Recent Advances in Single-Electron Reduction-Induced Ring Opening of N-Acyl Cyclic Amines

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Abstract Cyclic amines represent ubiquitous structural motifs in organic chemistry, prominently featured natural products and pharmaceuticals. The development of synthetic methodologies targeting cyclic has attracted considerable interest, given their significance medicinal chemistry. These transformations can be broadly categorized into two main types: (1) peripheral modification (2) skeletal remodeling. Recent advancements late-stage C–H functionalization have showcased the potential strategies. Conversely, remodeling, particularly through ring opening amines, emerged as a powerful approach to access structurally diverse amines. Ring initiated by C–N bond cleavage, predominantly relies on two-electron mechanisms. Strained readily undergo such transformations, while those with larger-membered ring, like pyrrolidines, present greater challenges. Oxidative von Braun-type approaches facilitated heterolytic offering broad applicability across various In contrast, reductive approaches, which enable homolytic provide unique radical-mediated transformations. This short review highlights recent progress single electron reduction induced ring-opening methodologies, focusing α-aminoketyl radical generation for selective amide cleavage. Advances aziridines, azetidines, other are discussed, along implications future prospects. 1 Introduction 2 Opening Aziridines 2.1 Hydrogenation Alkylation 2.2 Isomerization 2.3 Arylation 3 Azetidines 4 Pyrrolidines Other Amines 5 Conclusion Outlook

Language: Английский

Vitamin B₁₂ and Micellar Solution Enable Regioselective Ring Opening of Epoxides and Aziridines with Electrophilic Olefins

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 23, 2025

Vitamin B12, a water-soluble cobalt complex, is inherently predisposed to catalyze reactions under aqueous conditions. Despite its potential, adopting this strategy for transformations of hydrophobic reagents has been challenging, because their low solubility. Here, we demonstrate that vitamin B12 promotes the reaction epoxides and aziridines with electrophilic olefins in micellar system. The desired products are obtained efficiently fully regioselective manner. This green catalytic approach further advances use sustainable catalysis providing valuable method synthesize important intermediates.

Language: Английский