The synthesis of complex natural products requires the development of selective methods to create molecular architecture. The utilization of palladium complexes as templates to achieve such selectivity is discussed in terms of effecting substitutions at allylic positions. The chemo-, regio-, and stereocontrol exhibited by such reactions is outlined. The facilitation of synthetic strategy is considered. Synthetic targets include steroids, macrolides, amino acids, and alkaloids and the total synthesis of representatives of each of these classes is presented. © IUPAC