|
|
过渡金属催化杂原子α位C-C偶联反应研究
|
Abstract:
有机分子中存在丰富的C(sp3)-H键，C(sp3)-H官能化反应是构建C-C键的有效方式。C(sp3)-H官能化反应可以改变有机分子的结构，从而改变化合反应的模式，缩短合成路线并提高原子经济性。在众多处于不同化学环境的C-H键中，杂原子α位的C(sp3)-H键因诱导效应使其相较于其他的C(sp3)-H键具有更高的反应活性，因此杂原子α位的C(sp3)-H键官能团化是一种非常实用的合成策略。本综述系统总结了近几年来过渡金属催化氮/氧杂原子α位C(sp3)-H键官能团化的研究进展。
Organic molecules contain abundant C(sp3)-H bonds, and C(sp3)-H functionalization reactions serve as an effective approach for constructing C-C bonds. These reactions can alter the structure of organic molecules, thereby modifying reaction patterns, shortening synthetic routes, and enhancing atom economy. Among the diverse C-H bonds in different chemical environments, heteroatom-adjacent α-C(sp3)-H bonds exhibit higher reactivity due to inductive effects compared to other C(sp3)-H bonds. Consequently, functionalizing heteroatom-adjacent α-C(sp3)-H bonds bonds represents a highly practical synthetic strategy. This review systematically summarizes recent advances in transition-metal-catalyzed functionalization of α-position C(sp3)-H bonds in nitrogen/oxygen heteroatoms.
| [1] | Gonnard, L., Guérinot, A. and Cossy, J. (2019) Transition Metal-Catalyzed α-Alkylation of Amines by C(sp3)-H Bond Activation. Tetrahedron, 75, 145-163. https://doi.org/10.1016/j.tet.2018.11.034 |
| [2] | Delost, M.D., Smith, D.T., Anderson, B.J. and Njardarson, J.T. (2018) From Oxiranes to Oligomers: Architectures of U.S. FDA Approved Pharmaceuticals Containing Oxygen Heterocycles. Journal of Medicinal Chemistry, 61, 10996-11020. https://doi.org/10.1021/acs.jmedchem.8b00876 |
| [3] | 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 |
| [4] | Lorente, A., Lamariano-Merketegi, J., Albericio, F. and Álvarez, M. (2013) Tetrahydrofuran-Containing Macrolides: A Fascinating Gift from the Deep Sea. Chemical Reviews, 113, 4567-4610. https://doi.org/10.1021/cr3004778 |
| [5] | Taylor, R.D., MacCoss, M. and Lawson, A.D.G. (2014) Rings in Drugs. Journal of Medicinal Chemistry, 57, 5845-5859. https://doi.org/10.1021/jm4017625 |
| [6] | Heitz, D.R., Tellis, J.C. and Molander, G.A. (2016) Photochemical Nickel-Catalyzed C-H Arylation: Synthetic Scope and Mechanistic Investigations. Journal of the American Chemical Society, 138, 12715-12718. https://doi.org/10.1021/jacs.6b04789 |
| [7] | Shen, Y., Gu, Y. and Martin, R. (2018) sp3 C-H Arylation and Alkylation Enabled by the Synergy of Triplet Excited Ketones and Nickel Catalysts. Journal of the American Chemical Society, 140, 12200-12209. https://doi.org/10.1021/jacs.8b07405 |
| [8] | Xu, S., Ping, Y., Li, W., Guo, H., Su, Y., Li, Z., et al. (2023) Enantioselective C(sp3)-H Functionalization of Oxacycles via Photo-Hat/Nickel Dual Catalysis. Journal of the American Chemical Society, 145, 5231-5241. https://doi.org/10.1021/jacs.2c12481 |
| [9] | Ping, Y., Xu, S. and Kong, W. (2025) Stereoselective Nondirected Α-C(sp3)-H Functionalization of Oxygen Heterocycles. Accounts of Chemical Research, 58, 2477-2495. https://doi.org/10.1021/acs.accounts.5c00355 |
| [10] | Spangler, J.E., Kobayashi, Y., Verma, P., Wang, D. and Yu, J. (2015) α-Arylation of Saturated Azacycles and n-Methylamines via Palladium(II)-Catalyzed C(sp3)-H Coupling. Journal of the American Chemical Society, 137, 11876-11879. https://doi.org/10.1021/jacs.5b06740 |
| [11] | Liu, Y. and Shi, H. (2023) α-C-H Arylation of n-Sulfonyl Amines by Dual Palladium Catalysis. ChemCatChem, 15, Article 392. https://doi.org/10.1002/cctc.202300392 |
| [12] | Wang, D., Hao, X., Wu, D. and Yu, J. (2006) Palladium-Catalyzed Oxidation of Boc-Protected n-Methylamines with IOAc as the Oxidant: A Boc-Directed sp3 C-H Bond Activation. Organic Letters, 8, 3387-3390. https://doi.org/10.1021/ol061384m |
| [13] | Baslé, O. and Li, C. (2007) Copper Catalyzed Oxidative Alkylation of sp3 C-H Bond Adjacent to a Nitrogen Atom Using Molecular Oxygen in Water. Green Chemistry, 9, 1047-1050. https://doi.org/10.1039/b707745a |
| [14] | Nishino, M., Hirano, K., Satoh, T. and Miura, M. (2011) Copper-Catalyzed Oxidative Direct Cyclization of n-Methylanilines with Electron-Deficient Alkenes Using Molecular Oxygen. The Journal of Organic Chemistry, 76, 6447-6451. https://doi.org/10.1021/jo2011329 |
| [15] | Huang, L., Niu, T., Wu, J. and Zhang, Y. (2011) Copper-Catalyzed Oxidative Cross-Coupling of n, n-Dimethylanilines with Heteroarenes under Molecular Oxygen. The Journal of Organic Chemistry, 76, 1759-1766. https://doi.org/10.1021/jo1023975 |
| [16] | Li, Z. and Li, C. (2004) CuBr-Catalyzed Efficient Alkynylation of sp3 C-H Bonds Adjacent to a Nitrogen Atom. Journal of the American Chemical Society, 126, 11810-11811. https://doi.org/10.1021/ja0460763 |
| [17] | Li, Z., Bohle, D.S. and Li, C. (2006) Cu-Catalyzed Cross-Dehydrogenative Coupling: A Versatile Strategy for C-C Bond Formations via the Oxidative Activation of sp3 C-H Bonds. Proceedings of the National Academy of Sciences, 103, 8928-8933. https://doi.org/10.1073/pnas.0601687103 |
| [18] | Zuo, Z., Ahneman, D.T., Chu, L., Terrett, J.A., Doyle, A.G. and MacMillan, D.W.C. (2014) Merging Photoredox with Nickel Catalysis: Coupling of α-Carboxyl sp3-Carbons with Aryl Halides. Science, 345, 437-440. https://doi.org/10.1126/science.1255525 |
| [19] | Shaw, M.H., Shurtleff, V.W., Terrett, J.A., Cuthbertson, J.D. and MacMillan, D.W.C. (2016) Native Functionality in Triple Catalytic Cross-Coupling: sp3 C-H Bonds as Latent Nucleophiles. Science, 352, 1304-1308. https://doi.org/10.1126/science.aaf6635 |
| [20] | Yang, T., Xiong, W., Sun, G., Yang, W., Lu, M. and Koh, M.J. (2024) Multicomponent Construction of Tertiary Alkylamines by Photoredox/Nickel-Catalyzed Aminoalkylation of Organohalides. Journal of the American Chemical Society, 146, 29177-29188. https://doi.org/10.1021/jacs.4c11602 |
| [21] | Le, C., Liang, Y., Evans, R.W., Li, X. and MacMillan, D.W.C. (2017) Selective sp3 C-H Alkylation via Polarity-Match-Based Cross-Coupling. Nature, 547, 79-83. https://doi.org/10.1038/nature22813 |
| [22] | Rand, A.W., Yin, H., Xu, L., Giacoboni, J., Martin-Montero, R., Romano, C., et al. (2020) Dual Catalytic Platform for Enabling sp3 αC-H Arylation and Alkylation of Benzamides. ACS Catalysis, 10, 4671-4676. https://doi.org/10.1021/acscatal.0c01318 |
| [23] | Li, L., Liu, Y. and Shi, H. (2021) Nickel-Catalyzed Enantioselective α-Alkenylation of n-Sulfonyl Amines: Modular Access to Chiral Α-Branched Amines. Journal of the American Chemical Society, 143, 4154-4161. https://doi.org/10.1021/jacs.1c00622 |
| [24] | Jun, C.H., Hwang, D.C. and Na, S.J. (1998) Chelation-Assisted Alkylation of Benzylamine Derivatives by Ruo Catalyst. Chemical Communications, 13, 1405-1406. https://doi.org/10.1039/a801298i |
| [25] | Chatani, N., Asaumi, T., Yorimitsu, S., Ikeda, T., Kakiuchi, F. and Murai, S. (2001) Ru3(CO)12-Catalyzed Coupling Reaction of sp3C-H Bonds Adjacent to a Nitrogen Atom in Alkylamines with Alkenes. Journal of the American Chemical Society, 123, 10935-10941. https://doi.org/10.1021/ja011540e |
| [26] | Schmitt, D.C., Lee, J., Dechert-Schmitt, A.R., Yamaguchi, E. and Krische, M.J. (2013) Ruthenium Catalyzed Hydroaminoalkylation of Isoprene via Transfer Hydrogenation: Byproduct-Free Prenylation of Hydantoins. Chemical Communications, 49, 6096-6098. https://doi.org/10.1039/c3cc43463j |
| [27] | Pastine, S.J., Gribkov, D.V. and Sames, D. (2006) sp3 C-H Bond Arylation Directed by Amidine Protecting Group: α-Arylation of Pyrrolidines and Piperidines. Journal of the American Chemical Society, 128, 14220-14221. https://doi.org/10.1021/ja064481j |
| [28] | Prokopcová, H., Bergman, S.D., Aelvoet, K., Smout, V., Herrebout, W., Van der Veken, B., et al. (2010) C-2 Arylation of Piperidines through Directed Transition-Metal-Catalyzed sp3 C-H Activation. Chemistry—A European Journal, 16, 13063-13067. https://doi.org/10.1002/chem.201001887 |
| [29] | Chatani, N., Asaumi, T., Ikeda, T., Yorimitsu, S., Ishii, Y., Kakiuchi, F., et al. (2000) Carbonylation at sp3 C-H Bonds Adjacent to a Nitrogen Atom in Alkylamines Catalyzed by Rhodium Complexes. Journal of the American Chemical Society, 122, 12882-12883. https://doi.org/10.1021/ja002561w |
| [30] | Davies, H.M.L., Hansen, T., Hopper, D.W. and Panaro, S.A. (1999) Highly Regio-, Diastereo-, and Enantioselective C-H Insertions of Methyl Aryldiazoacetates into Cyclic N-Boc-Protected Amines. Asymmetric Synthesis of Novel C2-Symmetric Amines and Threo-Methylphenidate. Journal of the American Chemical Society, 121, 6509-6510. https://doi.org/10.1021/ja9910715 |
| [31] | Anschuber, M., Pollice, R. and Schnürch, M. (2018) Rhodium-Catalyzed Direct Alkylation of Benzylic Amines Using Alkyl Bromides. Monatshefte für Chemie—Chemical Monthly, 150, 127-138. https://doi.org/10.1007/s00706-018-2305-9 |
| [32] | Greßies, S., Klauck, F.J.R., Kim, J.H., Daniliuc, C.G. and Glorius, F. (2018) Ligand-Enabled Enantioselective C-H Activation of Tetrahydroquinolines and Saturated Aza-Heterocycles by Rh. Angewandte Chemie International Edition, 57, 9950-9954. https://doi.org/10.1002/anie.201805680 |
