Generation of Aryl Radicals through Reduction of Hypervalent Iodine(III) Compounds with TEMPONa: Radical Alkene Oxyarylation

A novel method for selective generation of aryl radicals from diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPONa) as a single‐electron transfer (SET) reducing reagent is described. In the presence of various alkenes, aryl radicals formed after S...

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Bibliographic Details
Published in:Chemistry : a European journal 2016-03, Vol.22 (10), p.3485-3490
Main Authors: Hartmann, Marcel, Li, Yi, Mück-Lichtenfeld, Christian, Studer, Armido
Format: Article
Language:English
Subjects:
Alkenes
Aromatic compounds
Chemistry
Cleaning
Computer applications
density functional calculations
Efficiency
Electron transfer
hypervalent compounds
Iodine
Iodine compounds
Olefins
radical reactions
Radicals
Reagents
Reduction
Salts
Sodium
synthetic methods
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Summary:A novel method for selective generation of aryl radicals from diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPONa) as a single‐electron transfer (SET) reducing reagent is described. In the presence of various alkenes, aryl radicals formed after SET‐reduction of hypervalent iodine compounds undergo alkene addition and the adduct radicals that are thus generated are efficiently trapped by the concomitantly generated TEMPO radical to eventually afford oxyarylated products in moderate to very good yields. The efficiency of aryl radical generation of various iodine(III) reagents is studied and the generation of an iodanylidene malonate aryl radical is also investigated by computational methods. Clean radicals: Reduction of diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPONa) allows for clean generation of aryl radicals (see scheme). Alkene oxyarylation is achieved when reduction is performed in the presence of an alkene radical acceptor.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201504852