Olefins are among the most abundant and widely available chemical feedstock, indispensable for both the synthetic and biological communities due to their unique reactivity profile. Thus, hydrogenation and hydrofunctionalisation of C-C double bonds are important transformations to access pharmaceutical and chemical compounds that are produced at an industrial scale. We have developed wide-scope, efficient protocols using Ir-based photocatalysts for the reduction and regioselective hydroaminoalkylation of electron-deficient alkenes.
The photocatalytic reduction opens a path for the development of greener and safer hydrogenation methodologies, avoiding the use of high-energy, strong reductants as well as the use of pressure equipment.
Radical addition to α,β-unsaturated carbonyl compounds has been widely investigated as a useful method for functionalisation at the β-position. The α-aminoalkyl radicals formed by photocatalytic oxidation are highly nucleophilic and consequently prone to attack electron-deficient alkenes at β-position via Giese-type reaction. There are examples of stereoselectivity control for this reaction, but regioselectivity is completely predetermined by the nature of the substrate. As a result of our research, we were able to direct radical addition to the α-position of α,β-unsaturated esters to produce potentially valuable β-amino acids. Importantly, our method overcomes relevant scope limitations of alternative approaches to these products, such as Mannich-type reactions.