ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Gold-Catalyzed Intramolecular Dearomatization Reactions of Indoles for the Synthesis of Spiroindolenines and Spiroindolines

  • Wen-Ting Wu
    Wen-Ting Wu
    State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 LinglingLu, Shanghai 200032, China
    More by Wen-Ting Wu
  • Lu Ding
    Lu Ding
    School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China
    More by Lu Ding
  • Liming Zhang*
    Liming Zhang
    Department of Chemistry & Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106, United States
    *E-mail: [email protected]
    More by Liming Zhang
  • , and 
  • Shu-Li You*
    Shu-Li You
    State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 LinglingLu, Shanghai 200032, China
    School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China
    *E-mail: [email protected]
    More by Shu-Li You
Cite this: Org. Lett. 2020, 22, 4, 1233–1238
Publication Date (Web):December 2, 2019
https://doi.org/10.1021/acs.orglett.9b03988
Copyright © 2019 American Chemical Society

    Article Views

    4405

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    A gold-catalyzed dearomatization reaction of indole derivatives was realized in the presence of JohnPhosAuCl/AgOMs to afford a series of spiroindolenines in excellent yields (≤99%). In addition, when the Hantzsch ester was used as the hydrogen transfer reagent, various spiroindolines were obtained in a cascade fashion starting from readily available indole derivatives in modest to good yields (≤79%). Both reactions feature readily available substrates, mild conditions, and good functional group tolerance.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.9b03988.

    • Experimental procedures and analysis data for all new compounds (PDF)

    Accession Codes

    CCDC 19159431915944 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.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 42 publications.

    1. Jiang Zhu, Jiaji Li, Lianjie Zhang, Shitao Sun, Lu Yang, Jiayue Fu, Hanyang Sun, Maosheng Cheng, Bin Lin, Yongxiang Liu. Gold(I)-Catalyzed Substitution-Controlled Syntheses of Spiro[indoline-3,3′-pyrrolidine] and Spiro[indoline-3,3′-piperidine] Derivatives. The Journal of Organic Chemistry 2023, 88 (15) , 10586-10598. https://doi.org/10.1021/acs.joc.3c00604
    2. Floris Buttard, Xavier Guinchard. Spiroindoles as Intermediates/Products in Transition Metal-Catalyzed Dearomatization of Indoles. ACS Catalysis 2023, 13 (14) , 9442-9475. https://doi.org/10.1021/acscatal.3c01417
    3. Kota Sugimoto, Io Mori, Takanari Kato, Koji Yasui, Ban Xu, Choon Hong Tan, Minami Odagi, Kazuo Nagasawa. Guanidinium Hypoiodite-Catalyzed Intramolecular Oxidative Coupling Reaction of Oxindoles with β-Dicarbonyls. The Journal of Organic Chemistry 2023, 88 (12) , 7660-7673. https://doi.org/10.1021/acs.joc.2c02500
    4. Qin Jiang, Ting Yang, Qi Li, Guang-Ming Liang, Yong Liu, Cheng-Yu He, Wen-Dao Chu, Quan-Zhong Liu. Synthesis of Cyclopenta[b]indoles via Sc(III)-Catalyzed Annulation of Vinyl Diazoacetates with Indole-Derived Unsaturated Imines. Organic Letters 2023, 25 (18) , 3184-3189. https://doi.org/10.1021/acs.orglett.3c00192
    5. Jiang Zhu, Jiaji Li, Lianjie Zhang, Shitao Sun, Zhaobo Wang, Xiang Li, Lu Yang, Maosheng Cheng, Bin Lin, Yongxiang Liu. Quantum Mechanical Prediction and Experimental Verification of Au(I)-Catalyzed Substitution-Controlled Syntheses of 1H-Pyrido[4,3-b]indole and Spiro[indoline-3,3′-pyridine] Derivatives. The Journal of Organic Chemistry 2023, 88 (9) , 5483-5496. https://doi.org/10.1021/acs.joc.2c03104
    6. Jun-An Xiao, Hai Peng, Huan Zhang, Ru-Fang Meng, Chenxiang Lin, Wei Su, Yanmin Huang. Synergistic Sc(III)/Au(I)-Catalyzed Dearomative Spiroannulation of 2-(Ethynyl)aryl Cyclopropanes with 2-Aryl Indoles. Organic Letters 2022, 24 (47) , 8709-8713. https://doi.org/10.1021/acs.orglett.2c03679
    7. Liangyong Mei, Jules Moutet, Savannah M. Stull, Thomas L. Gianetti. Synthesis of CF3-Containing Spirocyclic Indolines via a Red-Light-Mediated Trifluoromethylation/Dearomatization Cascade. The Journal of Organic Chemistry 2021, 86 (15) , 10640-10653. https://doi.org/10.1021/acs.joc.1c01313
    8. Guzhou Chen, Peng-Yu Liu, Huanhuan Zou, Jiadong Hu, Xiaowu Fang, Dongyang Xu, Yu-Peng He, Hongbo Wei, Weiqing Xie. Au(I)-Catalyzed Domino Cyclization of 1,6-Diynes Incorporated with Indole. Organic Letters 2021, 23 (6) , 2279-2284. https://doi.org/10.1021/acs.orglett.1c00411
    9. Xue-Song Li, Dan-tong Xu, Zhi-Jie Niu, Ming Li, Wei-Yu Shi, Cui-Tian Wang, Wan-Xu Wei, Yong-Min Liang. Gold-Catalyzed Tandem Annulations of Pyridylhomopropargylic Alcohols with Propargyl Alcohols. Organic Letters 2021, 23 (3) , 832-836. https://doi.org/10.1021/acs.orglett.0c04070
    10. Haruka Homma, Shingo Harada, Tsubasa Ito, Ayaka Kanda, Tetsuhiro Nemoto. Atypical Dearomative Spirocyclization of β-Naphthols with Diazoacetamides Using a Silver Catalyst. Organic Letters 2020, 22 (20) , 8132-8138. https://doi.org/10.1021/acs.orglett.0c03110
    11. Yan-Xue Zhang, Ling-Yan Chen, Jian-Ting Sun, Chang-Mei Si, Bang-Guo Wei. Gold-Catalyzed Addition–N-Boc Cleavage–Cyclization of N,O-Acetal with Ynamides for Construction of 6-(tert-Butyldimethylsilyl)oxy-tetrahydropyrrolo[1,2-c][1,3]oxazin-1-ones. The Journal of Organic Chemistry 2020, 85 (19) , 12603-12613. https://doi.org/10.1021/acs.joc.0c01776
    12. Euan B. McLean, Francesca M. Cutolo, Orla J. Cassidy, David J. Burns, Ai-Lan Lee. Selectivity Control in Gold-Catalyzed Hydroarylation of Alkynes with Indoles: Application to Unsymmetrical Bis(indolyl)methanes. Organic Letters 2020, 22 (17) , 6977-6981. https://doi.org/10.1021/acs.orglett.0c02526
    13. Jun Ueda, Shingo Harada, Ayaka Kanda, Hiroki Nakayama, Tetsuhiro Nemoto. Silver-Catalyzed, Chemo- and Enantioselective Intramolecular Dearomatization of Indoles to Access Sterically Congested Azaspiro Frameworks. The Journal of Organic Chemistry 2020, 85 (16) , 10934-10950. https://doi.org/10.1021/acs.joc.0c01580
    14. Valentin Magné, Youssouf Sanogo, Charles S. Demmer, Pascal Retailleau, Angela Marinetti, Xavier Guinchard, Arnaud Voituriez. Chiral Phosphathiahelicenes: Improved Synthetic Approach and Uses in Enantioselective Gold(I)-Catalyzed [2 + 2] Cycloadditions of N-Homoallenyl Tryptamines. ACS Catalysis 2020, 10 (15) , 8141-8148. https://doi.org/10.1021/acscatal.0c01819
    15. Nazarii Sabat, Feryel Soualmia, Pascal Retailleau, Alhosna Benjdia, Olivier Berteau, Xavier Guinchard. Gold-Catalyzed Spirocyclization Reactions of N-Propargyl Tryptamines and Tryptophans in Aqueous Media. Organic Letters 2020, 22 (11) , 4344-4349. https://doi.org/10.1021/acs.orglett.0c01370
    16. Manda Rajesh, Ravi Kumar, Surendra Puri, Jagadeesh Babu Nanubolu, Maddi Sridhar Reddy. Lewis-Acid-Catalyzed Decarboxylative Annulation of 2-Aminoindole-3-Carboxylate with Ynals Involving [3 + 2] Spirocycloaddition and 2,3-Aza Migration. Organic Letters 2020, 22 (3) , 1117-1123. https://doi.org/10.1021/acs.orglett.9b04626
    17. Xiao-Bao Wu, Jun-Xiu Shi, Yi-Ming Ou, Hua-Jie Jiang, Yi-Jun Fang, Qi-Ming Wang, Quan Gao, Jie Yu. Sequential enantioselective Ugi-4CR/post-Ugi transformation strategy: a precise construction of structurally diverse azaspiro polycyclic scaffolds. Science China Chemistry 2024, 67 (2) , 576-586. https://doi.org/10.1007/s11426-023-1782-9
    18. Zhen Liu, Mitch Mathiew, Jichao Chen, Xiangdong Yu, Dandan Shang, Javey Khiapeng Tan, Philip Wai Hong Chan, Weidong Rao. Gold catalyzed spirocyclization of 1-ene-4,9- and 3-ene-1,7-diyne esters to azaspiro[4.4]nonenones and azaspiro[4.5]decadienones. Organic Chemistry Frontiers 2024, 11 (3) , 761-768. https://doi.org/10.1039/D3QO01655B
    19. Suchita S. Gadekar, Rajesh A. Joshi, Balaji R. Madje, Shrikrishna T. Salunke, Suryakant B. Sapkal. PIPES-ZnO NPs coupled catalyst for the synthesis of 2-((1H-indol-3-yl)(phenyl)methyl)-5,5-dimethylcyclohexane-1,3-diones. Results in Chemistry 2023, 6 , 101074. https://doi.org/10.1016/j.rechem.2023.101074
    20. Claire Fleurisson, Nessrine Graidia, Yann Foricher, Erica Benedetti, Laurent Micouin. Intramolecular Buchwald–Hartwig N -arylation of bicyclic hydrazines: practical access to spiro[indoline-2,3′-piperidines]. Organic & Biomolecular Chemistry 2023, 21 (17) , 3542-3546. https://doi.org/10.1039/D3OB00406F
    21. Shitao Sun, Jinle Hao, Maosheng Cheng, Yongxiang Liu, Bin Lin. Computational insight into gold( i )-catalyzed intramolecular regioselectivity of tryptamine-ynamide cycloisomerizations. Organic & Biomolecular Chemistry 2023, 21 (12) , 2610-2619. https://doi.org/10.1039/D3OB00079F
    22. Yongjie Yang, Kai Jiang, Guohui Zeng, Biaolin Yin. Transition Metal‐Catalyzed Dearomative Vinylation of Electron Rich Benzenes, Naphthalenes and Indoles with Alkynes. Advanced Synthesis & Catalysis 2023, 365 (3) , 270-294. https://doi.org/10.1002/adsc.202201285
    23. Hongmei Qin, Qimei Xie, Long He. Synthesis of spiroindolenine-bearing chroman scaffolds based on a cyclization reaction of para -Quinone methides. New Journal of Chemistry 2022, 46 (21) , 9985-9988. https://doi.org/10.1039/D2NJ00936F
    24. Wang Wang, Pei-Sen Zou, Li Pang, Yao Lei, Zi-Yi Huang, Nan-Ying Chen, Dong-Liang Mo, Cheng-Xue Pan, Gui-Fa Su. Synthesis of spiroindolenine-3,3′-pyrrolo[2,1- b ]quinazolinones through gold( i )-catalyzed dearomative cyclization of N -alkynyl quinazolinone-tethered indoles. Organic & Biomolecular Chemistry 2022, 20 (10) , 2069-2074. https://doi.org/10.1039/D1OB02492B
    25. Yunhe Li, Yi Zhou, Jie Zhang, Ruiyu Liu, Xiang Zhao, Youliang Wang. A DFT study on gold-catalyzed domino cyclization for post-Ugi synthesis of spiroindolines: insights on the origin of remarkable diastereoselectivity. Catalysis Science & Technology 2022, 12 (5) , 1678-1684. https://doi.org/10.1039/D1CY01453F
    26. Yanyu Chen, Zhaobo Wang, Wutong Zhao, Shitao Sun, Lu Yang, Junpeng Zhang, Di Zhang, Maosheng Cheng, Bin Lin, Yongxiang Liu. Ag( i )/PPh 3 -catalyzed diastereoselective syntheses of spiro[indole-3,4′-piperidine] derivatives via cycloisomerizations of tryptamine-ynamides. Chemical Communications 2022, 58 (18) , 3051-3054. https://doi.org/10.1039/D1CC07298F
    27. Wang Wang, Nan‐Ying Chen, Pei‐Sen Zou, Li Pang, Dong‐Liang Mo, Cheng‐Xue Pan, Gui‐Fa Su. Gold(I)‐Catalyzed Selective Cyclization and 1,2‐Shift to Prepare Pseudorutaecarpine Derivatives. Advanced Synthesis & Catalysis 2022, 364 (4) , 787-793. https://doi.org/10.1002/adsc.202101054
    28. Ali Osman Karatavuk. One-pot gold( i )-catalyzed synthesis of 2-pyridonyl alcohols. Organic & Biomolecular Chemistry 2021, 19 (48) , 10617-10621. https://doi.org/10.1039/D1OB01950C
    29. Xiaohui Wei, Xuewu Liang, Yazhou Li, Qi Liu, Xuyi Liu, Yu Zhou, Hong Liu. I 2 -induced cascade cyclization and dearomatization of indoles for the highly efficient synthesis of iodinated and vinylic spiroindolenines. Green Chemistry 2021, 23 (22) , 9165-9171. https://doi.org/10.1039/D1GC02713A
    30. Jia‐Hao Xie, Chao Zheng, Shu‐Li You. Palladium‐Catalyzed Dearomative Methoxyallylation of 3‐Nitroindoles with Allyl Carbonates. Angewandte Chemie 2021, 133 (41) , 22358-22362. https://doi.org/10.1002/ange.202107139
    31. Jia‐Hao Xie, Chao Zheng, Shu‐Li You. Palladium‐Catalyzed Dearomative Methoxyallylation of 3‐Nitroindoles with Allyl Carbonates. Angewandte Chemie International Edition 2021, 60 (41) , 22184-22188. https://doi.org/10.1002/anie.202107139
    32. Jun Ueda, Shingo Harada, Mayu Kobayashi, Mai Yanagawa, Tetsuhiro Nemoto. Maleic Acid/Thiourea‐Catalyzed Dearomative ipso ‐Friedel–Crafts Reaction of Indoles to Produce Functionalized Spiroindolenines. European Journal of Organic Chemistry 2021, 2021 (29) , 3999-4006. https://doi.org/10.1002/ejoc.202100215
    33. Anvar Mirzaei, Gábor Turczel, Márton Nagyházi, Vajk Farkas, Áron Balla, Hai Dang Vu, Robert Tuba. Cyclative MCRs of Azines and Azinium Salts. European Journal of Organic Chemistry 2021, 2021 (3) , 326-356. https://doi.org/10.1002/ejoc.202001048
    34. Debojyoti Bag, Sanghapal D. Sawant. Heteroarene‐tethered Functionalized Alkyne Metamorphosis. Chemistry – A European Journal 2021, 27 (4) , 1165-1218. https://doi.org/10.1002/chem.202002154
    35. Qiang-Qiang Liu, Chao Zheng, Shu-Li You. Silica gel-promoted synthesis of multisubstituted spiroindolenines from tryptamines and γ-chloro-α,β-unsaturated ketones. Tetrahedron 2021, 77 , 131765. https://doi.org/10.1016/j.tet.2020.131765
    36. Yunhe Li, Xiang Zhao. Importance of Counterions in Gold‐hydrogen Bonding Cooperative Catalytic Approach to Spirocyclic Rings: Insights on Mechanism and Origins. ChemCatChem 2020, 12 (24) , 6265-6271. https://doi.org/10.1002/cctc.202001303
    37. Xiaoshuang Gao, Yao Yuan, Xiaomin Xie, Zhaoguo Zhang. Visible-light-induced cascade dearomatization cyclization between alkynes and indole-derived bromides: a facile strategy to synthesize spiroindolenines. Chemical Communications 2020, 56 (90) , 14047-14050. https://doi.org/10.1039/D0CC05672C
    38. Antonella Ilenia Alfano, Angela Zampella, Ettore Novellino, Margherita Brindisi, Heiko Lange. Harnessing interrupted Fischer in continuous flow: sustainable synthesis of (spiro)indolenine and (spiro)indoline privileged scaffolds. Reaction Chemistry & Engineering 2020, 5 (11) , 2091-2100. https://doi.org/10.1039/D0RE00329H
    39. Yunhe Li, Xiang Zhao. Assessing counterion effects in gold-catalyzed domino spirocyclization: an industrial perspective on hydrogen bonding. Physical Chemistry Chemical Physics 2020, 22 (35) , 19606-19612. https://doi.org/10.1039/D0CP03367G
    40. Abdullah S. Alshreimi, Guanqun Zhang, Tyler W. Reidl, Ricardo L. Peña, Nicholas‐George Koto, Shahidul M. Islam, Donald J. Wink, Laura L. Anderson. Synthesis of Spirocyclic 1‐Pyrrolines from Nitrones and Arynes through a Dearomative [3,3′]‐Sigmatropic Rearrangement. Angewandte Chemie 2020, 132 (35) , 15356-15360. https://doi.org/10.1002/ange.202004652
    41. Abdullah S. Alshreimi, Guanqun Zhang, Tyler W. Reidl, Ricardo L. Peña, Nicholas‐George Koto, Shahidul M. Islam, Donald J. Wink, Laura L. Anderson. Synthesis of Spirocyclic 1‐Pyrrolines from Nitrones and Arynes through a Dearomative [3,3′]‐Sigmatropic Rearrangement. Angewandte Chemie International Edition 2020, 59 (35) , 15244-15248. https://doi.org/10.1002/anie.202004652
    42. Motakatla Venkata Krishna Reddy, Gokanapalli Anusha, Peddiahgari Vasu Govardhana Reddy. Sterically enriched bulky 1,3-bis( N , N ′-aralkyl)benzimidazolium based Pd-PEPPSI complexes for Buchwald–Hartwig amination reactions. New Journal of Chemistry 2020, 44 (27) , 11694-11703. https://doi.org/10.1039/D0NJ01294G

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect