5,8‐Methanoquinazolines fused with imidazoles 4a‐4b, thiadiazoles 5–6, pyrimidines 7, 9, 11 and 12, and 1,3,5‐triazine 13 were prepared starting from (5R,8S)‐2‐amino‐8,9,9‐trimethyl‐5,6,7,8‐tetrahydro‐5,8‐methanoquinazoline 3. Most compounds possessed central nervous system stimulant activities.