Oxidative Generation of Boron-Centered Radicals in Carboranes,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Oxidative Generation of Boron-Centered Radicals in Carboranes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-02-19 , DOI: 10.1021/jacs.0c00300
Harrison A Mills ₁ , Joshua L Martin ₁ , Arnold L Rheingold ₂ , Alexander M Spokoyny _{1,

3}

Affiliation

We report the first indirect observation and use of boron ver-tex-centered carboranyl radicals generated by the oxidation of modified carboranyl precursors. These radical intermediates are formed by the direct oxidation of a B-B bond between a boron cluster cage and an exopolyhedral boron-based substit-uent (e.g., -BF3K, -B(OH)2). The in situ generated radical species are shown to be competent substrates in reactions with oxygen-based radicals, dichalcogenides, and N-heterocycles, yielding the corresponding substituted carboranes containing B-O, B-S, B-Se, B-Te, and B-C bonds. Remarkably, this chemistry tolerates various electronic environments, providing access to facile substitution chemistry at both electron-rich and electron-poor B-H vertices in carboranes.

中文翻译：

碳硼烷中硼中心自由基的氧化生成

我们报告了首次间接观察和使用由改性碳硼烷基前体氧化产生的以硼顶点为中心的碳硼烷基自由基。这些自由基中间体是通过硼簇笼和外多面体硼基取代基（例如-BF3K、-B(OH)2）之间的BB键直接氧化而形成的。原位产生的自由基物质被证明是与氧基自由基、二硫属化物和N-杂环反应的有效底物，产生相应的含有BO、BS、B-Se、B-Te和BC键的取代碳硼烷。值得注意的是，这种化学反应可以耐受各种电子环境，从而可以在碳硼烷的富电子和贫电子 BH 顶点进行轻松的取代化学反应。

更新日期：2020-02-19

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南