瑞士苏黎世联邦理工学院Morandi Bill团队报道了利用受挫离子对偶联非活化烷基亲电试剂。相关研究成果于2024年11月20日发表在国际知名学术期刊《自然》。

交叉亲电偶联反应已经发展成为快速组装重要有机分子的主要策略。两种易于获得的亲电试剂偶联形成新的C-C键，与需要预先形成反应性有机金属物种的传统交叉偶联策略相比，具有关键优势。然而，形成几乎所有有机化合物核心的C（sp3）-C（sp3)键的形成，仍然是当前方法的一大挑战，需要设计创新的新策略。。

该文中，研究人员报告了一种独特的、无过渡金属的平台，可以形成这种键，而不需要激活或稳定偶联伴侣上的基团。该反应是由受抑离子对中不寻常的单电子转移实现的，它可以耦合含有官能团的片段，这在相关的过渡金属催化过程中是具有挑战性的。

此外，研究人员可以在其他反应的设计中进一步利用这种新的机制，展示这种反应的广泛潜力。研究预计，该研究结果将为进一步探索这种反应模式提供一个框架，以解决有机合成中的挑战性问题。

附：英文原文

Title: Coupling of unactivated alkyl electrophiles using frustrated ion pairs

Author: Roediger, Sven, Le Saux, Emilien, Boehm, Philip, Morandi, Bill

Issue&Volume: 2024-11-20

Abstract: Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important organic molecules1. Two readily accessible electrophiles are coupled to form new C–C bonds, providing a key advantage over traditional cross-coupling strategies that require the preformation of reactive organometallic species. Yet, the formation of C(sp3)–C(sp3) bonds that form the core of nearly all organic compounds remains highly challenging with current approaches, calling for the design of innovative new strategies. Here we report a distinct, transition-metal-free platform to form such bonds without the need for activating or stabilizing groups on the coupling partners. The reaction is enabled by an unusual single-electron transfer in a frustrated ion pair, and it can couple fragments containing functional groups that would be challenging in related transition-metal-catalysed processes. Moreover, we could further leverage this new mechanistic manifold in the design of other reactions, showing the broad potential of this type of reactivity. We anticipate that our results will provide a framework for further exploration of this reactivity pattern to tackle challenging problems in organic synthesis.

DOI: 10.1038/s41586-024-08195-1

Source: https://www.nature.com/articles/s41586-024-08195-1