化学
充氧
催化作用
羧酸
脱羧
有机化学
医学
内科学
作者
Luca Mareen Denkler,Meghana Aladahalli Shekar,Tak Shing Jason Ngan,Luke Wylie,Dinar Abdullin,Marianne Engeser,Gregor Schnakenburg,Tobias Hett,Frank Hendrik Pilz,Barbara Kirchner,Olav Schiemann,Patrycja Kielb,Ala Bunescu
出处
期刊:Angewandte Chemie
[Wiley]
日期:2024-05-12
卷期号:63 (32): e202403292-e202403292
被引量:41
标识
DOI:10.1002/anie.202403292
摘要
We 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.
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