Synthesis of Arylamines via Aminium Radicals. Issue 47 (24th October 2017)

• Record Type: Journal Article
• Authors: Svejstrup, Thomas D.; Ruffoni, Alessandro; Juliá, Fabio; Aubert, Valentin M.; Leonori, Daniele
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 47(2017)
• Page Start: 14948
• Page End: 14952
• Publication Date: 2017-10-24
• Subjects: aminium radicals -- aryl amines -- late-stage amination -- N-arylation -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201708693
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Arylamines constitute the core structure of many therapeutic agents, agrochemicals, and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but still challenging. We demonstrate that protonated electron‐poor O‐aryl hydroxylamines give aminium radicals in the presence of Ru(bpy)3 Cl2 . These highly electrophilic species undergo polarized radical addition to aromatic compounds in high yield and selectivity. We successfully applied this method to the late‐stage modification of chiral catalyst templates, therapeutic agents, and natural products. Abstract : A radical solution : Protonated electron‐poor O‐aryl hydroxylamines give aminium radicals in the presence of Ru(bpy)3 Cl2 . These highly electrophilic species undergo polarized radical addition to aromatic compounds to give arylamines in high yield and selectivity. This method has a broad reaction scope and was successfully applied to the late‐stage modification of chiral catalyst templates, therapeutic agents, and natural products.