Photochemical diazidation of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer.
Photochemical diazidation of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer.
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DOI：
10.1038/s41467-022-35560-3
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发表时间：
2022-12-23
影响因子：
16.6
通讯作者：
West, Julian G.
中科院分区：
文献类型：
--
作者：
Bian, Kang-Jie;Kao, Shih-Chieh;Nemoto, David, Jr.;Chen, Xiao-Wei;West, Julian G.
邻位二胺是化学中的特殊合成基序，因为它们在生物活性分子、药物和过渡金属配体设计中的普遍性和强大应用。随着有机二叠氮化物被视为邻二胺的模块化前体，人们付出了巨大的努力来开发有效的策略来获取由烯烃（本身是常见的原料化学品）产生的有机二叠氮化物。然而，最先进的烯烃二叠氮化方法依赖于使用腐蚀性和昂贵的氧化剂或复杂的电化学装置，极大地限制了这些方法的大规模基材耐受性和实用性。为了克服这些限制，我们在这里展示了通过铁介导的配体到金属电荷转移（LMCT）和自由基配体转移（RLT）进行烯烃的光化学二叠氮化。利用这两个反应流的合并，我们利用稳定的、地球丰富的且廉价的铁盐来充当自由基引发剂和终止剂。证明了温和的条件、广泛的烯烃范围和连续流动化学的适应性，使得光催化转化。初步机理研究支持光化学二叠氮化中协同过程的激进性质，表明该方法是烯烃双官能化的有力手段。烯烃的双官能化可以有效构建复杂的分子。作者结合配体到金属电荷转移（LMCT）和自由基配体转移（RLT），展示了使用铁盐的光化学二叠氮化作用，可以快速制备邻位二胺和其他特殊的合成基序。
Vicinal diamines are privileged synthetic motifs in chemistry due to their prevalence and powerful applications in bioactive molecules, pharmaceuticals, and ligand design for transition metals. With organic diazides being regarded as modular precursors to vicinal diamines, enormous efforts have been devoted to developing efficient strategies to access organic diazide generated from olefins, themselves common feedstock chemicals. However, state-of-the-art methods for alkene diazidation rely on the usage of corrosive and expensive oxidants or complicated electrochemical setups, significantly limiting the substrate tolerance and practicality of these methods on large scale. Toward overcoming these limitations, here we show a photochemical diazidation of alkenes via iron-mediated ligand-to-metal charge transfer (LMCT) and radical ligand transfer (RLT). Leveraging the merger of these two reaction manifolds, we utilize a stable, earth abundant, and inexpensive iron salt to function as both radical initiator and terminator. Mild conditions, broad alkene scope and amenability to continuous-flow chemistry rendering the transformation photocatalytic were demonstrated. Preliminary mechanistic studies support the radical nature of the cooperative process in the photochemical diazidation, revealing this approach to be a powerful means of olefin difunctionalization. The difunctionalization of alkenes allows for efficient construction of molecular complexity. Combining Ligand-to-Metal Charge transfer (LMCT) and Radical Ligand Transfer (RLT), the authors show a photochemical diazidation using iron salts, allowing rapid preparation of vicinal diamines and other privileged synthetic motifs.
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影响因子：
12.9
作者：
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