AbstractThe acid catalyzed reaction of 3‐thiophenamines with aldehydes in the presence of selenophenol as the reducing agent, gives 2‐alkyl‐3‐miophenamines. Without reduction, bis(3‐amino‐2‐thienyl)methane derivatives have been obtained and transformed into dithieno[3,2‐b:2′,3′‐e]pyridines by thermal and acidic treatment when the substrates are primary amines. These new tricyclic heterocycles can be synthesized in a one‐pot procedu