1,1,1,3,3,3‐Hexafluoroisopropanol‐Enhanced Redox‐Mediated Diels–Alder Cycloadditions of Anthracenes: Experimental and Computational Study

This study presents a detailed study on the effect of presence of 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) on redox‐mediated Diels–Alder reaction between anthracenes and chalcones induced by oxidation by Ag II SO 4 . The introduction of even a minimal amount, 1% (v/v), of HFIP is shown to have a significant effect on the reaction rate. The optimization of the DA reaction protocol in the examined system leads to substantial rise of yields (up to 25 times) or reduction of reaction time (up to >100 times), allowing facile synthesis of cycloadducts from poorly active reactants which are otherwise difficult to obtain. Experimental and computational results point to the role of HFIP as the enhancement of solubilization of (Anth) +• through complexation of the [Ag I SO 4 ] − counterion, while the alcohol itself does not interact strongly with radical cations involved in the reaction.