The Resorcinarene Hexameric Capsule as a Supramolecular Photoacid to Trigger Olefin Hydroarylation in Confined Space

The self-assembled resorcinarene capsule C6 shows remarkable photoacidity upon light irradiation, which is here exploited to catalyze olefin hydroarylation reactions in confined space. An experimental pKa* value range of -3.3--2.8 was estimated for the photo-excited hexameric capsule C6*, and consequently an increase in acidity of 8.8 log units was observed with respect to its ground state (pKa=5.5-6.0). This makes the hexameric capsule the first example of a self-assembled supramolecular photoacid. The photoacid C6* can catalyze hydroarylation reaction of olefins with aromatic substrates inside its cavity, while no reaction occurred between them in the absence of irradiation and/or capsule. DFT calculations corroborated a mechanism in which the photoacidity of C6* plays a crucial role in the protonation step of the aromatic substrate. A further proton transfer to olefin with a concomitant C-C bond formation and a final deprotonation step lead to product releasing. Under light irradiation the hexameric resorcinarene capsule increases in acidity of 8.8 log units with respect to its ground state, becoming the first example of a self-assembled supramolecular photoacid. The photoacidity of the hexameric capsule was here exploited to boost the olefin hydroarylation reactions in confined space while no reaction occurred in the absence of irradiation and/or capsule. DFT calculations strongly corroborated a mechanism in which the photoacidity of C6* plays a crucial role. image