Electrophilic Additions to a 2-Methylenebicyclo[2.1.1]hexane System:  Probing π-Face Selectivity for Electrostatic and Orbital Effects

5-exo-Bicyclo[2.1.1]hexane derivatives with remote electron-withdrawing substituents exhibit very modest face selectivity during electrophilic additions due to interplay of several electronic factors. These experimental results have been probed through ab initio MESP maps, bond density calculations, and energetics involved in pre-reaction complexation.