We investigate the efficiency of domain-specific heuristic strategies in mastering and predicting pericyclic six-electron rearrangements. Based on recent research findings on these types of reactions a new concept has been developed that should help students identify and describe six-electron rearrangements more readily in complex molecules. The goal of this qualitative study with chemistry majors is to understand the way students cope with this new concept depending on their prior knowledge, and to reveal the merits and limitations of this approach. The results suggest that the use of domain-specific heuristic strategies provides the students with process-orientated thinking skills to identify six-electron rearrangements and to determine as well as predict reaction mechanisms and outcomes. The explicit emphasis on recurrent patterns and structure-property relationship fosters the conceptual thinking of the learner. (Contains 1 table, 1 scheme, and 10 figures.)