Frame‐Shifted Synthesis of Oligoheterocycles as a Platform for Molecular Design

Abstract Chemists continue to develop strategies that leverage abundant feedstocks to accelerate the production of medicines, agrochemicals, and materials. Oligoheterocycles are a broad class of molecules that span these disciplines. Cross‐coupling strategies are commonly used to assemble oligoheterocycles; however, these methods can be challenging and often rely on precious metal catalysts and building blocks whose production entails significant environmental and economic costs. We present a strategy for the iterative construction of oligoheterocycles that leverages sustainable building blocks designed around high‐oxidation‐state carbon. By utilizing feedstocks from the base of the chemical supply chain, we generate bifunctional building blocks that chemoselectively engage with a variety of partners through simple condensation manifolds. This approach has enabled the creation of novel scaffolds previously inaccessible by conventional means, exemplifying sustainable design strategies.