Abstract
High-level ab initio calculations demonstrate that alkoxythiocarbonyl radicals (ROC.=S) undergo β-scission significantly faster than alkoxycarbonyl radicals (ROC.=O) despite having similar exothermicities. The relatively low reactivity of the ROC.=O radicals is reduced further by electron-donating R groups and arises from the large polarization of the C.-O bonds of the reactant radicals. The results suggest that the generation of alkyl radicals from ROC.=S should be particularly efficient when the R group bears radical-stabilizing and/or electron-accepting groups, such as CN.
Original language | English |
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Pages (from-to) | 4996-4999 |
Number of pages | 4 |
Journal | Journal of Organic Chemistry |
Volume | 71 |
Issue number | 13 |
DOIs | |
Publication status | Published - 1 Jun 2006 |
Externally published | Yes |