This study provides a practical route to synthesize tetrasubstituted alkenes that involves Co(III)-catalyzed C–H bond activation and regioselective insertion of the alkyne, followed by chelation of the substrate hydroxyl to Co and migration of the pyridine group. Density functional theory studies revealed the origin of regioselectivity and elucidated the crucial role of the hydroxyl group for the migration of pyridine. The method can be conducted on a gram scale, is compatible with a wide range of substrates, and has a high functional group tolerance. To demonstrate its significance, the method was used for the late-stage modification of Fasudil. Furthermore, the synthetic significance of the method was demonstrated by the various derivatizations of the products, many of which exhibit intriguing fluorescence characteristics.

中文翻译：

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羟基辅助和钴（III） 催化的氧化还原中性 C-H 活化/定向基团迁移 2-吡啶酮与丙炔醇：四取代烯烃的合成


本研究提供了一种合成四取代烯烃的实用途径，涉及 Co（III） 催化的 C-H 键活化和炔烃的区域选择性插入，然后底物羟基与 Co 的螯合和吡啶基团的迁移。密度泛函理论研究揭示了区域选择性的来源，并阐明了羟基在吡啶迁移中的关键作用。该方法可以在克级上进行，与多种底物兼容，并具有很高的官能团耐受性。为了证明其重要性，该方法被用于 Fasudil 的后期修饰。此外，产物的各种衍生化证明了该方法的合成意义，其中许多衍生化表现出有趣的荧光特性。