Chemists are often inspired by nature’s chemical structures to develop syntheses. Sometimes, structures not produced naturally initiate the development of exciting new methods, concepts and principles. Our interest in this area is focused on the dendralenes, one of the four fundamental classes of conjugated hydrocarbon structures. In earlier studies, we reported the first chemical synthesis of this hydrocarbon family, previously believed to be too unstable to prepare. One of our major advances in this reporting period includes the first practical synthesis of dendralene and a demonstration of its use in the rapid formation of different polycyclic frameworks. Upon publication, the work was selected as a “Hot paper” by the editors of Angewandte Chemie. Another important development involves the preparation of the first saturated hydrocarbon with a helical structure. We have also uncovered new and unexpected reactivity patterns of these fundamental compounds. The results have led to a better understanding of the stability and reactivity of unsaturated organic compounds in a more general sense.