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Absolute Rate Constants for the Addition of the 1-(tert-Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution

✍ Scribed by Hanns Fischer; Bernhard Knühl; Sylvain R. A. Marque

Publisher
John Wiley and Sons
Year
2006
Tongue
German
Weight
46 KB
Volume
89
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical ^.^CHMeCO~2~(__t‐__Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain.

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