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Factors Affecting the Relative and Absolute Rates of β-Scission of Alkoxythiocarbonyl Radicals and Alkoxycarbonyl Radicals

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Michelle L. Coote,*^† Christopher J. Easton,^† and Samir Z. Zard^‡

ARC Centre of Excellence in Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia, and Laboratoire de Synthese Organique associe au CNRS, Ecole Polytechnique, 91128 Palaiseau, France %mcoote@rsc.anu.edu.au

J. Org. Chem., 2006, 71 (13), pp 4996–4999

DOI: 10.1021/jo0607313

Publication Date (Web): May 26, 2006

To whom correspondence should be addressed.

†

Australian National University.

‡

Ecole Polytechnique.

Abstract

High-level ab initio calculations demonstrate that alkoxy-thiocarbonyl 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.

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Published In Issue June 23, 2006
Received April 6, 2006

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Factors Affecting the Relative and Absolute Rates of β-Scission of Alkoxythiocarbonyl Radicals and Alkoxycarbonyl Radicals

Abstract

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SciFinder Links

History

Recommend & Share

Related Content

Efficient, “Tin-Free” Radical Cyclization to Aromatic Systems. Synthesis of 5,6,8,9,10,11- Hexahydroindolo[2,1-a]isoquinolines

Stabilization Energies of Extensively Conjugated Propargylic Radicals

Halo Substituent Effects on Intramolecular Cycloadditions Involving Furanyl Amides

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