Li Xin, Yang Weiping, Yue Junping, Li Jieyuan, Shen Shujie, Chen Ruimin, Wang Jielin, Dan Huimin, Yu Dagang, Dong Fan
Research Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, 611731, China.
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.
Nat Commun. 2025 Apr 15;16(1):3590. doi: 10.1038/s41467-025-58840-0.
Electro/photocatalytic C-N coupling acts as a key build-block to the next generation of chemicals like amides for wide applications in energy, pharmaceuticals and chemical industries. However, the uncontrolled intermediates coupling challenges the efficient amide production regarding yield or selectivity. Here we propose a photocatalytic radical addition route, where the fundamental active species, including oxygen and photogenerated electron-hole pairs, are regulated for selective intermediates generation and efficient acetamide synthesis from mild co-oxidation of CHCHOH and NH. Sufficient CHCHOH is provided to accumulate the stable intermediate (CHCHO). Meanwhile, the limited NH concentration ensures the controllable generation and fast addition of the transient radical (NH) on CHCHO. Through the directed coupling of stable-transient intermediates, the acetamide synthesis rate is pushed forward to a hundred-mmol level (105.61 ± 4.86 mmol·g·h) with a selectivity of 99.17% ± 0.39%, reaching a gram-scale yield (1.82 g) of acetamide. These results illuminate valuable opportunities for the photocatalysis-driven synthetic industry.
电/光催化C-N偶联是合成新一代化学品（如酰胺）的关键组成部分，酰胺在能源、制药和化工行业有广泛应用。然而，不受控制的中间体偶联在产率或选择性方面对高效酰胺生产构成挑战。在此，我们提出一种光催化自由基加成途径，通过调控包括氧气和光生电子-空穴对在内的基本活性物种，实现选择性中间体生成以及由CHCHOH和NH的温和共氧化高效合成乙酰胺。提供足够的CHCHOH以积累稳定中间体（CHCHO）。同时，有限的NH浓度确保了瞬态自由基（NH）在CHCHO上可控生成并快速加成。通过稳定-瞬态中间体的定向偶联，乙酰胺合成速率提升至百毫摩尔水平（105.61±4.86 mmol·g·h），选择性为99.17%±0.39%，实现了克级乙酰胺产率（1.82 g）。这些结果为光催化驱动的合成工业带来了宝贵机遇。
