Lindner Henry, Carreira Erick M
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2024 Aug 26;63(35):e202407827. doi: 10.1002/anie.202407827. Epub 2024 Jul 25.
We report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well as aromatic groups participate as migrating groups, yielding a variety of α,α-disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, and substituted arenes. The operationally simple and fully catalytic conditions prescribe 1 mol % benzothiazinoquinoxaline as organophotocatalyst, 0.5 mol % Co-salen, and 10 mol % lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. We showcase the utility of the protocol in late-stage drug diversifications.
我们报道了一种用于未活化烯丙醇半频哪醇重排的光化学方法。脂肪族和芳香族基团均可作为迁移基团参与反应，生成多种α,α-二取代酮。该反应在温和条件下进行，且与醚、酯、卤化物、腈、氨基甲酸酯和取代芳烃兼容。操作简单且完全催化的反应条件规定使用1 mol%的苯并噻嗪并喹喔啉作为有机光催化剂、0.5 mol%的Co-salen和10 mol%的三氟甲磺酸二甲基吡啶鎓，重要的是，该反应表现出与使用布朗斯特酸的方法互补的反应活性。我们展示了该方法在后期药物多样化中的应用。
