The base-mediated formation of a bridgehead double bond in a bicyclo[2.2.1]heptane system (anit-Bredt molecules) is described. The synthesis of exocyclic norbornyl enones by Wittig reaction of α-diketones is reported. These enones and their Michael adducts are used as substrates for the generation of transient bridgehead enones and their trapping with MeOH and H2 O. Bridgehead alcohols are easily synthesized from norbornyl enones and are exploited for the diversity oriented synthesis of frameworks of natural and unnatural products.