Shevchenko Grigory A, Oppelaar Barry, List Benjamin
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
Angew Chem Int Ed Engl. 2018 Aug 13;57(33):10756-10759. doi: 10.1002/anie.201804445. Epub 2018 Jun 28.
The first direct and asymmetric α-aryloxylation of cyclic ketones via enol catalysis has been achieved using quinones as the reaction partners. Catalytic amounts of a phosphoric acid promote the exclusive formation of α,α-disubstituted ketones from the corresponding α-substituted ketones in good yields and enantioselectivities (up to 96.5:3.5 er). Preliminary mechanistic experiments suggest that this reaction proceeds via a proton-coupled electron transfer (PCET) followed by radical recombination.
通过烯醇催化实现了环状酮与醌作为反应伙伴的首次直接且不对称的α-芳氧基化反应。催化量的磷酸能促使相应的α-取代酮以良好的产率和对映选择性（高达96.5:3.5的对映体比例）专一性地生成α,α-二取代酮。初步的机理实验表明，该反应通过质子耦合电子转移（PCET）接着自由基重组进行。
