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Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues

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    Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues
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    † Institute of Toxicology, 1, Bekhterev St., St. Petersburg, 192019, Russian Federation
    ‡ NRC Kurchatov Institute, 1, Acad. Kurchatov Sq., Moscow, 123182, Russian Federation
    § A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28, Vavilov St., Moscow, 119991 Russian Federation
    *(K.A.K.) E-mail: [email protected]
    *(V.N.K.) E-mail: [email protected]
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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2014, 14, 8, 3975–3982
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    https://doi.org/10.1021/cg500570u
    Published July 10, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    1-Alkyl-5-(5-nitro-2-N-morpholinobenzylidene) barbituric acids undergo tert-amino effect reactions (T-reactions) yielding 1-alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrene derivatives as a mixture of (S*,S*)- and (S*,R*)-diastereomers. A novel heterophase modification of the T-reaction is proposed, which makes it possible to afford nearly pure (S*,S*)-diastereomers in high yields, whereas rearrangement reactions in solutions usually lack stereoselectivity. To our best knowledge, this is the first example of deliberate tuning stereodirection of a T-reaction by external conditions. Using X-ray diffraction analysis, we demonstrate that this diastereoselectivity of the solid state T-reaction is due to a peculiar crystal structure of starting 5-arylidene barbiturates, which accommodates only one specific conformation fixed by a strong intramolecular C–H···π interaction.

    Copyright © 2014 American Chemical Society

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    This article is cited by 5 publications.

    1. Hong-Wu Zhao, Ting Tian, Bo Li, Zhao Yang, Hai-Liang Pang, Wei Meng, Xiu-Qing Song, and Xiao-Qin Chen . Diastereoselective Synthesis of Dispirobarbiturates through Et3N-Catalyzed [3 + 2] Cycloaddition of Barbiturate-Based Olefins with 3-Isothiocyanato Oxindoles. The Journal of Organic Chemistry 2015, 80 (20) , 10380-10385. https://doi.org/10.1021/acs.joc.5b01810
    2. Kuo Wang, Yue Zhang, Yu‐Hang Mi, Hong‐Wu Zhao, Xiu‐Qing Song, Jin‐Tao Li, Fang Zhang. Rh(II)‐Catalyzed Homocoupling/[4+1] Cycloaddition Cascade of Diazobarbiturates with Diazopyrazolones to Prepare Spirobarbiturates. Advanced Synthesis & Catalysis 2024, 366 (11) , 2596-2601. https://doi.org/10.1002/adsc.202400064
    3. Devanshi Magoo, Anju Srivastava, Shruti Gupta, Reena Jain, Soma Mondal Ghorai, Yashna Dawer, Sumedha Sengupta, Soni Rani. Developments in Synthesis Strategies of Spiro-Barbiturate Compounds: A Classified Study. Mini-Reviews in Organic Chemistry 2024, 21 (2) , 246-270. https://doi.org/10.2174/1570193X20666230428112212
    4. Konstantin A. Krasnov, Alexandra A. Krasnova, Viktor G. Kartsev, Pavel V. Dorovatovskii, Yan V. Zubavichus, Ekaterina V. Dobrokhotova, Ekaterina K. Kultyshkina, Victor N. Khrustalev. Stereodirected synthesis of alkaloid-like quinolizidine systems. Natural Product Research 2020, 34 (2) , 269-277. https://doi.org/10.1080/14786419.2018.1528588
    5. Hong‐Wu Zhao, Ting Tian, Hai‐Liang Pang, Bo Li, Xiao‐Qin Chen, Zhao Yang, Wei Meng, Xiu‐Qing Song, Yu‐Di Zhao, Yue‐Yang Liu. Organocatalytic [3+2] Cycloadditions of Barbiturate‐Based Olefins with 3‐Isothiocyanato Oxindoles: Highly Diastereoselective and Enantioselective Synthesis of Dispirobarbiturates. Advanced Synthesis & Catalysis 2016, 358 (16) , 2619-2630. https://doi.org/10.1002/adsc.201600270
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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2014, 14, 8, 3975–3982
    Click to copy citationCitation copied!
    https://doi.org/10.1021/cg500570u
    Published July 10, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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