Iodine as Polarity-Reversal Catalyst: Synthesis of a Fused Heterocycle with Contiguous Stereocenters

作者：Li‐Sheng Wang, Yu-Man Song, You Zhou, Yong‐Xing Tang, Chun‐Yan Wu, Zhi‐Cheng Yu, Hui Zhou, Kai‐Lu Zheng, An‐Xin Wu · 发表于：Organic Letters · 年份：2024 · DOI：10.1021/acs.orglett.4c03936 · 被引用次数：7 · 研究领域：Oxidative Organic Chemistry Reactions、Catalytic C–H Functionalization Methods、Asymmetric Synthesis and Catalysis

We report an unconventional I 2 -catalyzed cascade reaction for the synthesis of angular triquinane derivatives with a fused heterocycle skeleton, leveraging enaminones and anilines as simple acyclic precursors. The key to success lies in I 2 functioning as a polar-reversal catalyst, which alters the reactivity at the α-position of the enaminone and facilitates the first hexa-functionalization of an enaminone along with the formation of highly congested continuous stereocenters.