Our research group is mostly concerned with the discovery and development of new reactions and processes that could be useful in organic synthesis. As is usually the case in scientific research, the interplay between conjecture and chance observation underlies much of our work. Unexpected events often bring a fresh lighting to the system being examined and open doors hitherto unsuspected. Misconception has thus played an important role by allowing us to uncover a number of new radical and non radical reactions of some generality involving sulfur compounds, acetylenes, oximes and related derivatives: we simply followed the logical consequences of our observations and went where the chemistry took us. In this lecture, the story behind the discovery of some of these reactions will be presented and the various mechanistic and synthetic implications will be discussed.