We report a conceptually distinct strategy for the synthesis of 1,1-diarylalkanes and triarylalkanes. Key to this approach is the use of light to simultaneously trigger (i) formation of a Co III −H species which undergoes H atom transfer (MHAT) to styrenes, giving a carbon-centered radical, and (ii) generation of a persistent (hetero)arene radical. Selective coupling of these two species yields Markovnikov hydroarylation products under mild conditions and without precious metals. In contrast to many previous approaches, electron-deficient (hetero)arene coupling partners are favored and it is possible to construct highly congested quaternary centers, including those with three different aryl groups.

Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β‐unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β‐unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4‐selective hydroboration, providing a straightforward and stereoselective route to rare syn‐aldol products in one‐pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.

While the use of visible light in conjunction with transition metal catalysis offersp owerfulo pportunities to switch betweeno n/-off states of catalytic activity, the next frontier wouldb et he ability to switcht he actual functiono ft he catalyst and resulting products.H ere we report such an example of multi-dimensionalc atalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reactiono utcomeb etween two widely employed transformations,o lefin migration and hydroboration, with visible light as the trigger.

A general strategy is introduced for the efficient synthetic access of disulfide linked artificial macrocycles via a Ugi four-component reaction (U4CR) followed by oxidative cyclization. The double-mercapto input is proposed for use in the Ugi reaction, thereby yielding all six topologically possible combinations. The protocol is convergent and short and enables the production of novel disulfide peptidomimetics in a highly general fashion.

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.

Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β‐unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β‐unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4‐selective hydroboration, providing a straightforward and stereoselective route to rare syn‐aldol products in one‐pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.

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.

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.