Enantioselective synthesis of mixed 3,3’-bisindoles via a phosphine-catalyzed umpolung γ-addition of 3’-indolyl-3-oxindoles to allenoates  

手性膦催化的3’-吲哚基-3-氧化吲哚对联烯酸酯的极性反转γ-加成反应:非对应选择性的合成混杂3,3’-双吲哚

作　　者：Yildiz Tasdan Guang-Jian Mei Yixin Lu Yildiz Tasdan;梅光建;卢一新(Department of Chemistry,National University of Singapore,Singapore 117543,Singapore;Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 359297,China;National University of Singapore(Suzhou)Research Institute,Suzhou Industrial Park,Suzhou 215123,China)

机构地区：[1]Department of Chemistry,National University of Singapore,Singapore 117543,Singapore [2]Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 359297,China [3]National University of Singapore(Suzhou)Research Institute,Suzhou Industrial Park,Suzhou 215123,China

出　　处：《Science Bulletin》2020年第7期557-563,M0004,共8页科学通报（英文版）

基　　金：Yixin Lu thanks the Singapore National Research Foundation,Prime Minister’s Office for the NRF Investigatorship Award(R-143-000-A15-281);Financial supports from the National University of Singapore(R-143-000-695-114 and C-141-000-092-001);the National Natural Science Foundation of China(21672158)are also gratefully acknowledged.

摘　　要：An enantioselective umpolung γ-addition reaction of 3’-indolyl-3-oxindoles to allenoates catalyzed by amino acid-derived bifunctional phosphine catalysts has been developed. A wide range of chiral mixed 3,3’-bisindole scaffolds containing an all-carbon quaternary stereogenic center were obtained in high yields and with excellent enantioselectivities. 3,3’-Bisindoles are valuable synthetic intermediates, the employment of which led to formal total syntheses of(+)-Chimonanthine,(+)-Folicanthine and(-)-Calycanthine, as well as facile creation of useful pyrrolidinoindoline core structure.该研究为3,3’双吲哚的不对称合成发展了一种高效方法.在氨基酸衍生的双官能团膦催化剂的催化下, 3’-吲哚基-3-氧化吲哚对联烯酸酯的极性反转γ-加成反应顺利发生.采用该方法,成功构建了一系列含有一个全碳季碳中性的手性3,3’-双吲哚结构单元,其具有高产率和高非对应选择性.该手性3,3’-双吲哚结构单元是合成中的重要中间体.从该中间体出发,本文成功地完成了天然生物碱(+)-Chimonanthine,(+)-Folicanthine和(-)-Calycanthine的形式全合成,以及构建了生物碱Gliocladin C及其家族成员的核心骨架-吡咯并二氢吲哚啉结构.

关 键 词：Umpolung c-addition Amino acid-derived bifunctional phosphine ALLENOATES Mixed 3 30-Bisindole Formal total syntheses 

分 类 号：O621.251[理学—有机化学] O626.1[理学—化学]