Palladium-catalyzed cross-coupling reactions and electrocyclic transformations as well as cycloadditions can efficiently be combined in one-pot sequences to build up complex molecules from simple precursors. 1,3-Dicyclopropyl-1,2-propadiene (1) could be coupled to various aryl halides, and the 1,3,5-hexatrienes resulting after rearrangement were trapped with different dienophiles. Further exploration of the highly reactive building block bicyclopropylidene (8) demonstrates the combinatorial potential of the two reaction modes in terms of two different three-component reactions, and even a novel four-component reaction was readily developed. Additional increase of complexity was gained by combining an intramolecular Heck reaction with consecutive trapping by 8, which can be carried out with or without 6pi-electrocyclization. Finally a Stille-Heck-coupling sequence of substituted 2-bromocycloalkenyl triflates with functionally substituted alkenylstannanes and acrylic esters led to highly substituted 1,3,5-hexatrienes. which smoothly underwent 6pi-electrocyclization at elevated temperatures to yield bi- and tricyclic skeletons. With this methodology at hand, a new versatile access to steroid-analogues with a diene moiety in the B ring and a functionality at C-7 was developed. (C) 2003 Elsevier B.V. All rights reserved.