Azobenzenes are important molecular switches that can still be difficult to functionalize selectively. A high yielding Pd-catalyzed cross-coupling method under mild conditions for the introduction of NHS esters to azobenzenes and diazocines has been established. Yields were consistently high with very few exceptions. The NHS functionalized azobenzenes react with primary amines quantitatively. These amines are ubiquitous in biological systems and in material science.
Keywords: N-hydroxysuccinimide; azobenzene; chemical biology; diazocine; molecular switches; palladium-catalyzed carbonylation; photo-switchable NHS ester.