Chinese Journal of Organic Chemistry >
Recent Advances in Hydrogen Atom Transfer Induced Selective C(sp3)—H Functionalization of Alkanes
Received date: 2024-07-14
Revised date: 2024-09-11
Online published: 2024-10-29
Supported by
Guangdong Provincial Science and Technology Department(2019QN01L151); Guangdong Provincial Science and Technology Department(2023A0505050137); Guangdong Provincial Science and Technology Department(2022A1515011215)
As a highly atom-economical and step-economic strategy, the functionalization of alkane C(sp3)—H bonds to directly convert alkanes into higher value-added chemicals has been a subject of great interest. However, due to the well-known inertness of alkane C(sp3)—H bonds, controlling the chemical selectivity and regioselectivity of non-activated C(sp3)—H bond functionalization poses a significant challenge. Recently, the utilization of hydrogen atom transfer (HAT) for achieving selectivity in C(sp3)—H bond functionalization has attracted renewed attention as a method distinct from traditional transition metal-catalyzed approaches. Herein, various HAT-mediated non-activated C(sp3)—H bond functionalization methods are analyzed based on selectivity of functionalization with a focus on methods that have achieved regioselectivity control. The current limitations of existing methods are summarized and the current challenges and future directions in this field are outlooked.
Miao Wang , Yahao Huang , Peng Hu . Recent Advances in Hydrogen Atom Transfer Induced Selective C(sp3)—H Functionalization of Alkanes[J]. Chinese Journal of Organic Chemistry, 2025 , 45(2) : 477 -497 . DOI: 10.6023/cjoc202407027
| [1] | Ward, J. M. Fuel Process. Technol. 1993, 35, 55. |
| [2] | Weitkamp, J. ChemCatChem 2012, 4, 292. |
| [3] | Wang, Y.; Hu, P.; Yang, J.; Zhu, Y.-A.; Chen, D. Chem. Soc. Rev. 2021, 50, 4299. |
| [4] | Khake, S. M.; Chatani, N. Trends Chem. 2019, 1, 524. |
| [5] | Gandeepan, P.; Müller, T.; Zell, D.; Cera, G.; Warratz, S.; Ackermann, L. Chem. Rev. 2018, 119, 2192. |
| [6] | Chu, J. C. K.; Rovis, T. Angew. Chem., Int. Ed. 2017, 57, 62. |
| [7] | Hartwig, J. F.; Larsen, M. A. ACS Cent. Sci. 2016, 2, 281. |
| [8] | He, J.; Wasa, M.; Chan, K. S. L.; Shao, Q.; Yu, J.-Q. Chem. Rev. 2016, 117, 8754. |
| [9] | Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. |
| [10] | Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417. |
| [11] | Davies, H. M. L.; Morton, D. ACS Cent. Sci. 2017, 3, 936. |
| [12] | Mayer, J. M. Acc. Chem. Res. 2010, 44, 36. |
| [13] | Capaldo, L.; Ravelli, D.; Fagnoni, M. Chem. Rev. 2021, 122, 1875. |
| [14] | Chang, L.; Wang, S.; An, Q.; Liu, L. W.; Wang, H.; Li, Y.; Feng, K.; Zuo, Z. Chem. Sci. 2023, 14, 6841. |
| [15] | Huang, C.-Y.; Li, J.; Li, C.-J. Chem. Sci. 2022, 13, 5465. |
| [16] | Capaldo, L.; Ravelli, D. Eur. J. Org. Chem. 2017, 2017, 2056. |
| [17] | Sarkar, S.; Cheung, K. P. S.; Gevorgyan, V. Chem. Sci. 2020, 11, 12974. |
| [18] | Taniguchi, T. Synthesis 2017, 49, 3511. |
| [19] | Cheng, S.; Li, Q.; Cheng, X.; Lin, Y.; Gong, L. Chin. J. Chem. 2022, 40, 2825. |
| [20] | Roberts, B. P. Chem. Soc. Rev. 1999, 28, 25. |
| [21] | Salamone, M.; Bietti, M. Acc. Chem. Res. 2015, 48, 2895. |
| [22] | Ravelli, D.; Fagnoni, M.; Fukuyama, T.; Nishikawa, T.; Ryu, I. ACS Catal. 2017, 8, 701. |
| [23] | Galeotti, M.; Salamone, M.; Bietti, M. Chem. Soc. Rev. 2022, 51, 2171. |
| [24] | Matsumoto, A.; Maruoka, K. Asian J. Org. Chem. 2024, 13, e202300580. |
| [25] | Wang, Y.; Li, G.-X.; Yang, G.; He, G.; Chen, G. Chem. Sci. 2016, 7, 2679. |
| [26] | He, Q.; Cao, Z.; Zhang, Y.; Chen, G.; Wang, Y. Adv. Synth. Catal. 2023, 365, 2711. |
| [27] | Fawcett, A.; Keller, M. J.; Herrera, Z.; Hartwig, J. F. Angew. Chem., Int. Ed. 2021, 60, 8276. |
| [28] | Zhao, J.; Zhang, J.; Fang, P.; Wu, J.; Wang, F.; Liu, Z.-Q. Green Chem. 2024, 26, 507. |
| [29] | Kuang, Y.; Cao, H.; Tang, H.; Chew, J.; Chen, W.; Shi, X.; Wu, J. Chem. Sci. 2020, 11, 8912. |
| [30] | Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J. Am. Chem. Soc. 1989, 111, 6749. |
| [31] | Sakaguchi, S.; Kato, S.; Iwahama, T.; Ishii, Y. Bull. Chem. Soc. Jpn. 1998, 71, 1237. |
| [32] | Kiyokawa, K.; Ito, R.; Takemoto, K.; Minakata, S. Chem. Commun. 2018, 54, 7609. |
| [33] | Paolillo, J. M.; Duke, A. D.; Gogarnoiu, E. S.; Wise, D. E.; Parasram, M. J. Am. Chem. Soc. 2023, 145, 2794. |
| [34] | Guo, S.; Zhang, X.; Tang, P. Angew. Chem., Int. Ed. 2015, 54, 4065. |
| [35] | Wu, H.; Xiao, Z.; Wu, J.; Guo, Y.; Xiao, J.-C.; Liu, C.; Chen, Q.-Y. Angew. Chem., Int. Ed. 2015, 54, 4070. |
| [36] | Zhao, Y.; Lin, J.-H.; Hang, X.-C.; Xiao, J.-C. J. Org. Chem. 2018, 83, 14120. |
| [37] | Mukherjee, S.; Maji, B.; Tlahuext-Aca, A.; Glorius, F. J. Am. Chem. Soc. 2016, 138, 16200. |
| [38] | Schirmer, T. E.; Rolka, A. B.; Karl, T. A.; Holzhausen, F.; K?nig, B. Org. Lett. 2021, 23, 5729. |
| [39] | Zhang, H.; Wang, Q.; Wang, Y.; Yuan, Z.; Gao, F.; Britton, R. Asian J. Org. Chem. 2021, 10, 2566. |
| [40] | Zhang, S.; Cao, S.; Lin, Y.-M.; Sha, L.; Lu, C.; Gong, L. Chin. J. Catal. 2022, 43, 564. |
| [41] | Antonchick, A. P.; Burgmann, L. Angew. Chem., Int. Ed. 2013, 52, 3267. |
| [42] | Fukuyama, T.; Nishikawa, T.; Yamada, K.; Ravelli, D.; Fagnoni, M.; Ryu, I. Org. Lett. 2017, 19, 6436. |
| [43] | Li, Y.; Lei, M.; Gong, L. Nat. Catal. 2019, 2, 1016. |
| [44] | Wang, M.; Zhang, Z.; Xiong, C.; Sun, P.; Zhou, C. ChemistrySelect 2022, 7, e202200816. |
| [45] | Wang, M.; Zhang, Y.; Yang, X.; Sun, P. Org. Biomol. Chem. 2022, 20, 2467. |
| [46] | Sheng, H.; Zhang, B.-B.; Liu, Q.; Yang, Z.-S.; Wang, Z.-X.; Chen, X.-Y. Sci. China: Chem. 2022, 65, 2494. |
| [47] | Li, Y.; Guo, S.-G.; Li, Q.; Zheng, K. Nat. Commun. 2023, 14, 6225. |
| [48] | Jha, R. K.; Rohilla, K.; Jain, S.; Parganiha, D.; Kumar, S. Chem.- Eur. J. 2024, 30, e202303537. |
| [49] | Zhang, X.; Yang, H.; Tang, P. Org. Lett. 2015, 17, 5828. |
| [50] | Day, C. S.; Fawcett, A.; Chatterjee, R.; Hartwig, J. F. J. Am. Chem. Soc. 2021, 143, 16184. |
| [51] | Ghosh, S. K.; Hu, M.; Comito, R. J. Chem.-Eur. J. 2021, 27, 17601. |
| [52] | Xia, J.-B.; Ma, Y.; Chen, C. Org. Chem. Front. 2014, 1, 468. |
| [53] | Zhang, X.; Guo, S.; Tang, P. Org. Chem. Front. 2015, 2, 806. |
| [54] | Aschmann, S. M.; Atkinson, R. Int. J. Chem. Kinet. 1995, 27, 613. |
| [55] | Russell, G. A. J. Am. Chem. Soc. 1958, 80, 4987. |
| [56] | Russell, G. A. J. Am. Chem. Soc. 1958, 80, 5002. |
| [57] | Dneprovskii, A. S.; Kuznetsov, D. V.; Eliseenkov, E. V.; Fletcher, B.; Tanko, J. M. J. Org. Chem 1998, 63, 8860. |
| [58] | Sutradhar, D.; Zeegers-Huyskens, T.; Chandra, A. K. Mol. Phys. 2015, 113, 3232. |
| [59] | Sumiyoshi, T.; Minegishi, H.; Fujiyoshi, R.; Sawamura, S. Chem. Lett. 2005, 34, 794. |
| [60] | Dooley, D. M.; Landin, J. A.; Rosenzweig, A. C.; Zumft, W. G.; Day, E. P. J. Am. Chem. Soc. 1991, 113, 8978. |
| [61] | Breslow, R.; Wiedenfeld, D. Tetrahedron Lett. 1993, 34, 1107. |
| [62] | Breslow, R.; Guo, T. Tetrahedron Lett. 1987, 28, 3187. |
| [63] | Jia, P.; Li, Q.; Poh, W. C.; Jiang, H.; Liu, H.; Deng, H.; Wu, J. Chem 2020, 6, 1766. |
| [64] | An, Q.; Wang, Z.; Chen, Y.; Wang, X.; Zhang, K.; Pan, H.; Liu, W.; Zuo, Z. J. Am. Chem. Soc. 2020, 142, 6216. |
| [65] | Cao, H.; Kong, D.; Yang, L.-C.; Chanmungkalakul, S.; Liu, T.; Piper, J. L.; Peng, Z.; Gao, L.; Liu, X.; Hong, X.; Wu, J. Nat. Synth. 2022, 1, 794. |
| [66] | Zheng, C.-Y.; Yue, J.-M. Nat. Commun. 2023, 14, 2399. |
| [67] | Bull, J. A.; Mousseau, J. J.; Pelletier, G.; Charette, A. B. Chem. Rev. 2012, 112, 2642. |
| [68] | Wang, B.; Pettenuzzo, C. A.; Singh, J.; Mccabe, G. E.; Clark, L.; Young, R.; Pu, J.; Deng, Y. ACS Catal. 2022, 12, 10441. |
| [69] | Zard, S. Z. Chem. Soc. Rev. 2008, 37, 1603. |
| [70] | Jeffrey, J. L.; Terrett, J. A.; MacMillan, D. W. C. Science 2015, 349, 1532. |
| [71] | Le, C.; Liang, Y.; Evans, R. W.; Li, X.; MacMillan, D. W. C. Nature 2017, 547, 79. |
| [72] | Matsumoto, A.; Yamamoto, M.; Maruoka, K. ACS Catal. 2022, 12, 2045. |
| [73] | Panferova, L. I.; Zubkov, M. O.; Kokorekin, V. A.; Levin, V. V.; Dilman, A. D. Angew. Chem., Int. Ed. 2021, 60, 2849. |
| [74] | Zachmann, A.; Drappeau, J.; Liu, S.; Alexanian, E. J. Angew. Chem., Int. Ed. 2024, 63, e202404879. |
| [75] | Zhang, Q.; An, B.; Lei, Y.; Gao, Z.; Zhang, H.; Xue, S.; Jin, X.; Xu, W.; Wu, Z.; Wu, M.; Yang, X.; Wu, W. Angew. Chem., Int. Ed. 2023, 62, e202304699. |
| [76] | Tzirakis, M. D.; Lykakis, I. N.; Orfanopoulos, M. Chem. Soc. Rev. 2009, 38, 2609. |
| [77] | N. Lykakis,, I.; Evgenidou, E.; Orfanopoulos, M. Curr. Org. Chem. 2012, 16, 2400. |
| [78] | Lazzaroni, S.; Ravelli, D.; Protti, S.; Fagnoni, M.; Albini, A. C. R. Chim. 2017, 20, 261. |
| [79] | Wang, Q.; Ni, S.; Yu, L.; Pan, Y.; Wang, Y. ACS Catal. 2022, 12, 11071. |
| [80] | Wang, Q.; Ni, S.; Wang, X.; Wang, Y.; Pan, Y. Sci. China: Chem. 2022, 65, 678. |
| [81] | Li, G.-X.; Hu, X.; He, G.; Chen, G. ACS Catal. 2018, 8, 11847. |
| [82] | Deno, N. C.; Gladfelter, E. J.; Pohl, D. G. J. Org. Chem. 1979, 44, 3728. |
| [83] | McMillan, A. J.; Sieńkowska, M.; Lorenzo, P. D.; Gransbury, G. K.; Chilton, N. F.; Salamone, M.; Ruffoni, A.; Bietti, M.; Leonori, D. Angew. Chem., Int. Ed. 2021, 60, 7132. |
| [84] | Lu, Z.-P.; Ju, M.; Wang, Y.; Meinhardt, J. M.; Martinez, J. I.; Villemure, E.; Terrett, J. A.; Lin, S. Nature 2023, 619, 514. |
| [85] | Schmidt, V. A.; Quinn, R. K.; Brusoe, A. T.; Alexanian, E. J. J. Am. Chem. Soc. 2014, 136, 14389. |
| [86] | Liu, Y.; Shi, B.; Zhao, L.; Gao, R.; Huang, C.; Alhumade, H.; Wang, S.; Qi, X.; Lei, A. J. Am. Chem. Soc. 2021, 143, 20863. |
| [87] | Carestia, A. M.; Ravelli, D.; Alexanian, E. J. Chem. Sci. 2018, 9, 5360. |
| [88] | Wang, Z.; Wang, F. Chin. J. Chem. 2022, 40, 1751. |
| [89] | Gonzalez, M. I.; Gygi, D.; Qin, Y.; Zhu, Q.; Johnson, E. J.; Chen, Y.-S.; Nocera, D. G. J. Am. Chem. Soc. 2022, 144, 1464. |
| [90] | Shu, C.; Noble, A.; Aggarwal, V. K. Nature 2020, 586, 714. |
| [91] | Sang, R.; Han, W.; Zhang, H.; Saunders, C. M.; Noble, A.; Aggarwal, V. K. J. Am. Chem. Soc. 2023, 145, 15207. |
| [92] | Tu, J.-L.; Hu, A.-M.; Guo, L.; Xia, W. J. Am. Chem. Soc. 2023, 145, 7600. |
| [93] | Zhong, P.-F.; Tu, J.-L.; Zhao, Y.; Zhong, N.; Yang, C.; Guo, L.; Xia, W. Nat. Commun. 2023, 14, 6530. |
| [94] | Cao, Y.; Huang, C.; Lu, Q. Nat. Synth. 2024, 3, 537. |
| [95] | Wei, W.; Wang, B.; Hom?lle, S. L.; Zhu, J.; Li, Y.; Münchow, T. von; Maksso, I.; Ackermann, L. CCS Chem. 2024, 6, 1430. |
| [96] | Fang, W.; Wang, H.-Q.; Zhou, W.; Luo, Z.-W.; Dai, J.-J. Chem. Commun. 2023, 59, 7108. |
| [97] | Wang, M.; Huang, Y.; Hu, P. Science 2024, 383, 537. |
| [98] | Jin, Y.; Wang, L.; Zhang, Q.; Zhang, Y.; Liao, Q.; Duan, C. Green Chem. 2021, 23, 9406. |
| [99] | Zou, L.; Xiang, S.; Sun, R.; Lu, Q. Nat. Commun. 2023, 14, 7992. |
| [100] | Li, Q.-Y.; Cheng, S.; Ye, Z.; Huang, T.; Yang, F.; Lin, Y.-M.; Gong, L. Nat. Commun. 2023, 14, 6366. |
| [101] | Takahira, Y.; Chen, M.; Kawamata, Y.; Mykhailiuk, P.; Nakamura, H.; Peters, B. K.; Reisberg, S. H.; Li, C.; Chen, L.; Hoshikawa, T.; Shibuguchi, T.; Baran, P. S. Synlett 2019, 30, 1178. |
| [102] | Saito, M.; Kawamata, Y.; Meanwell, M.; Navratil, R.; Chiodi, D.; Carlson, E.; Hu, P.; Chen, L.; Udyavara, S.; Kingston, C.; Tanwar, M.; Tyagi, S.; McKillican, B. P.; Gichinga, M. G.; Schmidt, M. A.; Eastgate, M. D.; Lamberto, M.; He, C.; Tang, T.; Malapit, C. A. J. Am. Chem. Soc. 2021, 143, 7859. |
| [103] | Zou, L.; Wang, X.; Xiang, S.; Zheng, W.; Lu, Q. Angew. Chem., Int. Ed. 2023, 62, e202301026. |
| [104] | Dai, Z.-Y.; Nong, Z.-S.; Song, S.; Wang, P.-S. Org. Lett. 2021, 23, 3157. |
| [105] | Jin, Y.; Fan, L.-F.; Wang, E.; Yu, L.; Hirao, H.; Gong, L.-Z. J. Am. Chem. Soc. 2023, 145, 22031. |
| [106] | Ge, L.; Wang, H.; Liu, Y.; Feng, X. J. Am. Chem. Soc. 2024, 146, 13347. |
| [107] | Ruan, X.-Y.; Wu, D.-X.; Li, W.-A.; Lin, Z.; Sayed, M.; Han, Z.-Y.; Gong, L.-Z. J. Am. Chem. Soc. 2024, 146, 12053. |
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