We have developed a one-step procedure to a variety of chiral lipophilic and conformationally rigid amines and heterocycles by decarboxylation of adamantane-oxazolidine-2-one. Triflic acid or aluminum triflate promote the addition of diverse nucleophiles to the oxazolidine-2-one moiety accompanied by the release of carbon dioxide. The resulting amine or heterocycle is then protonated/metalated by the catalyst (promotor). Additionally, the starting racemic material, adamantane-oxazolidine-2-one, was resolved into single enantiomers using a chiral auxiliary to access enantio-enriched products and to study the racemization pathway of chiral 1,2-disubstituted adamantane derivatives.