Wang Ai, Yin Yu-Yun, Wang Le-Quan, Jin Jia-Hui, Shen Yong-Miao
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, P.R. China.
Zhejiang Sci-Tech University Shengzhou Innovation Research Institute, Shengzhou 312400, P.R. China.
J Org Chem. 2023 Oct 6;88(19):13871-13882. doi: 10.1021/acs.joc.3c01483. Epub 2023 Sep 8.
An efficient approach for 1,2-difunctionalization of aromatic olefins and the synthesis of functionalized 1,4-diols monoethers has been established via a photoinduced three-component reaction of an α-alkoxycarboxylic acid, an aromatic olefin, and an aldehyde. The reaction proceeds by photoinduced oxidative decarboxylation of the carboxylic acid followed by the addition of the α-alkoxyalkyl radical to the olefin, one-electron reduction of the addition radical, and the nucleophilic attack of the resulting carbanion to the aldehyde. Besides the convenient one-pot protocol of the three-component reaction, this method offers several other advantages, including good functional group tolerance for the three substrates, gentle reaction conditions, and ease of scaling up. The reaction mechanism has been investigated through free radical trapping experiment and isotope labeling experiments.
通过α-烷氧基羧酸、芳族烯烃和醛的光诱导三组分反应，建立了一种高效的芳族烯烃1,2-双官能化方法以及官能化1,4-二醇单醚的合成方法。该反应通过羧酸的光诱导氧化脱羧进行，随后α-烷氧基烷基自由基加成到烯烃上，加成自由基进行单电子还原，以及所得碳负离子对醛的亲核进攻。除了三组分反应方便的一锅法操作外，该方法还具有其他几个优点，包括对三种底物具有良好的官能团耐受性、温和的反应条件以及易于放大。通过自由基捕获实验和同位素标记实验对反应机理进行了研究。
