使用吡啶氧化物作为氢原子抽象剂的脂肪族碳氢键官能团化反应
Aliphatic C-H Functionalization Using Pyridine -Oxides as H-Atom Abstraction Agents.
作者信息
Schlegel Marcel, Qian Siran, Nicewicz David A
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
出版信息
ACS Catal. 2022 Aug 19;12(16):10499-10505. doi: 10.1021/acscatal.2c02997. Epub 2022 Aug 10.
Abstract
The alkylation and heteroarylation of unactivated tertiary, secondary, and primary C(sp)-H bonds was achieved by employing an acridinium photoredox catalyst along with readily available pyridine oxides as hydrogen atom transfer (HAT) precursors under visible light. Oxygen-centered radicals, generated by single-electron oxidation of the oxides, are the proposed key intermediates whose reactivity can be easily modified by structural adjustments. A broad range of aliphatic C-H substrates with electron-donating or -withdrawing groups as well as various olefinic radical acceptors and heteroarenes were well tolerated.
摘要
通过使用吖啶鎓光氧化还原催化剂以及易于获得的吡啶氧化物作为氢原子转移（HAT）前体，在可见光条件下实现了未活化的叔、仲和伯C(sp³)-H键的烷基化和杂芳基化。由氧化物的单电子氧化产生的以氧为中心的自由基是提出的关键中间体，其反应性可通过结构调整轻松改变。具有供电子或吸电子基团的各种脂肪族C-H底物以及各种烯烃自由基受体和杂芳烃都具有良好的耐受性。
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