Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue

• Published in: Angewandte Chemie International Edition Vol. 57; no. 24; pp. 7205 - 7209
• Main Authors: Maity, Asim, Hyun, Sung‐Min, Wortman, Alan K., Powers, David C.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.06.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: aerobic oxidation; Autoxidation; Catalysis; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Disproportionation; hypervalent iodine; Intermediates; Iodine; Organic chemistry; Oxidants; Oxidation; Oxidizing agents; Periodinane; Physical Sciences; Reagents; Science & Technology; Substrates; sustainable chemistry; hypervalent iodine; SELECTIVE OXIDATION; autoxidation; EFFECTIVE CORE POTENTIALS; MOLECULAR-ORBITAL METHODS; aerobic oxidation; CLEAVAGE; IN-SITU GENERATION; SECONDARY ALCOHOLS; O-IODOXYBENZOIC ACID; ELECTRON-TRANSFER; sustainable chemistry; PERACETIC-ACID; IBX
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201804159

Hypervalent iodine(V) reagents, such as Dess–Martin periodinane (DMP) and 2‐iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to generate these reagents from dioxygen (O2) would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. The developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis. Aerobic oxidation of iodobenzenes is coupled with disproportionation of iodine(III) compounds to generate iodine(V) reagents. The aerobically generated iodine(V) reagents exhibit substrate oxidation chemistry analogous to that of Dess–Martin periodinane. Examples of aerobic oxidation catalyzed by the hypervalent iodine species include coupling of O2 reduction with oxidation of alcohols, diols, and amines.