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化物活化以形成 C（sp3）–C（sp3）键的自由基置换工艺

连接的硼自由基（LBR）已成为通过卤素原子转移（XAT）在自由基转化中激活烷基卤化物的有效工具。然而，未活化的烷基氯仍然对这种策略提出了一个公开的挑战。我们在这里描述了 LBR 的一种新活化模式，用于活化未活化的烷基氯以构建 C（sp³）–C（sp³）键。机理研究表明，该方案的成功取决于 LBR 和未活化烷基氯之间的自由基置换过程，形成烷基硼烷中间体作为烷基自由基前体。在添加剂 K₃PO₄ 的帮助下，烷基硼烷随后发生单电子氧化，生成烷基自由基。掺入自由基置换活化模型以激活未活化的烷基氯显着丰富了 LBR 化学，其已应用于通过 XAT 激活烷基碘、烷基溴和活化烷基氯。

更新日期：2024-09-12

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