文献类型：期刊文献

英文题名：Diastereo- and Enantioselective Synthesis of Bisbenzannulated Spiroketals and Spiroaminals by Ir/Ag/Acid Ternary Catalysis

作者：Yang, Wu-Lin[1,2];Shang, Xin-Yu[1,2];Ni, Tao[1,2];Yan, Hui[1,2];Luo, Xiaoyan[1,2];Zheng, Hanliang[3];Li, Zhong[1,2];Deng, Wei-Ping[1,2,3]

机构：[1]East China Univ Sci & Technol, Shanghai Key Lab Chem Biol, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Zhejiang Normal Univ, Dept Chem, Minist Educ Adv Catalysis Mat, Key Lab, Jinhua 321004, Zhejiang, Peoples R China

年份：2022

卷号：61

期号：42

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20223512632610);WOS:【SCI-EXPANDED(收录号:WOS:000841823300001)，CCR-EXPANDED(收录号:WOS:000841823300001)】；

基金：This work was supported by National Natural Science Foundation of China (Nos. 22171081 and 21971062), National Key Research and Development Program of China (No. 2021YFA0804900) and Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism.

语种：英文

外文关键词：Allylation; Asymmetric Synthesis; Iridium; Spiroketals; Ternary Catalysis

摘要：We reported herein an iridium/silver/acid ternary catalytic system to access bisbenzannulated [6,6]-spiroketals in high efficiency with generally high diastereo- and enantioselectivities (up to >20 : 1 dr, >99 % ee). In this procedure, readily available o-alkynylacetophenones undergo cycloisomerization to generate isochromenes in situ that participate in stereoselective allylation/spiroketalization sequence with 2-(1-hydroxyallyl)phenols. Meanwhile, 2-(1-hydroxyallyl)anilines were also compatible in this cascade reaction, furnishing structurally novel bisbenzannulated [6,6]-spiroaminals with good diastereoselectivities (8 : 1-12 : 1 dr) and excellent enantioselectivities (98 %->99 % ee). Moreover, experimental studies and theoretical calculations were performed to illustrate the reaction mechanism and stereochemistry.