Linear Paired Electrolysis Enables Redox-Neutral (3 + 2) Annulation of Benzofuran with Vinyldiazo Compounds

Electrosynthesis has emerged as a versatile and sustainable tool in organic chemistry, offering an efficient pathway for the construction of complex molecular architectures under mild and environmentally benign conditions. Traditional electrochemical approaches, however, predominantly rely on either anodic oxidation or cathodic reduction, limiting their capacity to achieve redox-neutral transformations using a single electrode. In this work, we introduce a linear paired electrolysis strategy that circumvents these limitations, enabling a redox-neutral (3 + 2) annulation of benzofuran with vinyldiazo compounds. This method facilitates the formation of benzofuran-fused tricyclic scaffolds, which are valuable in synthetic chemistry and medicinal applications. The transformation proceeds through sequential anodic oxidation and cathodic reduction, leveraging a radical cation pathway to deliver polycyclic compounds with high selectivity. The efficiency and mechanism of this process are thoroughly validated using cyclic voltammetry and <i>in situ</i> electrochemical mass spectrometry (EC-MS) and supported by theoretical calculations, shedding light on the potential of redox-neutral electrochemical transformations.