Synthesis, Characterization, and Chemistry of Bridgehead-Functionalized Bicyclo[2.2.2]Octanes: Reactions at Neopentyl Sites

This paper reports the synthesis and characterization of a series of 15 new, symmetric, 1,4-disubstituted bicyclo[2.2.2]octyl derivatives. Beyond detailing their syntheses and spectral properties, it describes the scope of synthetic transformations that can be effected at these neopentyl-like centers. The question of a possible direct displacement by hydride at such a site, as per an earlier literature report, is considered, and the limits of this and related substitution reactions are delineated. The scope of reactions at sp²centers attached to these positions is also defined.