Factors affecting the relative and absolute rates of ß-scission of alkoxythiocarbonyl radicals and alkoxycarbonyl radicals

Michelle Coote 1 Christopher Easton 1 Samir Zard 2
1 ARC Centre of Excellence in Free Radical Chemistry and Biotechnology
2 DCSO - Laboratoire de synthèse organique
Abstract : High-level ab initio calculations demonstrate that alkoxythiocarbonyl radicals (ROC.=S) undergo ß-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. © 2006 American Chemical Society.
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Michelle Coote, Christopher Easton, Samir Zard. Factors affecting the relative and absolute rates of ß-scission of alkoxythiocarbonyl radicals and alkoxycarbonyl radicals. Journal of Organic Chemistry, American Chemical Society, 2006, 71 (13), pp.4996-4999. ⟨10.1021/jo0607313⟩. ⟨hal-00951308⟩

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