Diastereofacial Selectivity in Atom Transfer Reactions of 5-Substituted (X) Adamant-2-yl Radicals: Nature of the Electronic Factor.
The diastereofacial selectivity in deuterium and halogen atom abstraction reactions of 5-fluoro- and 5-(trimethylstannyl)-2-adamantyl radicals has been investigated. Significant preferential syn (or zu) and anti (or en) face selectivity, respectively, is observed for these substituents of distinctly opposite electronic character. Although the observations are in accord with predictions from Cieplak's transition state hyperconjugation model, an alternative explanation can be advanced based on an early reactant-like TS model.
Adcock
William
W
Department of Chemistry, The Flinders University of South Australia, Adelaide, Australia 5001.
Lünsmann
Dieter
D
Trout
Neil A.
NA