Benzylidene acetone reacts with thiocyanates derived from secondary amines in a one-pot reaction to give 4-aminobicyclo[2.2.2]octan-2-ones. The reaction mixture was investigated for the presence of possible intermediates using GC-MS. These intermediates - diketones and enamines - were prepared and exposed to the same reaction conditions to examine the reaction mechanism. The reaction of ethyl styryl ketone with thiocyanates of secondary amines yielded cyclohexanone derivatives instead of the expected bicyclo- octanones. Their structures were established by means of a single crystal structure analysis.