Yang Dan, Mei Yu-Tong, Guo Zi-Yi, Hou Qiu-Yao, Zhang Hui, Zheng Yu-Xuan, Jing Lin-Hai, Cheng De-Jun, Shi Ming-Song
Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, China.
Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemical Engineering Sichuan University of Science & Engineering, Zigong 643000, China.
J Org Chem. 2025 Mar 14;90(10):3665-3672. doi: 10.1021/acs.joc.4c03047. Epub 2025 Feb 28.
Carboxylic acids are bench-stable and readily available chemical feedstocks that function as optimal and fundamental synthetic platforms for the construction of C(sp)-C(sp) bonds via decarboxylation processes. We present a novel and practical protocol for the decarboxylative alkylation of Morita-Baylis-Hillman acetates with various carboxylic acids via a photoinduced iron-mediated ligand-to-metal charge transfer (LMCT) process under redox-neutral conditions. This method exhibits remarkable tolerance to a wide array of carboxylic acids, including primary, secondary, and tertiary carboxylic acids, obviating the requirement for preactivated radical precursors. The preliminary mechanistic analyses indicate that a radical pathway is involved in this catalytic transformation.
羧酸是易于储存且容易获得的化学原料，是通过脱羧过程构建C(sp)-C(sp)键的理想且基础的合成平台。我们提出了一种新颖且实用的方法，即在氧化还原中性条件下，通过光诱导铁介导的配体到金属的电荷转移（LMCT）过程，实现了各种羧酸与森田-贝利斯-希尔曼乙酸酯的脱羧烷基化反应。该方法对包括伯、仲和叔羧酸在内的多种羧酸具有显著的耐受性，无需预活化的自由基前体。初步的机理分析表明，该催化转化过程涉及自由基途径。
