The past decades have witnessed tremendous progress on radical reactions. However, in comparison with carbon, nitrogen, oxygen, and other main group element centered radicals, the synthetic chemistry of boron centered radicals was less studied, mainly due to the high electron-deficiency and instability of such 3-center–5-electron species. In the 1980s, Roberts and co-workers found that the coordination of a Lewis base (amines or phosphines) with the boron center could form 4-center–7-electron boryl radicals (Lewis base–boryl radicals, LBRs) that are found to be more stable. However, only limited synthetic applications were developed. In 2008, Curran and co-workers achieved a breakthrough with the discovery of N-heterocyclic carbene (NHC) boryl radicals, which could enable a range of radical reduction and polymerization reactions. Despite these exciting findings, more powerful and valuable synthetic applications of LBRs would be expected, given that the structures and reactivities of LBRs could be easily modulated, which would provide ample opportunities to discover new reactions. In this Account, a summary of our key contributions in LBR-enabled radical borylation reactions and selective activation of inert carbon–heteroatom bonds will be presented.

中文翻译：

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路易斯碱-硼基自由基使碳-杂原子键的硼化反应和选择性活化成为可能

过去几十年见证了激进反应的巨大进步。然而，与碳、氮、氧等主族元素中心基团相比，硼中心基团的合成化学研究较少，主要是由于这种三中心五电子物种的高缺电子性和不稳定性。 . 在 1980 年代，Roberts 及其同事发现路易斯碱（胺或膦）与硼中心的配位可以形成 4-中心-7-电子硼自由基（路易斯碱-硼自由基，LBRs）被发现更稳定。然而，只开发了有限的合成应用。2008 年，Curran 及其同事发现了N-杂环卡宾 (NHC) 硼基自由基，可以实现一系列自由基还原和聚合反应。尽管有这些令人兴奋的发现，但鉴于 LBR 的结构和反应性可以轻松调节，这将为发现新反应提供充足的机会，因此预计 LBR 的更强大和更有价值的合成应用。在这篇文章中，我们将总结我们在 LBR 激活的自由基硼化反应和选择性激活惰性碳-杂原子键方面的主要贡献。