Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis.

Although considerable advances have been made in developing chemoselective transformations of ubiquitous carboxylic acid groups, many challenges still exist. For instance, their selective reduction is problematic if both more nucleophilic and more electrophilic groups are present in the starting material. Here, we address this problem with a simple and mild protocol using bench-stable reagents at ambient temperatures. This platform is able to tolerate a diverse range of functionality, leaving ketones, esters, nitro-groups, olefins, nitriles and amides untouched. A combination of experimental and computational mechanistic experiments demonstrate that this reaction proceeds via hidden borane catalysis with small quantities of in situ generated BH3 playing a key role in the exquisite selectivity that is observed.

Controlling Chemoselectivity of Catalytic Hydroboration with Light.

The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction of a functional handle for cross-coupling or act as mild method for reducing polar functionality, these platforms rarely deal with more complex systems where multiple potentially reactive sites exist. Here we demonstrate, for the first time, the ability to use light to distinguish between ketones and carboxylic acids in more complex molecules. By taking advantage of different activation modes, a single catalytic system can be used for hydroboration, with the chemoselectivity dictated only by the presence or absence of visible light.

Using Light to Modify the Selectivity of Transition Metal Catalysed Transformations.

Light has a remarkable and often unique ability to promote chemical reactions. In combination with transition metal catalysis, it offers exciting opportunities to modify catalyst function in a non-invasive manner, most frequently being reported to switch on or accelerate reactions that do not occur in the dark. However, the ability to completely change reactivity or selectivity between two different reaction outcomes is considerably less common. In this Minireview we bring together examples of this concept and highlight their mechanistically distinct approaches. Our overview demonstrates how these non-natural, photo-switchable systems provide key fundamental mechanistic insights, enhancing our understanding and stimulating development of new catalytic activity, and how this might lead to tangible applications, impacting fields such as polymer chemistry.