Kiaku Cyrille, Kaltenberger Simon, Raydan Daniel, Morlacci Valerio, Claringbold Bini, Goodall Charles A I, Palombi Laura, Poole Darren L, Lam Kevin
School of Science, Faculty of Engineering and Science, University of Greenwich, Chatham, Kent ME4 4TB, U.K.
Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi di L'Aquila, Via Vetoio, 67100 Coppito, Italy.
Org Lett. 2025 Jan 10;27(1):147-152. doi: 10.1021/acs.orglett.4c04093. Epub 2024 Dec 17.
Traditional etherification methods, although staples in synthetic chemistry, often fall short in the efficient construction of sterically hindered dialkyl ethers, especially under mild and practical conditions. Recent advances have attempted to address these limitations, typically relying on transition metal catalysts, external reductants, or harsh reaction conditions. In this work, we disclose a novel electrochemical approach that enables the synthesis of sterically hindered ethers from economically relevant and readily accessible alcohols without the need for sacrificial oxidants. Our protocol exploits mild conditions to generate reactive carbocations, which are subsequently captured by alcohol nucleophiles to yield the desired ethers. This method is cost-effective, practical, and broad in scope, providing a valuable addition to chemists' synthetic toolkit for ether synthesis.
传统的醚化方法虽然是合成化学中的常用方法，但在空间位阻二烷基醚的高效构建方面往往存在不足，尤其是在温和且实际可行的条件下。最近的进展试图解决这些局限性，通常依赖过渡金属催化剂、外部还原剂或苛刻的反应条件。在这项工作中，我们披露了一种新颖的电化学方法，该方法能够从经济上相关且易于获得的醇类合成空间位阻醚，而无需使用牺牲性氧化剂。我们的方案利用温和的条件生成活性碳正离子，随后这些碳正离子被醇亲核试剂捕获，从而生成所需的醚。该方法具有成本效益、实用性强且适用范围广，为化学家用于醚合成的合成工具包增添了有价值的内容。
