Jozeliūnaitė Augustina, Guo Shen-Yi, Sakai Naomi, Matile Stefan
Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
National Centre of Competence in Research (NCCR) Molecular Systems Engineering, BPR, 1095, Basel, Switzerland.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202417333. doi: 10.1002/anie.202417333. Epub 2024 Nov 14.
The control over the movement of electrons during chemical reactions with oriented external electric fields (OEEFs) has been predicted to offer a general approach to catalysis. Recently, we suggested that many problems to realize electric-field catalysis in practice under scalable bulk conditions could possibly be solved on multiwalled carbon nanotubes in electromicrofluidic reactors. Here, we selected monoterpene cyclizations to assess the scope of our system in organic synthesis. We report that electric-field catalysis can function by stabilizing both anionic and cationic transition states, depending on the orientation of the applied field. Moreover, electric-field catalysis can promote reactions which are barely accessible by general Brønsted and Lewis acids and field-free anion-π and cation-π interactions, and drive chemoselectivity toward intrinsically disfavored products without the need for pyrene interfacers attached to the substrate to prolong binding to the carbon nanotubes. Finally, interfacing with chiral organocatalysts is explored and evidence against contributions from redox chemistry is provided.
利用定向外部电场（OEEF）控制化学反应过程中电子的移动，有望为催化提供一种通用方法。最近，我们提出，在可扩展的宏观条件下，在电微流体反应器中的多壁碳纳米管上，有可能解决实际实现电场催化的许多问题。在此，我们选择单萜环化反应来评估我们的体系在有机合成中的适用范围。我们报告称，电场催化可通过稳定阴离子和阳离子过渡态来发挥作用，这取决于外加电场的方向。此外，电场催化可以促进一般的布朗斯特酸和路易斯酸以及无场阴离子-π和阳离子-π相互作用几乎无法实现的反应，并将化学选择性导向本质上不利的产物，而无需在底物上连接芘界面剂以延长与碳纳米管的结合。最后，我们探索了与手性有机催化剂的结合，并提供了反对氧化还原化学作用的证据。
