A four component reaction involving the coupling of functionalized aldehydes, amines, acid chlorides, and [pi]- and organometallic nucleophiles has been developed to prepare multifunctional substrates that may be employed in subsequent ring-forming reactions to generate diverse arrays of functionalized heterocyclic scaffolds. Allyl metals, Grignard reagents, silyl ketene acetals, silyl enol ethers, and silyloxy furans have been utilized as the nucleophile in the four component reaction (4CR). The 4CR has been sequenced with intramolecular Heck reactions, Diels-Alder and [3+2] cycloadditions, ring closing metathesis (RCM), and Dieckmann condensations to provide a number of diverse heterocyclic structures. The practical utility of this approach to diversity-oriented synthesis (DOS) was further exemplified by its application to the first total synthesis of the isopavine alkaloid roelactamine, which was completed in only four steps from commercially available materials. The application of this methodology towards the synthesis of the Aspidosperma alkaloids rosicine and pseudotabersonine is also presented. To this end, an imine pentadienylation/double RCM strategy has been adopted to rapidly access the pentacyclic core of the aspidospermine alkaloids. This sequence involved the use of a pentadienyl aluminum reagent, which was found to react with aryl imines to give branched products in good yields. / text