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Anion Relay Chemistry (ARC), an effective multi-component union protocol, recently developed and employed in our laboratory, holds great potential for chemists requiring rapid increase of molecular complexity in a single operation, with precise control of stereogenicity on route to both natural and "natural product-like" targets for biomedical research.1 Employing this technique, a large number of diverse structures can be assembled rapidly from a small number of initiating nucleophiles, bifunctional linchpins, and electrophiles in a controlled, multi-component coupling reaction.Efforts to expand the scope of this tactic include the construction of natural products,2 as well as libraries of "natural product-like" compounds,3 which highlight the robust nature of this protocol.Evolution of the ARC tactic, involving both Type Ⅰ and Type Ⅱ protocols, will be presented with illustrations arising from alkaloid and polyketide/macrolide total synthetic ventures currently ongoing in our laboratory.In addition, observations regarding the intersection of the ARC Type Ⅱ protocol with previously reported reaction pathways,4 notably in the area of Pd-mediated Takeda5 and Hiyama/Denmark6,7 cross-coupling reactions, will be presented.