Chinese Journal of Organic Chemistry >
Divergent Hydrogenation of Indoles and Its Applications in Total Syntheses of (±)-α- and γ-Lycoranes
Received date: 2025-01-13
Revised date: 2025-02-19
Online published: 2025-03-10
Supported by
National Natural Science Foundation of China(82225041)
Hydroindoles are highly enriched in a variety of medicines, natural products, materials, and agrochemicals, however rapid and efficient access of this type of structure is still formidable. Herein, the construction of hydroindoles via hydrogenation of substituted indoles under atmospheric pressure of H2 at relatively low temperatures utilizing Pd/C as the catalyst is reported. And the controlled divergent hydrogenation of substituted indoles to dihydroindoles, tetrahydroindoles, hexahydroindoles, or octahydroindoles could be achieved by careful manipulation of reaction parameters, including reaction solvents, catalyst loading, and temperature. The efficiency of this method was demonstrated by the divergent syntheses of (±)-α- and γ-lycoranes in a three-step synthetic route.
Key words： total synthesis; α-lycorane; γ-lycorane; hydroindole; hydrogenation
Shoule Han , Mingliang Lou , Xiaolei Liu , Gen Li , Xin Wang , Qingcui Wu , Xiangbing Qi . Divergent Hydrogenation of Indoles and Its Applications in Total Syntheses of (±)-α- and γ-Lycoranes[J]. Chinese Journal of Organic Chemistry, 2025 , 45(3) : 913 -924 . DOI: 10.6023/cjoc202501010
| [1] | Luo, R. S.; Weng, J.; Ai, H. B.; Lu, G.; Chan, A. S. C. Adv. Synth. Catal. 2009, 351, 2449. |
| [2] | Hurst, M.; Jarvis, B. Drugs 2001, 61, 867. |
| [3] | (a) Faulkner, A.; Bower, J. F. Angew. Chem., Int. Ed. 2012, 51, 1675. |
| [3] | (b) Sofack-Kreutzer, J.; Martin, N.; Renaudat, A.; Jazzar, R.; Baudoin, O. Angew. Chem., Int. Ed. 2012, 51, 10399. |
| [3] | (c) Diethelm, S.; Schindler, C. S.; Carreira, E. M. Chem. Eur. J. 2014, 20, 6071. |
| [3] | (d) Feng, M.; Jiang, X. Chem. Commun. 2014, 50, 9690. |
| [3] | (e) Han, Y.; Zheng, B.; Peng, Y. Adv. Synth. Catal. 2015, 357, 1136. |
| [3] | (f) Gan, P.; Smith, M. W.; Braffman, N. R.; Snyder, S. A. Angew. Chem., Int. Ed. 2016, 55, 3625. |
| [3] | (g) MacLeod, B. L.; Pienkos, J. A.; Wilson, K. B.; Sabat, M.; Myers, W. H.; Harman, W. D. Organometallics 2016, 35, 370. |
| [3] | (h) Kalaitzakis, D.; Triantafyllakis, M.; Ioannou, G. I.; Vassilikogiannakis, G. Angew. Chem., Int. Ed. 2017, 56, 4020. |
| [3] | (i) Yang, H.; Hou, S.; Tao, C.; Liu, Z.; Wang, C.; Cheng, B.; Li, Y.; Zhai, H. Chem. Eur. J. 2017, 23, 12930. |
| [3] | (j) Zhao, Q.-S.; Xu, G.-Q.; Xu, J.-T.; Wang, Z.-Y.; Xu, P.-F. Chem. Commun. 2020, 56, 2206. |
| [3] | (k) Wang, F.; Xu, X.-H.; Yan, Y.-T.; Zhang, J.-Y.; Bai, W.-J.; Chen, J.-W.; Yang, Y. Org. Lett. 2023, 25, 6853. |
| [4] | (a) Wang, D.-S.; Chen, Q.-A.; Lu, S.-M.; Zhou, Y.-G. Chem. Rev. 2011, 112, 2557. |
| [4] | (b) Wiesenfeldt, M. P.; Nairoukh, Z.; Dalton, T.; Glorius, F. Angew. Chem., Int. Ed. 2019, 58, 10460. |
| [4] | (c) Kim, A. N.; Stoltz, B. M. ACS Catal. 2020, 10, 13834. |
| [4] | (d) Lückemeier, L.; Pierau, M.; Glorius, F. Chem. Soc. Rev. 2023, 52, 4996. |
| [5] | (a) Xu, L.; Zhang, C.; He, Y.; Tan, L.; Ma, D. Angew. Chem., Int. Ed. 2015, 55, 321. |
| [5] | (b) Yang, Y.; Li, R.; Zhao, Y.; Zhao, D.; Shi, Z. J. Am. Chem. Soc. 2016, 138, 8734. |
| [5] | (c) Yang, Y.; Qiu, X.; Zhao, Y.; Mu, Y.; Shi, Z. J. Am. Chem. Soc. 2016, 138, 495. |
| [5] | (d) Yang, Y.; Gao, P.; Zhao, Y.; Shi, Z. Angew. Chem., Int. Ed. 2017, 57, 3966. |
| [5] | (e) Qiu, X.; Wang, P.; Wang, D.; Wang, M.; Yuan, Y.; Shi, Z. Angew. Chem., Int. Ed. 2018, 58, 1504. |
| [6] | (a) Kuwano, R.; Sato, K.; Kurokawa, T.; Karube, D.; Ito, Y. J. Am. Chem. Soc. 2000, 122, 7614. |
| [6] | (b) Kuwano, R. K.; Kaneda, K.; Ito, T.; Sato, K.; Kurokawa, T.; Ito, Y. Org. Lett. 2004, 6, 2213. |
| [6] | (c) Kuwano, R.; Kashiwabara, M. Org. Lett. 2006, 8, 2653. |
| [6] | (d) Baeza, A.; Pfaltz, A. Chem. Eur. J. 2010, 16, 2036. |
| [6] | (e) Wang, D.-S.; Chen, Q.-A.; Li, W.; Yu, C.-B.; Zhou, Y.-G.; Zhang, X. J. Am. Chem. Soc. 2010, 132, 8909. |
| [6] | (f) Li, C.; Chen, J.; Fu, G.; Liu, D.; Liu, Y.; Zhang, W. Tetrahedron 2013, 69, 6839. |
| [6] | (g) Duan, Y.; Li, L.; Chen, M.-W.; Yu, C.-B.; Fan, H.-J.; Zhou, Y.-G. J. Am. Chem. Soc. 2014, 136, 7688. |
| [6] | (h) Núñez-Rico, J. L.; Fernández-Pérez, H.; Vidal-Ferran, A. Green Chem. 2014, 16, 1153. |
| [6] | (i) Yang, Z.; Chen, F.; He, Y.; Yang, N.; Fan, Q. H. Angew. Chem., Int. Ed. 2016, 55, 13863. |
| [6] | (j) Touge, T.; Arai, T. J. Am. Chem. Soc. 2016, 138, 11299. |
| [6] | (k) Wen, J.; Fan, X.; Tan, R.; Chien, H.-C.; Zhou, Q.; Chung, L. W.; Zhang, X. Org. Lett. 2018, 20, 2143. |
| [6] | (l) Ge, Y.; Wang, Z.; Han, Z.; Ding, K. Chem. Eur. J. 2020, 26, 15482. |
| [6] | (m) Liu, G.; Zheng, L.; Tian, K.; Wang, H.; Wa Chung, L.; Zhang, X.; Dong, X.-Q. CCS Chem. 2023, 5, 1398. |
| [7] | (a) Clarisse, D.; Fenet, B.; Fache, F. Org. Biomol. Chem. 2012, 10, 6587. |
| [7] | (b) Wollenburg, M.; Moock, D.; Glorius, F. Angew. Chem., Int. Ed. 2018, 57, 6549. |
| [7] | (c) Ling, L.; He, Y.; Zhang, X.; Luo, M.; Zeng, X. Angew. Chem., Int. Ed. 2019, 58, 6554. |
| [7] | (d) Wagener, T.; Pierau, M.; Heusler, A.; Glorius, F. Adv. Synth. Catal. 2022, 364, 3366. |
| [7] | (e) Zhang, F.; Sasmal, H. S.; Daniliuc, C. G.; Glorius, F. J. Am. Chem. Soc. 2023, 145, 15695. |
| [8] | (a) Aminzai, M. T.; Azizi, N.; Nural, Y.; Yabalak, E. Monatsh. Chem.-Chem. Mon. 2024, 155, 115. |
| [8] | (b) Luo, C.; Wu, C.; Wang, X.; Han, Z.; Wang, Z.; Ding, K. J. Am. Chem. Soc. 2024, 146, 35043. |
| [8] | (c) Williams, S.; Qi, L.; Cox, R. J.; Kumar, P.; Xiao, J. Org. Biomol. Chem. 2024, 22, 1010. |
| [8] | (d) Luckemeier, L.; Pierau, M.; Glorius, F. Chem. Soc. Rev. 2023, 52, 4996. |
| [8] | (e) Yang, Z.-Y.; Luo, H.; Zhang, M.; Wang, X.-C. ACS Catal. 2021, 11, 10824. |
| [8] | (f) Wagener, T.; Lückemeier, L.; Daniliuc, C. G.; Glorius, F. Angew. Chem., Int. Ed. 2021, 60, 6425. |
| [8] | (g) Zhang, X.; Ling, L.; Luo, M.; Zeng, X. Angew. Chem., Int. Ed. 2019, 58, 16785. |
| [8] | (h) Chen, F.; Li, W.; Sahoo, B.; Kreyenschulte, C.; Agostini, G.; Lund, H.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2018, 130, 14696. |
| [8] | (i) Cai, X.-F.; Huang, W.-X.; Chen, Z.; Zhou, Y.-G. Chem. Commun. 2014, 50, 9588. |
| [9] | Welin, E. R.; Ngamnithiporn, A.; Klatte, M.; Lapointe, G.; Pototschnig, G. M.; McDermott, M. S. J.; Conklin, D.; Gilmore, C. D.; Tadross, P. M.; Haley, C. K.; Negoro, K.; Glibstrup, E.; Grünanger, C. U.; Allan, K. M.; Virgil, S. C.; Slamon, D. J.; Stoltz, B. M. Science 2018, 363, 270. |
| [10] | (a) Liu, X.; Lou, M.; Bai, S.; Sun, G.; Qi, X. J. Org. Chem. 2022, 87, 5199. |
| [10] | (b) Han, S.; Lou, M.; Qi, X. Synlett 2023, 35, 586. |
| [10] | (c) Lou, M.; Liu, X.; Han, S.; Bai, S.; Qi, X. Chem. Commun. 2024, 60, 3842. |
| [11] | Colomer, I.; Chamberlain, A. E. R.; Haughey, M. B.; Donohoe, T. J. Nat. Rev. Chem. 2017, 1, 1. |
| [12] | McNulty, J.; Nair, J. J.; Little, J. R. L.; Brennan, J. D.; Bastida, J. Bioorg. Med. Chem. Lett. 2010, 20, 5290. |
| [13] | Hao, B.; Shen, S.-F.; Zhao, Q.-J. Molecules 2013, 18, 2458. |
| [14] | (a) Liu, X.-S.; Jiang, J.; Jiao, X.-Y.; Wu, Y.-E.; Lin, J.-J.; Cai, Y.-M. Cancer Lett. 2009, 274, 16. |
| [14] | (b) Lamoral-Theys, D.; Andolfi, A.; Van Goietsenoven, G.; Cimmino, A.; Le Calvé, B.; Wauthoz, N.; Mégalizzi, V.; Gras, T.; Bruyère, C.; Dubois, J.; Mathieu, V.; Kornienko, A.; Kiss, R.; Evidente, A. J. Med. Chem. 2009, 52, 6244. |
| [14] | (c) Wang, P.; Yuan, H.-H.; Zhang, X.; Li, Y.-P.; Shang, L.-Q.; Yin, Z. Molecules 2014, 19, 2469. |
| [15] | (a) Xiao, J.; Zhou, G. H.; Zhou, A. X.; Ji, C. B. Chem. Biodiversity 2022, 19, e202200410. |
| [15] | (b) Bautista, D. D.; Vilchis Reyes, M. A.; Blé González, E. A.; Bugarin, A. Eur. J. Org. Chem. 2023, 26, e202300404. |
| [15] | (c) Yoshizaki, H.; Satoh, H.; Sato, Y.; Nukui, S.; Shibasaki, M.; Mori, M. J. Org. Chem. 1995, 60, 2016. |
| [15] | (d) Ikeda, M.; Ohtani, S.; Sato, T.; Ishibashi, H. Synthesis 1998, 1998, 1803. |
| [15] | (e) Banwell, M. G.; Harvey, J. E.; Hockless, D. C. R. J. Org. Chem. 2000, 65, 4241. |
| [15] | (f) Dong, L.; Xu, Y.-J.; Cun, L.-F.; Cui, X.; Mi, A.-Q.; Jiang, Y.-Z.; Gong, L.-Z. Org. Lett. 2005, 7, 4285. |
| [15] | (g) Hong, B. C.; Nimje, R. Y.; Wu, M. F.; Sadani, A. A. Eur. J. Org. Chem. 2008, 2008, 1449. |
| [15] | (h) El Bialy, S. A. A. Nat. Prod. Res. 2008, 22, 1176. |
| [15] | (i) Wang, Y.; Luo, Y.-C.; Zhang, H.-B.; Xu, P.-F. Org. Biomol. Chem. 2012, 10, 8211. |
| [15] | (j) Li, G.; Xie, J. H.; Hou, J.; Zhu, S. F.; Zhou, Q. L. Adv. Synth. Catal. 2013, 355, 1597. |
| [15] | (k) Rana, N. K.; Huang, H.; Zhao, J. C. G. Angew. Chem., Int. Ed. 2014, 53, 7619. |
| [15] | (l) Sun, Z.; Zhou, M.; Li, X.; Meng, X.; Peng, F.; Zhang, H.; Shao, Z. Chem. Eur. J. 2014, 20, 6112. |
| [15] | (m) Meng, X.-L.; Liu, T.; Sun, Z.-W.; Wang, J.-C.; Peng, F.-Z.; Shao, Z.-H. Org. Lett. 2014, 16, 3044. |
| [15] | (n) Nishimura, K.; Fukuyama, N.; Yasuhara, T.; Yamashita, M.; Sumiyoshi, T.; Yamamoto, Y.; Yamada, K.-i.; Tomioka, K. Tetrahedron 2015, 71, 7222. |
| [15] | (o) Chen, Y. J.; Cai, S. L.; Wang, C. C.; Cheng, J. D.; Kramer, S.; Sun, X. W. Chem. Asian J. 2017, 12, 1309. |
| [15] | (p) Iida, H.; Yuasa, Y.; Kibayashi, C. J. Am. Chem. Soc. 1978, 100, 3598. |
| [15] | (q) Padwa, A.; Brodney, M. A.; Lynch, S. M. J. Org. Chem. 2001, 66, 1716. |
| [15] | (r) Miranda, L. D.; Zard, S. Z. Org. Lett. 2002, 4, 1135. |
| [15] | (s) Zhang, H.; Shao, Z.; Chen, J.; Huang, R.; Wang, C.; Li, L. Synlett 2003, 2228. |
| [15] | (t) Gao, S.; Tu, Y. Q.; Song, Z.; Wang, A.; Fan, X.; Jiang, Y. J. Org. Chem. 2005, 70, 6523. |
| [15] | (u) Jung, Y.-G.; Lee, S.-C. L.; Cho, H.-K.; Darvatkar, N. B.; Song, J.-Y.; Cho, C.-G. Org. Lett. 2013, 15, 132. |
| [15] | (v) Liu, D.; Ai, L.; Li, F.; Zhao, A.; Chen, J.; Zhang, H.; Liu, J. Org. Biomol. Chem. 2014, 12, 3191. |
| [15] | (w) Yu, W. L.; Nunns, T.; Richardson, J.; Booker-Milburn, K. I. Org. Lett. 2018, 20, 1272. |
| [15] | (x) Rocaboy, R.; Dailler, D.; Baudoin, O. Org. Lett. 2018, 20, 772. |
| [15] | (y) Wilson, K. B.; Nedzbala, H. S.; Simpson, S. R.; Ericson, M. N.; Westendorff, K. S.; Chordia, M. D.; Dickie, D. A.; Harman, W. D. Helv. Chim. Acta 2021, 104, e2100103. |
/
| 〈 |
|
〉 |
