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Catalytic Asymmetric Oxidative α-C–H N,O-Ketalization of Ketones by Chiral Primary Amine
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    Catalytic Asymmetric Oxidative α-C–H N,O-Ketalization of Ketones by Chiral Primary Amine
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    Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China
    Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300071, China
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    Organic Letters

    Cite this: Org. Lett. 2015, 17, 17, 4392–4395
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    https://doi.org/10.1021/acs.orglett.5b02322
    Published August 21, 2015
    Copyright © 2015 American Chemical Society

    Abstract

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    A highly enantioselective primary amine catalyzed α,α-bis-functionalization of β-ketocarbonyls and cyclohexanones is described. This transformation employs N-hydroxycarbamates as both nitrogen and oxygen sources under aerobic oxidative conditions to furnish chiral N,O-ketals with high yields and enantioselectivities.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.5b02322.

    • Experimental procedures, characterization data, and copies of 1H NMR and 13C NMR spectra and HPLC traces (PDF)

    • Crystallographic data for 10c (CIF)

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    This article is cited by 19 publications.

    1. Mao Cai, Long Zhang, Wenzhao Zhang, Qifeng Lin, Sanzhong Luo. Enantioselective Transformations by “1 + x” Synergistic Catalysis with Chiral Primary Amines. Accounts of Chemical Research 2024, 57 (10) , 1523-1537. https://doi.org/10.1021/acs.accounts.4c00128
    2. Jun Zhang, Saeedeh Torabi Kohlbouni, Babak Borhan. Cu-Catalyzed Oxidation of C2 and C3 Alkyl-Substituted Indole via Acyl Nitroso Reagents. Organic Letters 2019, 21 (1) , 14-17. https://doi.org/10.1021/acs.orglett.8b03185
    3. Lihui Zhu, Dehong Wang, Zongbin Jia, Qifeng Lin, Mouxin Huang, Sanzhong Luo. Catalytic Asymmetric Oxidative Enamine Transformations. ACS Catalysis 2018, 8 (6) , 5466-5484. https://doi.org/10.1021/acscatal.8b01263
    4. Santiago Cañellas, Carles Ayats, Andrea H. Henseler, and Miquel A. Pericàs . A Highly Active Polymer-Supported Catalyst for Asymmetric Robinson Annulations in Continuous Flow. ACS Catalysis 2017, 7 (2) , 1383-1391. https://doi.org/10.1021/acscatal.6b03286
    5. Samson Afewerki and Armando Córdova . Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis. Chemical Reviews 2016, 116 (22) , 13512-13570. https://doi.org/10.1021/acs.chemrev.6b00226
    6. Quanbin Jiang, Jie Luo, Xiaodan Zhao. Enantioselective cross-dehydrogenative coupling enabled by organocatalysis. Green Chemistry 2024, 26 (4) , 1846-1875. https://doi.org/10.1039/D3GC04154A
    7. Mao Cai, Runze Zhang, Chunming Yang, Sanzhong Luo. Bio‐inspired Small Molecular Catalysis. Chinese Journal of Chemistry 2023, 41 (5) , 548-559. https://doi.org/10.1002/cjoc.202200628
    8. Akira Yanagisawa, Shiho Kasahara, Akihiro Takeishi, Tomoki Marui. Enantioselective Synthesis of α-Hydroxyamino Ketones by a Chiral Phosphine–Silver Complex Catalyzed N-Nitroso Aldol Reaction. Synlett 2022, 33 (20) , 2019-2025. https://doi.org/10.1055/a-1955-2016
    9. . Enamine‐Metal Combined Catalysis. 2022, 39-74. https://doi.org/10.1002/9783527345939.ch3
    10. Nuno R. Candeias, Alexander Efimov. Thiopyrans and Their Benzo Derivatives. 2022, 512-670. https://doi.org/10.1016/B978-0-12-818655-8.00020-2
    11. Zongbin Jia, Sanzhong Luo. Asymmetric Oxidative α-Functionalization of Carbonyls Via C-O/C-N Bond Formation. 2022https://doi.org/10.1016/B978-0-32-390644-9.00025-1
    12. Deqian Sun, Shuang Yang, Xinqiang Fang. Asymmetric catalytic construction of fully substituted carbon stereocenters using acyclic α-branched β-ketocarbonyls: the “Methyl Rule” widely exists. Organic Chemistry Frontiers 2020, 7 (21) , 3557-3577. https://doi.org/10.1039/D0QO00673D
    13. Samson Afewerki, Armando Córdova. Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates. Topics in Current Chemistry 2019, 377 (6) https://doi.org/10.1007/s41061-019-0267-y
    14. Gang Zhang, Courtney C. Aldrich. Macozinone: revised synthesis and crystal structure of a promising new drug for treating drug-sensitive and drug-resistant tuberculosis. Acta Crystallographica Section C Structural Chemistry 2019, 75 (8) , 1031-1035. https://doi.org/10.1107/S2053229619009185
    15. Si-Qing He, Jing Wang, Dan-Dan Wu, Xiao-Jing Sang, Fang Su, Zai-Ming Zhu, Lan-Cui Zhang. Preparation of carboxyethyltin group-functionalized highly ordered mesoporous organosilica composite material with double acid sites. Journal of Materials Science 2019, 54 (6) , 4601-4618. https://doi.org/10.1007/s10853-018-03207-8
    16. Jingchuan Zhang, Kai Fu, Lili Lin, Yan Lu, Xiaohua Liu, Xiaoming Feng. Efficient Catalytic Enantioselective Hydroxyamination of α‐Aryl‐α‐Cyanoacetates with 2‐Nitrosopyridines. Chemistry – A European Journal 2018, 24 (17) , 4289-4293. https://doi.org/10.1002/chem.201800592
    17. Akira Yanagisawa, Yuqin Lin, Akihiro Takeishi, Kazuhiro Yoshida. Enantioselective Nitroso Aldol Reaction Catalyzed by a Chiral Phosphine–Silver Complex. European Journal of Organic Chemistry 2016, 2016 (32) , 5355-5359. https://doi.org/10.1002/ejoc.201601143
    18. Andrea Gualandi, Luca Mengozzi, Elisabetta Manoni, Pier Giorgio Cozzi. From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions. The Chemical Record 2016, 16 (3) , 1228-1243. https://doi.org/10.1002/tcr.201500299
    19. Changming Xu, Long Zhang, Sanzhong Luo. ChemInform Abstract: Catalytic Asymmetric Oxidative α‐C—H N,O‐Ketalization of Ketones by Chiral Primary Amine.. ChemInform 2016, 47 (3) https://doi.org/10.1002/chin.201603054

    Organic Letters

    Cite this: Org. Lett. 2015, 17, 17, 4392–4395
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.orglett.5b02322
    Published August 21, 2015
    Copyright © 2015 American Chemical Society

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