Selective Late‐Stage Oxygenation of Sulfides with Ground‐State Oxygen by Uranyl Photocatalysis. (8th August 2019)

• Record Type: Journal Article
• Authors: Li, Yiming; Rizvi, S. Aal‐e‐Ali; Hu, Deqing; Sun, Danwen; Gao, Anhui; Zhou, Yubo; Li, Jia; Jiang, Xuefeng
• Is Part Of: Angewandte Chemie. Volume 131:Number 38(2019)
• Page Start: 13633
• Page End: 13640
• Publication Date: 2019-08-08
• Subjects: Oxygenierung -- Photokatalyse -- Sauerstoff -- Sulfide -- Uranyl-Katalyse; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201906080
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late‐stage oxygenation of sulfur‐containing complex molecules with ground‐state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO2 2+ ) enabled the efficient synthesis of sulfones. The ligand‐to‐metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a U V center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late‐stage oxygenation in an atom‐ and step‐efficient manner. Abstract : Die Oxygenierung schwefelhaltiger komplexer Moleküle gelang mit Sauerstoff im Grundzustand unter Umgebungsbedingungen. Die Verwendung des Uranyl‐Kations (UO2 2+ ) als aktivem Photokatalysator ermöglichte die atomökonomische Synthese von Sulfon‐ und Sulfoxid‐Derivaten von 32 Wirkstoffen.