Abstract：
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.
摘要：
我们报告了一种光化学方法，用于未活化的烯丙醇的半频哪醇重排。脂肪族和芳香族基团作为迁移基团参与，产生多种α，α-二取代的酮。反应在温和的条件下进行，与醚相容，酯类,卤化物,腈，氨基甲酸酯,和替代芳烃。操作简单且完全催化的条件规定1mol％的苯并噻嗪并喹喔啉作为有机光催化剂，0.5mol%Co-salen,和10摩尔%的三氟甲磺酸鲁丁铵，重要的是,显示与使用布朗斯台德酸的程序互补的反应性。我们展示了该方案在后期药物多样化中的实用性。
