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A Formal Approach to Xylosmin and Flacourtosides E and F: Chemoenzymatic Total Synthesis of the Hydroxylated Cyclohexenone Carboxylic Acid Moiety of Xylosmin

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Department of Chemistry and Centre for Biotechnology, Brock University, St. Catharines, ON L2S 3A1, Canada
Cite this: Org. Lett. 2017, 19, 5, 1156–1159
Publication Date (Web):February 10, 2017
https://doi.org/10.1021/acs.orglett.7b00194
Copyright © 2017 American Chemical Society

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    Abstract

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    The hydroxylated cyclohexenone carboxylic acid moiety of xylosmin was synthesized in eight steps from benzoic acid. The key steps in the synthesis involved the enzymatic dihydroxylation of benzoic acid by the whole cell fermentation with Ralstonia eutrophus B9, and Henbest epoxidation. Early attempts led to the synthesis of a C6 epimer of the methyl ester of the hydroxylated cyclohexenone carboxylic acid moiety. The absolute stereochemistry of an advanced intermediate was confirmed by X-ray crystallography. Complete characterization of the previously reported but not fully characterized hydroxylated cyclohexenone carboxylic acid is provided.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.7b00194.

    • Experimental and spectral data are provided for the compounds 5b, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 19, 20, 21, 22, 23, and 24 (PDF)

    • X-ray data is provided for 25 (CIF)

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    Cited By

    This article is cited by 13 publications.

    1. Aleksi Eronen, Martin Nieger, Tommi A. Kajander, Timo Repo. Stereospecific Synthesis of Cyclohexenone Acids by [3,3]-Sigmatropic Rearrangement Route. The Journal of Organic Chemistry 2023, 88 (18) , 12914-12923. https://doi.org/10.1021/acs.joc.3c00757
    2. Andrew J. Paterson, Petter Dunås, Martin Rahm, Per-Ola Norrby, Gabriele Kociok-Köhn, Simon E. Lewis, Nina Kann. Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes: Chirality Transfer via a Heck-Type Mechanism. Organic Letters 2020, 22 (6) , 2464-2469. https://doi.org/10.1021/acs.orglett.0c00708
    3. Tomas Hudlicky. Benefits of Unconventional Methods in the Total Synthesis of Natural Products. ACS Omega 2018, 3 (12) , 17326-17340. https://doi.org/10.1021/acsomega.8b02994
    4. Nagi Reddy Modugu, Goverdhan Mehta. Synthesis of the Polyoxygenated Cyclohexanoid Core of Bioactive Glycosides Xylosmin and Flacourtosides E and F. The Journal of Organic Chemistry 2018, 83 (17) , 10573-10579. https://doi.org/10.1021/acs.joc.8b01389
    5. Emma King-Smith, Christian R. Zwick, III, and Hans Renata . Applications of Oxygenases in the Chemoenzymatic Total Synthesis of Complex Natural Products. Biochemistry 2018, 57 (4) , 403-412. https://doi.org/10.1021/acs.biochem.7b00998
    6. Rodrigo Duarte-Casar, Juan Carlos Romero-Benavides. Xylosma G. Forst. Genus: Medicinal and Veterinary Use, Phytochemical Composition, and Biological Activity. Plants 2022, 11 (9) , 1252. https://doi.org/10.3390/plants11091252
    7. Phuc-Dam Nguyen, Charlotte Sayagh, Georges Massiot, Catherine Lavaud. Phenyl glycosides from the leaves of Flacourtia indica (Burm. f.) Merr (Salicaceae). Phytochemistry 2021, 190 , 112891. https://doi.org/10.1016/j.phytochem.2021.112891
    8. Thierry Prangé, Catherine Lavaud, Georges Massiot. A reappraisal of the structure of xylosmin. Phytochemistry Letters 2021, 41 , 123-124. https://doi.org/10.1016/j.phytol.2020.11.007
    9. Korey Bedard, Tomas Hudlicky. Enzymatic dihydroxylation of aromatic compounds: Nature's unique reaction and its impact on the synthesis of natural products. 2021, 53-97. https://doi.org/10.1016/B978-0-12-822212-6.00006-0
    10. Xiao‐Wei Liang, Yunlong Zhao, Xu‐Ge Si, Meng‐Meng Xu, Jia‐Hao Tan, Zhi‐Mao Zhang, Cheng‐Gong Zheng, Chao Zheng, Quan Cai. Enantioselective Synthesis of Arene cis ‐Dihydrodiols from 2‐Pyrones. Angewandte Chemie International Edition 2019, 58 (41) , 14562-14567. https://doi.org/10.1002/anie.201908284
    11. Xiao‐Wei Liang, Yunlong Zhao, Xu‐Ge Si, Meng‐Meng Xu, Jia‐Hao Tan, Zhi‐Mao Zhang, Cheng‐Gong Zheng, Chao Zheng, Quan Cai. Enantioselective Synthesis of Arene cis ‐Dihydrodiols from 2‐Pyrones. Angewandte Chemie 2019, 131 (41) , 14704-14709. https://doi.org/10.1002/ange.201908284
    12. JiaJia Dong, Elena Fernández‐Fueyo, Frank Hollmann, Caroline E. Paul, Milja Pesic, Sandy Schmidt, Yonghua Wang, Sabry Younes, Wuyuan Zhang. Biokatalytische Oxidationsreaktionen – aus der Sicht eines Chemikers. Angewandte Chemie 2018, 130 (30) , 9380-9404. https://doi.org/10.1002/ange.201800343
    13. JiaJia Dong, Elena Fernández‐Fueyo, Frank Hollmann, Caroline E. Paul, Milja Pesic, Sandy Schmidt, Yonghua Wang, Sabry Younes, Wuyuan Zhang. Biocatalytic Oxidation Reactions: A Chemist's Perspective. Angewandte Chemie International Edition 2018, 57 (30) , 9238-9261. https://doi.org/10.1002/anie.201800343

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