Affiliation:
1. Kekulé Institute for Organic Chemistry and Biochemistry Universität Bonn Gerhard-Domagk-Straße1 53121 Bonn Germany
2. Mulliken Center for Theoretical Chemistry Clausius Institute for Physical and Theoretical Chemistry Universität Bonn Beringstraße 4 53115 Bonn Germany
3. Clausius Institute for Physical and Theoretical Chemistry Universität Bonn Wegelerstraße 12 53115 Bonn Germany
4. Transdisciplinary Research Area' Building Blocks of Matter and Fundamental Interactions (TRA Matter) University of Bonn 53115 Bonn Germany
5. Institute of Inorganic Chemistry Universität Bonn Gerhard-Domagk-Straße1 53121 Bonn Germany
Abstract
AbstractWe report an iron‐catalyzed decarboxylative C(sp3)−O bond‐forming reaction under mild, base‐free conditions with visible light irradiation. The transformation uses readily available and structurally diverse carboxylic acids, iron photocatalyst, and 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) derivatives as oxygenation reagents. The process exhibits a broad scope in acids possessing a wide range of stereoelectronic properties and functional groups. The developed reaction was applied to late‐stage oxygenation of a series of bio‐active molecules. The reaction leverages the ability of iron complexes to generate carbon‐centered radicals directly from carboxylic acids by photoinduced carboxylate‐to‐iron charge transfer. Kinetic, electrochemical, EPR, UV/Vis, HRMS, and DFT studies revealed that TEMPO has a triple role in the reaction: as an oxygenation reagent, an oxidant to turn over the Fe‐catalyst, and an internal base for the carboxylic acid deprotonation. The obtained TEMPO adducts represent versatile synthetic intermediates that were further engaged in C−C and C‐heteroatom bond‐forming reactions using commercial organo‐photocatalysts and nucleophilic reagents.
Funder
Deutsche Forschungsgemeinschaft
H2020 European Research Council
Cited by
3 articles.
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