Glass Vials Coated with Polymer‐Supported‐Catalysts as Reaction Vessels: <i>Stir, Pour, Rinse and Reuse</i>

Abstract Lightly crosslinked polymeric gel‐supported catalysts have the potential to retain the recyclability and ease of product isolation of traditional polymer‐supported catalysts, while at the same time, they can provide greater homogeneity of catalytic sites and improved reaction rates, especially in the solvent‐swollen state. In the present study, a strategy is devised to covalently anchor a film of swellable crosslinked polymer onto a suitably surface‐derivatized glass vial, and have utilized this coating to bind to Cu, Pd, and Au catalysts; these coated vials are then utilized for azide‐alkyne click, Suzuki coupling and catalytic reduction reactions, respectively. In all cases, simply stirring the reactant mixture in the vial delivers high yields, and the vials can be rinsed and reused several times with little loss of activity. Several control experiments confirm that the catalysis largely occurred within the coated gel film and is not due to leached‐out metal in the reaction medium. Importantly, this strategy can be very useful, when adapted for critical labeling reactions of biomolecules, wherein reactions are often carried out on very small scales, and ease of product isolation with zero contamination is critical.