Capaldo Luca, Wan Ting, Mulder Robin, Djossou Jonas, Noël Timothy
Flow Chemistry Group, Van 't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands
Department of Chemistry, SynCat Lab, Life Sciences and Environmental Sustainability, University of Parma 43124 Parma Italy
Chem Sci. 2024 Aug 13;15(36):14844-50. doi: 10.1039/d4sc02962c.
Photoinduced halogen-atom transfer (XAT) has rapidly emerged as a programmable approach to generate carbon-centered radical intermediates, mainly relying on silyl and α-aminoalkyl radicals as halogen abstractors. More recently, ligated boryl radicals have also been proposed as effective halogen abstractors under visible-light irradiation. In this study, we describe the use of this approach to enable C(sp)-C(sp) bond formation radical addition of carbon-centered radicals generated XAT onto chloroalkynes. Our mechanistic investigation reveals a complex interplay of highly reactive radical intermediates which, under optimized conditions, delivered the targeted vinyl chlorides in excellent yields and : ratios. Finally, we demonstrated the synthetic value of these products in transition metal-based cross-coupling reactions.
光致卤原子转移（XAT）已迅速成为一种生成碳中心自由基中间体的可编程方法，主要依赖硅基和α-氨基烷基自由基作为卤素抽取剂。最近，连接的硼基自由基也被提议作为可见光照射下有效的卤素抽取剂。在本研究中，我们描述了使用这种方法通过XAT产生的碳中心自由基对氯炔烃进行自由基加成来实现C(sp)-C(sp)键的形成。我们的机理研究揭示了高活性自由基中间体之间复杂的相互作用，在优化条件下，以优异的产率和E:Z比得到了目标氯乙烯。最后，我们展示了这些产物在过渡金属基交叉偶联反应中的合成价值。
