The growing understanding of transition-metal catalysis has provided the opportunity to design reactions that convert simple, readily available building blocks in one step into an array of biologically relevant products. Described herein is the application of this approach to the construction of various biologically relevant products, including pyrroles, imidazoles, beta-lactams, oxazoles, alpha-amino acids, propargyl amides, functionalized pyridines, and others. These catalytic reactions rely upon several synthetic operations occurring in sequence, in which the reactivity of transition-metal complexes both activates basic building blocks towards reaction, and controls how multiple versions of these substrates come together. Overall, this allows the synthesis of each these products in one step, in high yield, with minimal waste, and with straightforward access to product diversity.