Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 28, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202104493
Keywords
amidyl radical; ion spectroscopy; nitrene; photocatalysis; reaction mechanisms
Categories
Funding
- European Research Council (ERC CoG) [682275]
- Netherlands Organization for Scientific Research (NWO, Start Up program) [740.018.022]
- Czech Science Foundation [17-14510S]
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This study investigates the reactivity of reactive radicals generated from sulfonyl azides through photocatalytic activation, and their involvement in C-H activation reactions. The reactivities of these radicals are found to be influenced by different mechanisms, which provide theoretical basis for controlling the reactivity of these intermediates.
Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N-2 and the resulting reactive species initiate C-H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C-H activation reactions. The sulfonyl nitrene radical anion is the least reactive and its reactivity is governed by the proton coupled electron transfer mechanism. In contrast, sulfonyl nitrene and sulfonyl amidyl radicals react via hydrogen atom transfer pathways. These reactivities and detailed characterization of the radicals with vibrational spectroscopy and with DFT calculations provide information necessary for taking control over the reactivity of these intermediates.
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