eFlow-Hydrogenation: Practical and Scalable Single-Pass Electrochemical Reduction Platform for Unsaturated Bonds

We report a flow electrochemical platform which is capable of reducing alkenes, alkynes, α,β-unsaturated carbonyls, ketones, and aldehydes using solvents and electrolytes as benign hydrogen sources. The system operates under mild conditions with simple current control and a fixed reactor design, enabling seamless translation from discovery to multigram scale without reoptimization. Gram-scale reactions proceed with short residence times of about 1 min, 59 examples with up to 96% yield are reported. The platform also enables two-step flow electrochemical hydrogenation by connecting undivided microreactors in series, allowing selective and sequential reduction of different functional groups within a continuous single flow process. A key engineering innovation is a three-electrode, dual-sided cathode architecture that enables efficient single-pass electroreduction and supports high throughput operation. With 16 parallel reactors a 100 g electrochemical reduction with >98% conversion and 96% isolated yield was achieved, delivering 19.1 g/h productivity under safe and hydrogen-free conditions.In this project, all data were generated using a continuous‑flow electrochemical setup, with full documentation of flow‑cell specifications, standard operating procedures, and analytical methods including NMR and HRMS. The data files (1H, 13C, 19F) are arranged according to the compound numbers used in the Manuscript and the Supporting Information. All NMR data were processed by MestReNova software, and HRMS data were provided in .pdf file.

本研究报道了一款流动电化学平台，该平台可利用溶剂与电解质作为温和氢源，实现烯烃、炔烃、α,β-不饱和羰基化合物、酮及醛的还原反应。该体系在温和条件下运行，仅需简单的电流调控与固定化反应器设计，无需重新优化即可实现从实验室发现到多克级规模制备的无缝放大。克级反应的停留时间仅约1分钟，本研究共报道59个反应实例，最高收率可达96%。

该平台还可通过串联无分隔微反应器实现两步流动电化学加氢，能够在连续单一流程中对不同官能团进行选择性分步还原。一项关键工程创新为三电极双侧阴极结构，该结构可实现高效的单程电还原并支持高通量运行。借助16个并联反应器，本研究实现了100克级电还原反应，转化率大于98%，分离收率达96%，在安全无氢的反应条件下实现了19.1 g/h的产率。

本项目所有数据均采用连续流动电化学装置生成，完整记录了流动池规格、标准操作规程以及包括核磁共振波谱（Nuclear Magnetic Resonance, NMR）和高分辨质谱（High Resolution Mass Spectrometry, HRMS）在内的分析方法。数据文件（1H、13C、19F谱图）按照论文及补充材料（Supporting Information）中使用的化合物编号进行整理。所有核磁共振数据均通过MestReNova软件处理，高分辨质谱数据以.pdf格式文件提供。