|
|
基于光介导氢原子转移的惰性C(sp3)-H键直接胺化研究进展
|
Abstract:
惰性C(sp3)-H键广泛存在于烷烃、天然产物和药物分子中，其直接胺化是构建C-N键和实现分子后期修饰的重要策略。近年来，光介导氢原子转移(HAT)反应因条件温和、选择性可调和绿色高效等优势，成为C(sp3)-H键官能化研究的热点。本文综述了直接HAT、间接HAT、LMCT及光诱导X-Y键均裂等策略在C(sp3)-H胺化中的研究进展，并总结其反应特点、机理基础与应用前景。
Inert C(sp3)-H bonds are widely present in alkanes, natural products, and pharmaceutical molecules, and their direct amination provides an efficient approach to C-N bond formation and late-stage molecular modification. In recent years, photo-mediated hydrogen atom transfer (HAT) has emerged as a powerful strategy for C(sp3)-H functionalization owing to its mild conditions, tunable selectivity, and green features. This review summarizes recent advances in C(sp3)-H amination enabled by direct HAT, indirect HAT, LMCT processes, and photoinduced X-Y bond homolysis, with emphasis on reaction modes, mechanistic features, and future applications.
| [1] | Zhang, Y.-F. and Shi, Z.-J. (2019) Upgrading Cross-Coupling Reactions for Biaryl Syntheses. Accounts of Chemical Research, 52, 161-169. https://doi.org/10.1021/acs.accounts.8b00408 |
| [2] | Guo, X., Fang, G., Li, G., Ma, H., Fan, H., Yu, L., et al. (2014) Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen. Science, 344, 616-619. https://doi.org/10.1126/science.1253150 |
| [3] | Castellino, N.J., Montgomery, A.P., Danon, J.J. and Kassiou, M. (2023) Late-Stage Functionalization for Improving Drug-Like Molecular Properties. Chemical Reviews, 123, 8127-8153. https://doi.org/10.1021/acs.chemrev.2c00797 |
| [4] | Vitaku, E., Smith, D.T. and Njardarson, J.T. (2014) Analysis of the Structural Diversity, Substitution Patterns, and Frequency of Nitrogen Heterocycles among U.S. FDA Approved Pharmaceuticals. Journal of Medicinal Chemistry, 57, 10257-10274. https://doi.org/10.1021/jm501100b |
| [5] | Roughley, S.D. and Jordan, A.M. (2011) The Medicinal Chemist’s Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates. Journal of Medicinal Chemistry, 54, 3451-3479. https://doi.org/10.1021/jm200187y |
| [6] | Ruiz-Castillo, P. and Buchwald, S.L. (2016) Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions. Chemical Reviews, 116, 12564-12649. https://doi.org/10.1021/acs.chemrev.6b00512 |
| [7] | Qiao, J.X. and Lam, P.Y.S. (2011) Copper-Promoted Carbon-Heteroatom Bond Cross-Coupling with Boronic Acids and Derivatives. Synthesis, 2011, 829-856. https://doi.org/10.1055/s-0030-1258379 |
| [8] | He, J., Wasa, M., Chan, K.S.L., Shao, Q. and Yu, J.-Q. (2017) Palladium-Catalyzed Transformations of Alkyl C-H Bonds. Chemical Reviews, 117, 8754-8786. https://doi.org/10.1021/acs.chemrev.6b00622 |
| [9] | Capaldo, L., Ravelli, D. and Fagnoni, M. (2022) Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C-H Bonds Elaboration. Chemical Reviews, 122, 1875-1924. https://doi.org/10.1021/acs.chemrev.1c00263 |
| [10] | Holmberg-Douglas, N. and Nicewicz, D.A. (2022) Photoredox-Catalyzed C-H Functionalization Reactions. Chemical Reviews, 122, 1925-2016. https://doi.org/10.1021/acs.chemrev.1c00311 |
| [11] | Cao, H., Tang, X., Tang, H., Yuan, Y. and Wu, J. (2021) Photoinduced Intermolecular Hydrogen Atom Transfer Reactions in Organic Synthesis. Chem Catalysis, 1, 523-598. https://doi.org/10.1016/j.checat.2021.04.008 |
| [12] | Chang, L., Wang, S., An, Q., Liu, L., Wang, H., Li, Y., et al. (2023) Resurgence and Advancement of Photochemical Hydrogen Atom Transfer Processes in Selective Alkane Functionalizations. Chemical Science, 14, 6841-6859. https://doi.org/10.1039/d3sc01118f |
| [13] | Garwood, J.J.A., Chen, A.D. and Nagib, D.A. (2024) Radical Polarity. Journal of the American Chemical Society, 146, 28034-28059. https://doi.org/10.1021/jacs.4c06774 |
| [14] | Ryu, I., Tani, A., Fukuyama, T., Ravelli, D., Montanaro, S. and Fagnoni, M. (2013) Efficient C-H/C-N and C-H/C-CO-N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate. Organic Letters, 15, 2554-2557. https://doi.org/10.1021/ol401061v |
| [15] | Bonassi, F., Ravelli, D., Protti, S. and Fagnoni, M. (2015) Decatungstate Photocatalyzed Acylations and Alkylations in Flow via Hydrogen Atom Transfer. Advanced Synthesis & Catalysis, 357, 3687-3695. https://doi.org/10.1002/adsc.201500483 |
| [16] | Papadopoulos, G.N. and Kokotos, C.G. (2016) One-Pot Amide Bond Formation from Aldehydes and Amines via a Photoorganocatalytic Activation of Aldehydes. The Journal of Organic Chemistry, 81, 7023-7028. https://doi.org/10.1021/acs.joc.6b00488 |
| [17] | Wan, T., Capaldo, L., Laudadio, G., Nyuchev, A.V., Rincón, J.A., García‐Losada, P., et al. (2021) Decatungstate‐Mediated C(sp³)-H Heteroarylation via Radical‐Polar Crossover in Batch and Flow. Angewandte Chemie International Edition, 60, 17893-17897. https://doi.org/10.1002/anie.202104682 |
| [18] | Lu, Y.-C., Kao, S.-C. and West, J.G. (2022) Decatungstate-Photocatalysed C(sp³)-H Azidation. Chemical Communications, 58, 4869-4872. https://doi.org/10.1039/d2cc00425a |
| [19] | Margrey, K.A., Czaplyski, W.L., Nicewicz, D.A. and Alexanian, E.J. (2018) A General Strategy for Aliphatic C-H Functionalization Enabled by Organic Photoredox Catalysis. Journal of the American Chemical Society, 140, 4213-4217. https://doi.org/10.1021/jacs.8b00592 |
| [20] | Wang, Y., Li, G.-X., Yang, G., He, G. and Chen, G. (2016) A Visible-Light-Promoted Radical Reaction System for Azidation and Halogenation of Tertiary Aliphatic C-H Bonds. Chemical Science, 7, 2679-2683. https://doi.org/10.1039/c5sc04169d |
| [21] | Rabet, P.T.G., Fumagalli, G., Boyd, S. and Greaney, M.F. (2016) Benzylic C-H Azidation Using the Zhdankin Reagent and a Copper Photoredox Catalyst. Organic Letters, 18, 1646-1649. https://doi.org/10.1021/acs.orglett.6b00512 |
| [22] | Nakafuku, K.M., Zhang, Z., Wappes, E.A., Stateman, L.M., Chen, A.D. and Nagib, D.A. (2020) Enantioselective Radical C-H Amination for the Synthesis of β-Amino Alcohols. Nature Chemistry, 12, 697-704. https://doi.org/10.1038/s41557-020-0482-8 |
| [23] | McAtee, R.C., Noten, E.A. and Stephenson, C.R.J. (2020) Arene Dearomatization through a Catalytic N-Centered Radical Cascade Reaction. Nature Communications, 11, Article No. 2528. https://doi.org/10.1038/s41467-020-16369-4 |
| [24] | Hu, A., Guo, J.-J., Pan, H. and Zuo, Z. (2018) Selective Functionalization of Methane, Ethane, and Higher Alkanes by Cerium Photocatalysis. Science, 361, 668-672. https://doi.org/10.1126/science.aat9750 |
| [25] | Hu, A., Guo, J.-J., Pan, H., Tang, H., Gao, Z. and Zuo, Z. (2018) δ-Selective Functionalization of Alkanols Enabled by Visible-Light-Induced Ligand-to-Metal Charge Transfer. Journal of the American Chemical Society, 140, 1612-1616. https://doi.org/10.1021/jacs.7b13131 |
| [26] | Yang, Q., Wang, Y.-H., Qiao, Y., Gau, M., Carroll, P.J., Walsh, P.J., et al. (2021) Photocatalytic C-H Activation and the Subtle Role of Chlorine Radical Complexation in Reactivity. Science, 372, 847-852. https://doi.org/10.1126/science.abd8408 |
| [27] | Jin, Y., Zhang, Q., Wang, L., Wang, X., Meng, C. and Duan, C. (2021) Convenient C(sp³)-H Bond Functionalisation of Light Alkanes and Other Compounds by Iron Photocatalysis. Green Chemistry, 23, 6984-6989. https://doi.org/10.1039/d1gc01563j |
| [28] | Ruos, M.E., Kinney, R.G., Ring, O.T. and Doyle, A.G. (2023) A General Photocatalytic Strategy for Nucleophilic Amination of Primary and Secondary Benzylic C-H Bonds. Journal of the American Chemical Society, 145, 18487-18496. https://doi.org/10.1021/jacs.3c04912 |
| [29] | Pandey, G. and Laha, R. (2015) Visible‐Light‐Catalyzed Direct Benzylic C(sp³)-H Amination Reaction by Cross‐Dehydrogenative Coupling. Angewandte Chemie International Edition, 54, 14875-14879. https://doi.org/10.1002/anie.201506990 |
| [30] | Li, G.-X., Morales-Rivera, C.A., Gao, F., Wang, Y., He, G., Liu, P., et al. (2017) A Unified Photoredox-Catalysis Strategy for C(sp³)-H Hydroxylation and Amidation Using Hypervalent Iodine. Chemical Science, 8, 7180-7185. https://doi.org/10.1039/c7sc02773g |
| [31] | Lee, W., Kim, D., Seo, S. and Chang, S. (2022) Photoinduced α‐C-H Amination of Cyclic Amine Scaffolds Enabled by Polar‐Radical Relay. Angewandte Chemie International Edition, 61, e202202971. https://doi.org/10.1002/anie.202202971 |
| [32] | Han, Y., Shi, J., Li, S., Dan, T., Yang, W. and Yang, M. (2022) Selective Editing of a Peptide Skeleton via C-N Bond Formation at N-Terminal Aliphatic Side Chains. Chemical Science, 13, 14382-14386. https://doi.org/10.1039/d2sc04909k |
| [33] | Chen, Y., Yang, B., Li, Q.-Y., Lin, Y.-M. and Gong, L. (2023) Selectfluor®-Enabled Photochemical Selective C(sp³)-H(sulfonyl)amidation. Chemical Communications, 59, 118-121. https://doi.org/10.1039/d2cc05569d |
