Challenging cross couplings, in water, aided by in situ iodination of (hetero)aromatic bromides.

Palladium-catalyzed reactions that involve functionalized substrates are oftentimes problematic. Those involving aryl or heteroaryl bromides that are either resistant to, or inefficient in such couplings present challenges that are difficult to overcome and may require development of an entirely new route, or worse, no opportunity to install the desired group using a standard coupling strategy. In this report, we describe a solution that allows for the in situ conversion of such bromo educts to transient iodide derivatives that can be made and used under environmentally responsible conditions, for subsequent reactions to highly functionalized, complex targets.

Direct formation of amide/peptide bonds from carboxylic acids: no traditional coupling reagents, 1-pot, and green.

Technology for generating especially important amide and peptide bonds from carboxylic acids and amines that avoids traditional coupling reagents is described. The 1-pot processes developed rely on thioester formation, neat, using a simple dithiocarbamate, and are safe and green, and rely on Nature-inspired thioesters that are then converted to the targeted functionality.