Activation of dioxygen by monooxygenase enzymes enables the oxidation of a rich variety of substrates mainly due to the compatibility of this process with redox active metals. The current study shows that similarly to monooxygenases, pyrrole‐proline 2,5‐diketopiperazine (DKP) organocatalyst, in the presence of Hantzsch ester and HFIP is compatible with copper(II) salts for the activation of dioxygen. These findings allow to selectively diverge the oxidation profile of boronic acids for the synthesis of phenols, bisphenols and diaryl ethers by DKP‐promoted aerobic oxidation and subsequent metal oxidative‐coupling or Chan‐Lam‐Evans type reaction of the formed phenols.
A mature science, combining the art of the total synthesis of complex natural structures and the practicality of delivering highly diverged lead compounds for biological screening, is the constant aim of the organic chemistry community. Delivering natural lead compounds became easier during the last two decades, with the evolution of green chemistry and the concepts of atom economy and protecting-group-free synthesis dominating the field of total synthesis. In this new era, total synthesis is moving towards natural efficacy by utilizing both the biosynthetic knowledge of divergent synthesis and the latest developments in radical chemistry. This contemporary review highlights recent total syntheses that incorporate the best of both worlds.
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