Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS).
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
Angew Chem Int Ed Engl. 2022 Jan 3;61(1):e202113658. doi: 10.1002/anie.202113658. Epub 2021 Nov 22.
The site-selective C-H functionalization of heteroarenes is of considerable importance for streamlining the rapid modification of bioactive molecules. Herein, we report a general strategy for visible-light-induced β-carbonyl alkylation at the C4 position of pyridines with high site selectivity using various cyclopropanols and N-amidopyridinium salts. In this process, hydrogen-atom transfer between the generated sulfonamidyl radicals and O-H bonds of cyclopropanols generates β-carbonyl radicals, providing efficient access to synthetically valuable β-pyridylated (aryl)ketones, aldehydes, and esters with broad functional-group tolerance. In addition, the mild method serves as an effective tool for the site-selective late-stage functionalization of complex and medicinally relevant molecules.
杂芳环的位点选择性 C-H 官能化对于简化生物活性分子的快速修饰具有重要意义。在此，我们报道了一种使用各种环丙烷醇和 N-酰胺吡啶盐通过可见光诱导在吡啶的 C4 位进行高位点选择性的β-羰基烷基化的通用策略。在这个过程中，生成的磺酰胺基自由基和环丙烷醇的 O-H 键之间的氢原子转移生成β-羰基自由基，为具有广泛官能团容忍度的合成有价值的β-吡啶基化（芳基）酮、醛和酯提供了有效途径。此外，该温和的方法可用作复杂和具有药物相关性的分子的位点选择性后期官能化的有效工具。
