Direct radical functionalization methods to access substituted adamantanes and diamondoids.

Direct radical functionalization methods to access substituted adamantanes and diamondoids.
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DOI:
10.1039/d1ob01916c
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发表时间:
2021-12-22
影响因子:
3.2
通讯作者:
--
中科院分区:
化学3区
文献类型:
--
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金刚烷衍生物由于其独特的结构、生物学和刺激响应特性等,在药物化学、催化剂开发和纳米材料领域具有多种应用。取代的金刚烷和取代的高级金刚烷的合成通常通过碳阳离子或自由基中间体实现,当与简单的烃衍生物相比时,碳阳离子或自由基中间体具有独特的稳定性和反应性。在这篇综述中,我们讨论了广泛的基于自由基的官能化反应,直接将金刚烷C-H键转化为C-C键,提供了各种各样的产品纳入不同的官能团(烯烃,炔,芳烃,羰基等)。在该领域的选择性C-H官能化的最新进展突出强调的H-原子抽象的物种和它们的能力,以激活特别强的C-H键,这些笼状烃的特性,提供的见解,可以应用到其他基板类的C-H官能化。
Adamantane derivatives have diverse applications in the fields of medicinal chemistry, catalyst development and nanomaterials, owing to their unique structural, biological and stimulus-responsive properties, among others. The synthesis of substituted adamantanes and substituted higher diamondoids is frequently achieved via carbocation or radical intermediates that have unique stability and reactivity when compared to simple hydrocarbon derivatives. In this review, we discuss the wide range of radical-based functionalization reactions that directly convert diamondoid C–H bonds to C–C bonds, providing a variety of products incorporating diverse functional groups (alkenes, alkynes, arenes, carbonyl groups, etc.). Recent advances in the area of selective C–H functionalization are highlighted with an emphasis on the H-atom abstracting species and their ability to activate the particularly strong C–H bonds that are characteristic of these caged hydrocarbons, providing insights that can be applied to the C–H functionalization of other substrate classes.
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