Gao Hao-Jie, Miao Yu-Hang, Sun Wen-Na, Zhao Rui, Xiao Xiao, Hua Yuan-Zhao, Jia Shi-Kun, Wang Min-Can, Mei Guang-Jian
College of Chemistry, Pingyuan Laboratory, Zhengzhou University, Zhengzhou, 450001, China.
Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou, 310014, China.
Adv Sci (Weinh). 2023 Dec;10(35):e2305101. doi: 10.1002/advs.202305101. Epub 2023 Oct 23.
Herein, the first diversity-oriented catalytic asymmetric dearomatization of indoles with o-quinone diimides (o-QDIs) is reported. The catalytic asymmetric dearomatization (CADA) of indoles is one of the research focuses in terms of the structural and biological importance of dearomatized indole derivatives. Although great achievements have been made in target-oriented CADA reactions, diversity-oriented CADA reactions are regarded as more challenging and remain elusive due to the lack of synthons featuring multiple reaction sites and the difficulty in precise control of chemo-, regio-, and enantio-selectivity. In this work, o-QDIs are employed as a versatile building block, enabling the chemo-divergent dearomative arylation and [4 + 2] cycloaddition reactions of indoles. Under the catalysis of chiral phosphoric acid and mild conditions, various indolenines, furoindolines/pyrroloindolines, and six-membered-ring fused indolines are collectively prepared in good yields with excellent enantioselectivities. This diversity-oriented synthesis protocol enriches the o-quinone chemistry and offers new opportunities for CADA reactions.
本文报道了首例以邻醌二亚胺（o-QDIs）为导向的吲哚的多样性催化不对称去芳构化反应。鉴于去芳构化吲哚衍生物的结构和生物学重要性，吲哚的催化不对称去芳构化（CADA）是研究热点之一。尽管在目标导向的CADA反应中已取得了巨大成就，但由于缺乏具有多个反应位点的合成子以及难以精确控制化学、区域和对映选择性，多样性导向的CADA反应被认为更具挑战性且仍然难以实现。在这项工作中，o-QDIs被用作通用的结构单元，实现了吲哚的化学发散性去芳构化芳基化反应和[4 + 2]环加成反应。在手性磷酸催化和温和条件下，各种吲哚啉、呋喃吲哚啉/吡咯吲哚啉以及六元环稠合吲哚啉均能以良好的收率和优异的对映选择性共同制备。这种多样性导向的合成方法丰富了邻醌化学，并为CADA反应提供了新的机会。
