Electrochemical Azidocyanation of Alkenes

• Published in: Angewandte Chemie International Edition Vol. 63; no. 6; pp. e202313273 - n/a
• Main Authors: Zheng, Yun‐Tao, Xu, Hai‐Chao
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 05.02.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkene; Alkenes; Aromatic compounds; Chemistry; Chemistry, Multidisciplinary; Copper; Electrocatalysis; Electrochemistry; Electron transfer; Enantiomers; Functional groups; Ligands; Nucleophiles; Oxidants; Oxidation; Oxidizing agents; Physical Sciences; Radical Reactions; Science & Technology; Substrates; DIFUNCTIONALIZATION; Electrocatalysis; Alkene; Radical Reactions; Oxidation; DIAZIDATION; Copper
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202313273

The difunctionalization of alkenes—a process that installs two functional groups in a single operation and transforms chemical feedstocks into value‐added products—is one of the most appealing synthetic methods in contemporary chemistry. However, the introduction of two distinct functional groups via two readily accessible nucleophiles remains a formidable challenge. Existing intermolecular alkene azidocyanation methods, which primarily focus on aryl alkenes and rely on stoichiometric chemical oxidants. We report herein an unprecedented electrochemical strategy for alkene azidocyanation that is compatible with both alkyl and aryl alkenes. This is achieved by harnessing the finely‐tuned anodic electron transfer and the strategic selection of copper/ligand complexes. The reactions of aryl alkenes were rendered enantioselective by employing a chiral ligand. Crucially, the mild conditions and well‐regulated electrochemical process assure exceptional tolerance for various functional groups and substrate compatibility with both terminal and internal alkyl alkenes. An electrochemical alkene azidocyanation reaction that is compatible with both alkyl and aryl alkenes was developed. The reactions involving aryl alkenes could be obtained with good enantioselectivities by employing a chiral ligand. Notably, this method of alkene difunctionalization employs readily accessible reagents and is distinguished by its demonstrated functional group tolerance.