Liu Chao, Tan Xiangwen, Zhan Lingzhi, Jing Yaru, Wu Wanqing, Ke Zhuofeng, Jiang Huanfeng
State Key Laboratory of Pulp and Paper Engineering, Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641, China.
School of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou, 510275, China.
Angew Chem Int Ed Engl. 2022 Dec 19;61(51):e202215020. doi: 10.1002/anie.202215020. Epub 2022 Nov 22.
A novel and expedient cascade strategy has been demonstrated for the synthesis of fused benzo-aza-oxa-[5-6-5] tetracycles in high yields and diastereoselectivities (up to 20 : 1 dr). The strategy was fulfilled through palladium-catalyzed oxidative convergent assembly of functionally divergent anilines and 3-butenoic acid with five chemical bonds constructed. Coupled with control experiments and deuterium labelled studies, DFT calculations were performed for the proposed mechanism. The utility of the illustrated strategy is emphasized by gram-scale syntheses, late-stage functionalization, and the transformation to a key core of natural products such as martinellic acid and seneciobipyrrolidine.
一种新颖且便捷的串联策略已被证明可用于高产率和非对映选择性（高达20:1的dr值）地合成稠合苯并氮杂-氧杂-[5-6-5]四环。该策略通过钯催化的功能不同的苯胺和3-丁烯酸的氧化收敛组装来实现，构建了五条化学键。结合对照实验和氘标记研究，对提出的机理进行了密度泛函理论（DFT）计算。克级合成、后期官能团化以及向天然产物如马丁宁酸和千里光双吡咯烷的关键核心的转化强调了所示策略的实用性。
