We report the annulation of heterocyclic building blocks to access pi-extended polycyclic aromatic hydrocarbons (PAHs). The method involves the trapping of short-lived hetarynes with catalytically-generated biaryl palladium intermediates and allows...

Organometallic complexes are ubiquitous in chemistry and biology. Whereas their preparation has historically relied on ligand synthesis followed by coordination to metal centers, the ability to efficiently diversify their structures remains a synthetic challenge. A promising yet underdeveloped strategy involves the direct manipulation of ligands that are already bound to a metal center, also known as chemistry-on-the-complex. Herein, we introduce a versatile platform for on-the-complex annulation reactions using transient aryne intermediates. In one variant, organometallic complexes undergo transition metal-catalyzed annulations with in situ generated arynes to form up to six new carbon–carbon bonds. In the other variant, an organometallic complex bearing a free aryne is generated and intercepted in cycloaddition reactions to access unique scaffolds. Our studies, centered around privileged polypyridyl metal complexes, provide an effective strategy to annulate organometallic complexes and access complex metal–ligand scaffolds, while furthering the synthetic utility of strained intermediates in chemical synthesis.

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With increasing marijuana legalization, there is a growing need for technology that can determine if an individual is impaired due to recent marijuana usage. The electrochemical oxidation of Δ 9 -THC to form its corresponding quinones can be used as a framework to develop an electrochemical sensor for Δ 9 -THC. This study describes an electrochemical oxidation of Δ 9 -THC that uses a copper anode, a platinum cathode, and an atmosphere of oxygen. The oxidation is feasible at nanomolar concentrations, which approaches the reactivity that is necessary for developing a real-world marijuana breathalyzer. Moreover, we show that vaporized Δ 9 -THC can be captured directly in an electrolyte medium and subjected to electrochemical oxidation, thus paving the way for use in future technology development.