Cover feature: inner‐sphere oxygen activation promoting outer‐sphere nucleophilic attack on olefins (Chem. Eur. J. 64/2019)

Abstract

Straightforward olefin oxyfunctionalization has been achieved by an outer‐sphere nucleophilic attack of alcohols and water to an olefin in an iridium(III) complex promoted by oxygen, activated by an inner‐sphere pathway. The reaction goes through a novel proton‐coupled electron‐transfer reaction step to give the diamagnetic hydroperoxide compound shown in the inset, rather than the most common electron‐transfer reaction to the peroxide complex. A reversible and easy exchange of the alkoxy or hydroxy groups in the complexes just by dissolving them in a different alcohol (R'OH) is also reported. More information can be found in the Full Paper by A. Lledós, C. Tejel, et al. on page 14546.