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Asymmetric Total Syntheses of Schizozygane Alkaloids

  • Wenqiang Zhou
    Wenqiang Zhou
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
  • Tao Zhou
    Tao Zhou
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Tao Zhou
  • Mengxing Tian
    Mengxing Tian
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
  • Yan Jiang
    Yan Jiang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Yan Jiang
  • Jiaojiao Yang
    Jiaojiao Yang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
  • Shuai Lei
    Shuai Lei
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Shuai Lei
  • Qi Wang
    Qi Wang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Qi Wang
  • Chongzhou Zhang
    Chongzhou Zhang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
  • Hanyue Qiu
    Hanyue Qiu
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Hanyue Qiu
  • Ling He
    Ling He
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Ling He
  • Zhen Wang
    Zhen Wang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Zhen Wang
  • Jun Deng
    Jun Deng
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    More by Jun Deng
  • , and 
  • Min Zhang*
    Min Zhang
    Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China
    *Email: [email protected]
    More by Min Zhang
Cite this: J. Am. Chem. Soc. 2021, 143, 47, 19975–19982
Publication Date (Web):November 19, 2021
https://doi.org/10.1021/jacs.1c10279
Copyright © 2021 American Chemical Society

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    Abstract

    Abstract Image

    The concise, collective, and asymmetric total syntheses of four schizozygane alkaloids, which feature a “Pan lid”-like hexacyclic core scaffold bearing up to six continuous stereocenters, including two quaternary ones, are described. A new method of dearomative cyclization of cyclopropanol onto the indole ring at C2 was developed to build the ABCF ring system of the schizozygane core with a ketone group. Another key skeleton-building reaction, the Heck/carbonylative lactamization cascade, ensured the rapid assembly of the hexacyclic schizozygane core and concurrent installation of an alkene group. By strategic use of these two reactions and through late-stage diversifications of the functionalized schizozygane core, the first and asymmetric total syntheses of (+)-schizozygine, (+)-3-oxo-14α,15α-epoxyschizozygine, and (+)-α-schizozygol and the total synthesis of (+)-strempeliopine have been accomplished in 11–12 steps from tryptamines.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c10279.

    • Experimental procedures and compound characterization (PDF)

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    CCDC 2110030, 2110033, 2110041, 2110043, and 2110195 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 13 publications.

    1. Daler Baidilov, Pavel K. Elkin, Sudhakar Athe, Viresh H. Rawal. Rapid Access to 2,2-Disubstituted Indolines via Dearomative Indolic-Claisen Rearrangement: Concise, Enantioselective Total Synthesis of (+)-Hinckdentine A. Journal of the American Chemical Society 2023, 145 (27) , 14831-14838. https://doi.org/10.1021/jacs.3c03611
    2. Hunter S. Sims, Mingji Dai. Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments. The Journal of Organic Chemistry 2023, 88 (8) , 4925-4941. https://doi.org/10.1021/acs.joc.2c02746
    3. Shuangwei Liu, Xiaojiao Su, Dan Jiang, Hongbing Xiong, Dingyin Miao, Lin Fu, Hanyue Qiu, Ling He, Min Zhang. Arylation of Cyclopropanol with Pyrrole: Asymmetric Synthesis of Indolizidine 167B, Indolizidine 209D, and Monomorine I. Organic Letters 2023, 25 (12) , 2058-2062. https://doi.org/10.1021/acs.orglett.3c00406
    4. Wen Zhang, Zhenzhen Wang, Guodan Lin, Yansong Xue, Mengjuan Wu, Pei Tang, Fener Chen. Stereoselective Total Syntheses of C18-Oxo Eburnamine-Vincamine Alkaloids. Organic Letters 2022, 24 (12) , 2409-2413. https://doi.org/10.1021/acs.orglett.2c00661
    5. Shengxian Zhai, Shuxian Qiu, Shuangtao Yang, Xingyuan Gao, Xinyu Feng, Chenzhe Yun, Ning Han, Yongsheng Niu, Jing Wang, Hongbin Zhai. Facile access to β-hydroxyl ketones via a cobalt-catalyzed ring-opening/hydroxylation cascade of cyclopropanols. Chinese Chemical Letters 2023, 34 (3) , 107657. https://doi.org/10.1016/j.cclet.2022.06.080
    6. Jingming Zhang, Chengkou Liu, Yaqi Qiao, Minghui Wei, Wenjing Guan, Ziren Mao, Hong Qin, Zheng Fang, Kai Guo. Intramolecular trapping of spiro radicals to produce unusual cyclization products from usual migration substrates. Chemical Science 2023, 14 (9) , 2461-2466. https://doi.org/10.1039/D2SC05768A
    7. Qiuyu Li, Yunchu Zhang, Pengyun Liu, Jing Zhong, Baihui Gong, Hequan Yao, Aijun Lin. Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes. Angewandte Chemie 2023, 135 (4) https://doi.org/10.1002/ange.202211988
    8. Qiuyu Li, Yunchu Zhang, Pengyun Liu, Jing Zhong, Baihui Gong, Hequan Yao, Aijun Lin. Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes. Angewandte Chemie International Edition 2023, 62 (4) https://doi.org/10.1002/anie.202211988
    9. Chenhao Lou, Leiyang Lv, Zhiping Li. Fe-catalyzed ring-opening reactions of siloxy cyclopropanes with alkenes and TBHP: Synthesis of 4-ester peroxides. Journal of Organometallic Chemistry 2022, 977 , 122467. https://doi.org/10.1016/j.jorganchem.2022.122467
    10. Hong Yan, Gregory S. Smith, Fen-Er Chen. Recent advances using cyclopropanols and cyclobutanols in ring-opening asymmetric synthesis. Green Synthesis and Catalysis 2022, 3 (3) , 219-226. https://doi.org/10.1016/j.gresc.2022.05.007
    11. Jianhua Wang, Xiaoxun Li. Asymmetric β-arylation of cyclopropanols enabled by photoredox and nickel dual catalysis. Chemical Science 2022, 13 (10) , 3020-3026. https://doi.org/10.1039/D1SC07237D
    12. Yan Jiang, Song Xi, Qi Wang, Lin Fu, Ling He, Zhen Wang, Min Zhang. Facile synthesis of δ-ketoesters via formal two-carbon insertion into β-ketoesters. Tetrahedron Letters 2022, 92 , 153656. https://doi.org/10.1016/j.tetlet.2022.153656
    13. . Total Synthesis of (+)-Schizozygine. Synfacts 2022, 0122. https://doi.org/10.1055/s-0041-1737237

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