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Remote Oxidation of Aliphatic C–H Bonds in Nitrogen-Containing Molecules

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    Remote Oxidation of Aliphatic C–H Bonds in Nitrogen-Containing Molecules
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    Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2015, 137, 46, 14590–14593
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    https://doi.org/10.1021/jacs.5b10299
    Published November 4, 2015
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    Abstract

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    Nitrogen heterocycles are ubiquitous in natural products and pharmaceuticals. Herein, we disclose a nitrogen complexation strategy that employs a strong Brønsted acid (HBF4) or an azaphilic Lewis acid (BF3) to enable remote, non-directed C(sp3)–H oxidations of tertiary, secondary, and primary amine- and pyridine-containing molecules with tunable iron catalysts. Imides resist oxidation and promote remote functionalization.

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    51. William G. Shuler, Shea L. Johnson, and Michael K. Hilinski . Organocatalytic, Dioxirane-Mediated C–H Hydroxylation under Mild Conditions Using Oxone. Organic Letters 2017, 19 (18) , 4790-4793. https://doi.org/10.1021/acs.orglett.7b02178
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    79. Masahito Kodera. Bioinspired Catalysts of Non-heme Iron Oxygenases. 2024, 8-40. https://doi.org/10.1039/9781837676484-00008
    80. Jin-Fay Tan, Yi Cheng Kang, John F. Hartwig. Catalytic undirected methylation of unactivated C(sp3)−H bonds suitable for complex molecules. Nature Communications 2024, 15 (1) https://doi.org/10.1038/s41467-024-52245-1
    81. Evgenii P. Talsi, Konstantin P. Bryliakov. Nonheme Fe Based Enzyme Mimics for Fine Organic Synthesis: Catalytic C−H and C=C Oxygenations. European Journal of Organic Chemistry 2024, 27 (40) https://doi.org/10.1002/ejoc.202400664
    82. Christine Mae F. Ancajas, Abiodun S. Oyedele, Caitlin M. Butt, Allison S. Walker. Advances, opportunities, and challenges in methods for interrogating the structure activity relationships of natural products. Natural Product Reports 2024, 41 (10) , 1543-1578. https://doi.org/10.1039/D4NP00009A
    83. Ravindra K. Shukla, Rajesh K. Yadav, Vittal L. Gole, Satyam Singh, Navneet Kumar Gupta, Jin‐Ook Baeg. Photocatalytic fixation and oxygenation of NAD + /NADP + and sulfides using solar light: Exploring mechanistic investigations and their impact on synthetic applications. Photochemistry and Photobiology 2024, 100 (5) , 1235-1246. https://doi.org/10.1111/php.13890
    84. Jinhong Chen, Clarence Tan, Jesus Rodrigalvarez, Shuai Zhang, Ruben Martin. Site‐Selective Distal C(sp 3 )−H Bromination of Aliphatic Amines as a Gateway for Forging Nitrogen‐Containing sp 3 Architectures. Angewandte Chemie 2024, 136 (33) https://doi.org/10.1002/ange.202406485
    85. Subhendu Ghosh, Tamanna Khandelia, Anjali Mahadevan, Pritishree Panigrahi, Piyush Kumar, Raju Mandal, Deepjyoti Boruah, Sugumar Venkataramani, Bhisma K. Patel. Photo‐Induced Generation of Oxygenated Quaternary Centers via EnT Enabled Singlet O 2 Addition to C3‐Maleimidated Quinoxaline: A Reagent‐Less Approach. Chemistry – A European Journal 2024, 30 (45) https://doi.org/10.1002/chem.202400219
    86. Jinhong Chen, Clarence Tan, Jesus Rodrigalvarez, Shuai Zhang, Ruben Martin. Site‐Selective Distal C(sp 3 )−H Bromination of Aliphatic Amines as a Gateway for Forging Nitrogen‐Containing sp 3 Architectures. Angewandte Chemie International Edition 2024, 63 (33) https://doi.org/10.1002/anie.202406485
    87. Milanpreet Kaur, Julian C. Cooper, Jeffrey F. Van Humbeck. Site-selective benzylic C–H hydroxylation in electron-deficient azaheterocycles. Organic & Biomolecular Chemistry 2024, 22 (24) , 4888-4894. https://doi.org/10.1039/D4OB00268G
    88. Ye Tao, Kaige Guo, Hao Chen, Guobing Yan, Ming Guo. Site-selective C(sp 3 )–H functionalization of primary aliphatic amines. Organic Chemistry Frontiers 2024, 11 (11) , 3270-3280. https://doi.org/10.1039/D4QO00324A
    89. Daiki Doiuchi, Nanako Shimoda, Koushi Okazaki, Tatsuya Uchida. Acid‐Cooperative Transition Metal‐Catalysed Oxygen‐Atom‐Transfer: Ruthenium‐Catalysed C−H Oxygenation. Advanced Synthesis & Catalysis 2024, 366 (9) , 2026-2034. https://doi.org/10.1002/adsc.202301453
    90. Adrija Ghosh, Vishal Kumar Parida, Debasis Banerjee. Challenges and opportunities on sustainable electrochemical transformations: application towards the synthesis of pharmaceuticals and precursors of drug-like molecules. Green Chemistry 2024, 26 (10) , 5770-5789. https://doi.org/10.1039/D3GC04881K
    91. Dung L. Golden, Kaitlyn M. Flynn, Santeri Aikonen, Christopher M. Hanneman, Dipannita Kalyani, Shane W. Krska, Robert S. Paton, Shannon S. Stahl. Radical chlorination of non-resonant heterobenzylic C‒H bonds and high-throughput diversification of heterocycles. Chem 2024, 10 (5) , 1593-1605. https://doi.org/10.1016/j.chempr.2024.04.001
    92. Katelyn Le, Jeffrey F. Van Humbeck. Neglected no longer: Selective C–H activation of the non-resonant C3 benzylic position of pyridine. Chem 2024, 10 (5) , 1334-1336. https://doi.org/10.1016/j.chempr.2024.04.007
    93. Thomas Magauer, Ondřej Kováč. [ N , N ′‐bis(2‐pyridylmethyl)]‐2,2′‐bipyrrolidinebis(acetonitrile)iron(II) hexafluoroantimonate (White–Chen catalyst; Fe( S , S ‐PDP) or Fe( R , R ‐PDP)). 2024, 1-4. https://doi.org/10.1002/047084289X.rn02370
    94. Konstantin P. Bryliakov. Bioinspired Selective Catalytic C‐H Oxygenation, Halogenation, and Azidation of Steroids. 2024, 369-387. https://doi.org/10.1002/9781119870647.ch17
    95. S. G. Zlotin, K. S. Egorova, V. P. Ananikov, A. A. Akulov, M. V. Varaksin, O. N. Chupakhin, V. N. Charushin, K. P. Bryliakov, A. D. Averin, I. P. Beletskaya, E. L. Dolengovski, Yu. H. Budnikova, O. G. Sinyashin, Z. N. Gafurov, A. O. Kantyukov, D. G. Yakhvarov, A. V. Aksenov, M. N. Elinson, V. G. Nenajdenko, A. M. Chibiryaev, N. S. Nesterov, E. A. Kozlova, O. N. Martyanov, I. A. Balova, V. N. Sorokoumov, D. A. Guk, E. K. Beloglazkina, D. A. Lemenovskii, I. Yu. Chukicheva, L. L. Frolova, E. S. Izmest'ev, I. A. Dvornikova, A. V. Popov, A. V. Kutchin, D. M. Borisova, A. A. Kalinina, A. M. Muzafarov, I. V. Kuchurov, A. L. Maximov, A. V. Zolotukhina. The green chemistry paradigm in modern organic synthesis. Russian Chemical Reviews 2023, 92 (12) , RCR5104. https://doi.org/10.59761/RCR5104
    96. Roman V. Ottenbacher, Anna A. Bryliakova, Vladimir I. Kurganskii, Petr V. Prikhodchenko, Alexander G. Medvedev, Konstantin P. Bryliakov. Bioinspired Non‐Heme Mn Catalysts for Regio‐ and Stereoselective Oxyfunctionalizations with H 2 O 2. Chemistry – A European Journal 2023, 29 (66) https://doi.org/10.1002/chem.202302772
    97. Qin He, Zehui Cao, Yangyang Zhang, Gong Chen, Yaxin Wang. Visible‐Light‐Promoted Aliphatic C−H Chlorination and Bromination Using Haloform as the Halogen Donor and Azidobenziodoxole as the Mediator. Advanced Synthesis & Catalysis 2023, 365 (16) , 2711-2717. https://doi.org/10.1002/adsc.202300416
    98. Hossay Abas, Peter Blencowe, Joanna L. Brookfield, Lucy A. Harwood. Selective Hydroxylation of C(sp 3 )−H Bonds in Steroids. Chemistry – A European Journal 2023, 29 (44) https://doi.org/10.1002/chem.202301066
    99. Rachel K. Chambers, Jacob D. Weaver, Jinho Kim, Jason L. Hoar, Shane W. Krska, M. Christina White. A preparative small-molecule mimic of liver CYP450 enzymes in the aliphatic C–H oxidation of carbocyclic N -heterocycles. Proceedings of the National Academy of Sciences 2023, 120 (29) https://doi.org/10.1073/pnas.2300315120
    100. Callum G. J. Hall, Helen F. Sneddon, Peter Pogány, David M. Lindsay, William J. Kerr. Experimental and computational insights into the mechanism of the copper( i )-catalysed sulfonylative Suzuki–Miyaura reaction. Chemical Science 2023, 14 (24) , 6738-6755. https://doi.org/10.1039/D3SC01337E
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    Cite this: J. Am. Chem. Soc. 2015, 137, 46, 14590–14593
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