Abstract
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.
Highlights
Organometallic complexes are ubiquitous in chemistry and biology
Organometallic complexes are prevalent in chemistry and biology, with applications ranging from usage as highly selective catalysts[1] to therapeutics[2] and enzyme cofactors[3]
Conventional synthetic approaches toward organometallic complexes involve reliance on ligand synthesis followed by coordination to a metal center (Fig. 1a)
Summary
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. 1234567890():,; Organometallic complexes are prevalent in chemistry and biology, with applications ranging from usage as highly selective catalysts[1] to therapeutics[2] and enzyme cofactors[3] Key to this versatility is the ability to tune function through manipulation of ligand structure. Conventional synthetic approaches toward organometallic complexes involve reliance on ligand synthesis followed by coordination to a metal center (Fig. 1a) This general approach remains modular and adaptable, accounting for the syntheses of the majority of known metal–ligand complexes. Divergent synthetic routes to organometallic complexes, analogous to those which have proven valuable in medicinal chemistry, are important for generating structurally diverse libraries of compounds Toward this end, a nascent synthetic approach that complements traditional coordination chemistry is chemistry-onthe-complex[8], whereby ligands are modified after being bound to a metal center. Examples include azide cycloadditions (click chemistry) and well-established condensation reactions, resulting in products such as 215 and 316, respectively
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