Free-Radical Rearrangements

In the field of free radical intermediates a lot of work has been devoted to intramolecular reactions. Probably the main reason is the very high selectivity often encountered in these reactions, which results in useful preparative methods.

Radical Cyclizations by Intramolecular Additions

Chapter 7 – Reduction of unsaturated carbon–carbon bonds

Substituent effects on the stability and reactivity of norbornenyl and nortricyclyl radicals

The products of addition of thioacetic acid to norbornadiene, and of tributyltin hydride and triphenyltin hydride reduction of exo-2-bromo- anti-7-thioacetoxynorborn-5-ene (7), and trans-5-bromo-3- thioacetoxynortricyclene (8), have been examined. In contrast to results obtained with the corresponding acetoxy compounds, the product ratios vary with the reducing reagent and the starting material and the ratio of (rate of rearrangement)/(rate of hydrogen atom abstraction) is significantly less for the thioacetoxy substituted radicals.

WR Jackson

Papers

Substituent effects on the stability and reactivity of norbornenyl and nortricyclyl radicals