A Metal-Free, Photocatalytic Method for Aerobic Alkane Iodination,Journal of the American Chemical Society

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A Metal-Free, Photocatalytic Method for Aerobic Alkane Iodination
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-11-15 , DOI: 10.1021/jacs.1c08499
Nathanael A Hirscher ₁ , Nidhi Ohri ₁ , Qiaomu Yang ₁ , Jiawang Zhou ₁ , Jessica M Anna ₁ , Eric J Schelter ₁ , Karen I Goldberg ₁

Affiliation

Halogenation is an important alkane functionalization strategy, but O₂ is widely considered the most desirable terminal oxidant. Here, the aerobic iodination of alkanes, including methane, was performed using catalytic [ⁿBu₄N]Cl and light irradiation (390 nm). Up to 10 turnovers of CH₃I were obtained from CH₄ and air, using a stop-flow microtubing system. Mechanistic studies using cyclohexane as the substrate revealed important details about the iodination reaction. Iodine (I₂) serves multiple roles in the catalysis: (1) as the alkyl radical trap, (2) as a precursor for the light absorber, and (3) as a mediator of aerobic oxidation. The alkane activation is attributed to Cl^• derived from photofragmentation of the electron donor–acceptor complex of I₂ and Cl^–. The kinetic profile of cyclohexane iodination showed that aerobic oxidation of I₃^– to produce I₂ in CH₃CN is turnover-limiting.

中文翻译：

一种无金属光催化好氧烷烃碘化方法

卤化是一种重要的烷烃官能化策略，但 O ₂被广泛认为是最理想的末端氧化剂。在这里，包括甲烷在内的烷烃的需氧碘化是使用催化 [ ⁿ Bu ₄ N]Cl 和光照射（390 nm）进行的。使用停流微管系统从 CH ₄和空气中获得多达 10 次 CH _{3 I 周转。}使用环己烷作为底物的机理研究揭示了碘化反应的重要细节。碘 (I ₂ ) 在催化中发挥多种作用：(1) 作为烷基自由基捕获剂，(2) 作为光吸收剂的前体，以及 (3) 作为有氧氧化的介质。烷烃活化归因于 Cl^•源自I ₂和Cl ^-的电子供体-受体复合物的光裂解。环己烷碘化的动力学曲线表明，有氧氧化 I ₃^-在 CH ₃ CN 中产生 I _{2是周转受限的。}

更新日期：2021-11-24

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