Hou Liuzhen, Yang Longqing, Yang Gaofei, Luo Zhe, Xiao Wanlong, Yang Linhan, Wang Fei, Gong Liu-Zhu, Liu Xiaohua, Cao Weidi, Feng Xiaoming
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
Center for Natural Products Research, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610061, China.
J Am Chem Soc. 2024 Aug 21;146(33):23457-23466. doi: 10.1021/jacs.4c06780. Epub 2024 Jul 11.
Developing novel strategies for catalytic asymmetric dearomatization (CADA) reactions is highly valuable. Visible light-mediated photocatalysis is demonstrated to be a powerful tool to activate aromatic compounds for further synthetic transformations. Herein, a catalytic asymmetric dearomative [2 + 2] photocycloaddition/ring-expansion sequence of indoles with simple alkenes was reported, providing a facile access to enantioenriched cyclopenta[]indoles with good to high yields and enantioselectivities by means of chiral lanthanide photocatalysis. This protocol exhibited a broad substrate scope and good functional group tolerance, as well as potential applications in the synthesis of bioactive molecules. Mechanistic studies, including control experiments, UV-vis absorption spectroscopy, emission spectroscopy, and DFT calculations, were carried out, shedding insights into the reaction mechanism and the origin of enantioselectivity.
开发催化不对称去芳构化（CADA）反应的新策略具有很高的价值。可见光介导的光催化被证明是激活芳香族化合物以进行进一步合成转化的有力工具。在此，报道了一种吲哚与简单烯烃的催化不对称去芳构化[2 + 2]光环加成/扩环序列，通过手性镧系光催化以良好至高收率和对映选择性提供了一种简便的方法来获得对映体富集的环戊并[ ]吲哚。该方法具有广泛的底物范围和良好的官能团耐受性，以及在生物活性分子合成中的潜在应用。进行了机理研究，包括对照实验、紫外可见吸收光谱、发射光谱和密度泛函理论计算，深入了解了反应机理和对映选择性的起源。
