We focus on the virtually neglected use of heuristic principles in understanding and teaching of organic chemistry. As human thinking is not comparable to computer systems employing factual knowledge and algorithms--people rarely make decisions through careful considerations of every possible event and its probability, risks or usefulness--research in science and teaching must include psychological aspects of the human decision making processes. Intuitive analogical and associative reasoning and the ability to categorize unexpected findings typically demonstrated by experienced chemists should be made accessible to young learners through heuristic concepts. The psychology of cognition defines heuristics as strategies that guide human problem-solving and deciding procedures, for example with patterns, analogies, or prototypes. Since research in the field of artificial intelligence and current studies in the psychology of cognition have provided evidence for the usefulness of heuristics in discovery, the status of heuristics has grown into something useful and teachable. In this tutorial review, we present a heuristic analysis of a familiar fundamental process in organic chemistry--the cyclic six-electron case, and we show that this approach leads to a more conceptual insight in understanding, as well as in teaching and learning.