Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation,Journal of the American Chemical Society

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Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-12 , DOI: 10.1021/jacs.4c10915
Chang-Zhen Fang ₁ , Bei-Bei Zhang ₁ , Yong-Liang Tu ₁ , Qiang Liu ₁ , Zhi-Xiang Wang _{1,

2} , Xiang-Yu Chen _{1,

2}

Affiliation

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in radical transformations through halogen-atom transfer (XAT). However, unactivated alkyl chlorides still present an open challenge for this strategy. We herein describe a new activation mode of the LBR for the activation of unactivated alkyl chlorides to construct a C(sp³)–C(sp³) bond. Mechanistic studies reveal that the success of the protocol relies on a radical replacement process between the LBR and unactivated alkyl chloride, forming an alkyl borane intermediate as the alkyl radical precursor. Aided with the additive K₃PO₄, the alkyl borane then undergoes one-electron oxidation, generating an alkyl radical. The incorporation of the radical replacement activation model to activate unactivated alkyl chlorides significantly enriches LBR chemistry, which has been applied to activate alkyl iodides, alkyl bromides, and activated alkyl chlorides via XAT.

中文翻译：

连接硼基自由基介导的未活化烷基氯活化以形成 C(sp3)–C(sp3) 键的自由基取代过程

连接硼基自由基（LBR）已成为通过卤素原子转移（XAT）在自由基转化中激活卤代烷的有效工具。然而，未活化的烷基氯仍然对这一策略提出了公开的挑战。我们在此描述了一种新的LBR活化模式，用于活化未活化的烷基氯以构建C(sp ³ )–C(sp ³ )键。机理研究表明，该方案的成功依赖于 LBR 和未活化的烷基氯之间的自由基取代过程，形成烷基硼烷中间体作为烷基自由基前体。在添加剂 K ₃ PO ₄的帮助下，烷基硼烷发生单电子氧化，产生烷基自由基。结合自由基取代活化模型来活化未活化的烷基氯显着丰富了 LBR 化学，该化学已应用于通过 XAT 活化烷基碘、烷基溴和活化的烷基氯。

更新日期：2024-09-12

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