Approach Matters: The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions.

Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels-Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained by surface-bound mass spectrometry (DART-HRMS).

Site-selective and inducible acylation of thrombin using aptamer-catalyst conjugates.

Two acyl-transfer catalysts were conjugated to thrombin-binding DNA aptamers to acylate thrombin. Modification occurred site-selectively on Lys (≫Ser) residues proximal to the respective aptamer-thrombin interface, was selective for thrombin in the presence of other proteins, and the activity of both DNA-catalysts could be controlled by an external trigger.

Dialyzable carbosilane dendrimers as soluble supports for the functionalization of pyridine fragments via palladium-catalyzed coupling reactions.

[reaction: see text] The use of carbosilane (CS) dendrimers as soluble supports in liquid phase organic synthesis (LPOS) is described. Control of the three key steps is perfectly achieved by covalently binding a pyridine fragment to the soluble support, modifying it via coupling reactions, and releasing it at the end. Nanofiltration (dialysis) allows facile purification of the supported molecules after each step.