Metal-catalyzed electrochemical diazidation of alkenes

Abstract

Vicinal diamines are a common structural motif in bioactive natural products, therapeutic agents, and molecular catalysts, motivating the continuing development of efficient, selective, and sustainable technologies for their preparation. We report an operationally simple and environmentally friendly protocol that converts alkenes and sodium azide-both readily available feedstocks-to 1,2-diazides. Powered by electricity and catalyzed by Earth-abundant manganese, this transformation proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility. Using standard protocols, the resultant 1,2-diazides can be smoothly reduced to vicinal diamines in a single step, with high chemoselectivity. Mechanistic studies are consistent with metal-mediated azidyl radical transfer as the predominant pathway, enabling dual carbon-nitrogen bond formation.

Catalyst‐Free Oxytrifluoromethylation of Alkenes through Paired Electrolysis in Organic‐Aqueous Media

“…Thus, electrochemical reactions are considered safe and “inherently green.” In this context, electrochemical difunctionalization of alkenes is a powerful and versatile synthetic tool very recently established . The group of Li has developed an elegant methodology for the radical diazidation, dichlorination, and chlorotrifluoromethylation of alkenes based on electrocatalysis mediated by Mn II salts, using TFA as sacrificial oxidant. More recently Mei, Du and Han have reported the oxysulfuration of alkenes using an undivided cell and Pt electrodes, whereas Lei has described oxy‐ and aminosulfuration of alkenes under similar conditions …”

Hexafluoro‐2‐Propanol‐Promoted Electro‐Oxidative [3+2] Annulation of 1,3‐Dicarbonyl Compounds and Alkenes

“…Electrosynthesis, which can avoid the external oxidants by employing the electrons to achieve the redox reaction, is considered as a versatile and eco‐friendly synthetic strategy and has experienced remarkable renaissance in recent years . The electrochemical alkene difunctionalization is emerging as a approach to construct C−C, C−N, C−O, C−Cl and so on . We envisioned acyclic 1,3‐dicarbonyl compounds, which has interested the chemists over the years due to the high oxidation potential of acyclic 1,3‐dicarbonyl compounds, might serve as C‐radical sources and nucleophilic oxygen sources to react with alkenes, achieving the electro‐oxidative [3+2] annulation with hydrogen evolution.…”

Recent Advances in Electrochemical Oxidative Cross‐Coupling of Alkenes with H2 Evolution

“…In 2017, Lin and co‐workers demonstrated diazidation of alkenes with MnBr 2 ⋅H 2 O as redox‐active catalyst, under electrolytic conditions (Scheme ) . Varieties of alkyl olefins, aryl olefins could participate in this reaction with good functional group compatibility.…”