined N‐heterocycles such as piperidines, pyrrolidines, iminosugars, and bicyclic amines from readily available starting materials by utilizing anodic oxidation as key transformations. The synthetic methods of nitrogen‐containing heterocycles by using electrochemically generated halogen cation species are also introduced.