AbstractThe electrophilic additions of 2‐nitrobenzenesulfenyl chloride to (1RS,2SR,4RS)‐spiro[bicyclo[2.2.1]hept‐5‐ene‐2,2′‐oxirane] (12) and (1RS,2SR,4RS)‐spiro[bicyclo[2.2.2]oct‐5‐ene‐2,2′‐oxirane] (14) were not regioselective under condition of kinetic control. However, good regioselectivity was observed for the addition of 2‐nitro‐benzenesulfenyl chloride to (1RS,2RS,4RS)‐spiro[bicyclo[2.2.1]hept‐5‐ene‐2,2′‐oxirane] (13), giving (1RS,2SR,4SR,5RS,6RS)‐6‐exo‐(2‐nitrophenylthio)spiro[bicyclo[2.2.1]heptane‐2.2′‐oxirane]‐5‐endo‐yl chloride (24) and for the exo addition to (1RS,2RS.4RS)‐spiro[bicyclo[2.2.2]oct05‐ene‐2,2′‐oxirane] (15), giving preferntially (1RS,2SR,4SR,5RS,6 RS)‐6‐exo‐(2‐nitrophenylthio) spiro[bicyxlo[2.2.2]octane‐2,2′‐oxirane]‐5‐endo‐yl chloride (30). The facial selectivity (electrophilic exo vs. endo attack on the bucyclic alkene) depended on the relative configuration of the spiroepoxide ring in the bicyclo[2.2.2]octenes 14 and 15. The exo‐epoxide 14 was attacked preferentially (6:1) on the endo face by sulfenyl whereas exo attack was preferred (7:2) in the case of the endo‐epoxide 15. No products resulting from transannular ring expansion of the spiro‐epoxide moieties could be detected.