过渡金属催化烯烃碳硅化反应研究进展

doi:10.6023/cjoc202507033

摘要/Abstract

有机硅化合物作为功能分子, 在有机合成、材料科学和药物研发等领域具有重要的应用. 烯烃碳硅化反应是合成结构丰富的有机硅化合物的关键反应, 在构建结构多样的有机硅化合物方面具有重要应用. 以不同亲电试剂参与的碳硅化反应为主线, 系统地综述了烯烃碳硅化反应的研究进展, 详细阐述了基本原理, 分析了各催化体系的优势及局限性, 并对烯烃碳硅化反应未来的发展方向进行了展望.

关键词: 过渡金属, 烯烃, 碳硅化

As functional molecules, organosilicon compounds have important applications in the fields of organic synthesis, materials science and drug development. Carbosilylation of alkenes is a key reaction for synthesizing structurally rich organosilicon compounds and has important applications in constructing structurally diverse organosilicon compounds. The research progress of alkene carbosilylation with different electrophile reagents is systematically reviewed, the basic principle is described in detail, the advantages and limitations of each catalytic system are analyzed, and the future development direction of alkene siliconization reaction is prospected.

Key words: transition metal, alkenes, carbosilylation

引用此文

刘猛, 刘涛波, 韩梅兰, 王舒扬, 桂智排措, 徐光利, 韩鸿萍. 过渡金属催化烯烃碳硅化反应研究进展[J]. 有机化学, 2026, 46(3): 840-858.

Meng Liu, Taobo Liu, Meilan Han, Shuyang Wang, Zhipaicuo Gui, Guangli Xu, Hongping Han. Research Progress on Transition Metal-Catalyzed Carbosilylation of Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 840-858.

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图/表 23

图1. 含硅药物分子

Figure 1. Drug molecules containing silicon

图式1. 钯催化联烯芳硅化反应及机理

Scheme 1. Palladium-catalyzed aromatic silicification of diene and its mechanism

图式2. 钯催化非活性烯烃芳硅化反应

Scheme 2. Palladium-catalyzed arylsilylation of inactive alkenes

图式3. 镍、铜双金属催化烯烃芳硅化反应及机理

Scheme 3. Nickel and copper bimetallic catalytic alkenes arylsilylation reaction and its mechanism

图式4. 铁、钌双金属催化烯烃芳硅化反应

Scheme 4. Iron/ruthenium bimetallic catalyzed hydroarylsilylation of alkenes

图式5. 镍催化1,3-共轭二烯芳硅基反应及机理

Scheme 5. Nickel-catalyzed 1,3-conjugated diene arylsilyl reaction and its mechanism

图式6. 铜催化烯烃芳硅化反应及机理

Scheme 6. Copper-catalyzed alkenes arylsilylation reaction and its mechanism

图式7. 铜催化烯烃芳硅化反应及机理

Scheme 7. Copper-catalyzed alkenes arylsilylation reaction and its mechanism

图式8. 碱催化烯烃芳硅化反应及机理

Scheme 8. Alkali-catalyzed alkenes arylsilylation reaction and its mechanism

图式9. 有机碱催化烯烃芳硅化反应

Scheme 9. Organic base catalyzed alkenes arylsilylation reaction

图式10. 光促进镍催化烯烃芳硅化反应及机理

Scheme 10. Photo-promoted nickel-catalyzed alkenes arylsilylation reactionand its mechanism

图式11. 光催化烯烃芳硅化反应

Scheme 11. Photocatalytic alkenes arylsilylation reaction

图式12. 钯催化1,3-共轭二烯硅烷化反应

Scheme 12. Palladium-catalyzed 1,3-conjugated diene silanization reaction

图式13. 钛催化烯烃硅烷化反应

Scheme 13. Titanium-catalyzed silanization of alkenes

图式14. 镍催化1,3-共轭二烯硅烷化反应

Scheme 14. Nickel catalyzed silanization of 1,3-conjugated diene

图式15. 镍催化丙烯腈硅烷化反应

Scheme 15. Nickel-catalyzed silanization of acrylonitrile

图式16. 镍催化非活性烯烃硅烷化反应

Scheme 16. Nickel catalyzed silanization of inactive alkenes

图式17. 铜催化烯烃硅基化羧基化反应

Scheme 17. Copper-catalyzed silicylation and carboxylation reactions of alkenes

图式18. 光催化烯烃硅基化羧基化反应

Scheme 18. Photocatalytic silicylation and carboxylation reactions of alkenes

图式19. 镍催化烯烃硅化酰基化反应

Scheme 19. Nickel-catalyzed silicification and acylation of alkenes

图式20. 光电化学促进铁、镍共催化烯烃硅酰化反应

Scheme 20. Photoelectrochemically promoted iron/nickel co-catalyzed hydrosilylation of alkenes

图式21. 钯催化联烯硅酰化反应

Scheme 21. Palladium-catalyzed siliconization and acylation of diene

图式22. 有机正离子催化烯烃炔基、硅基化反应

Scheme 22. Organic cation-catalyzed alkenyne silylation reaction

参考文献 47

[1]	(a) Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835. doi: 10.1021/ar020001r
	(b) Pozdnyakov, A.; Kuznetsova, N.; Ivanova, A.; Bolgova, Y.; Semenova, T.; Trofimova, O.; Prozorova, G.; Emel'yanov, A. Mater. Today Chem. 2023, 34, 101808.
	(c) Wang, Z.-L.; Zhu, R. J. Am. Chem. Soc. 2024, 146, 19377. doi: 10.1021/jacs.4c05524
	(d) Yamashita, D.; Fang, N.; Fujii, S.; Kato, K. Y. Adv. Opt. Mater. 2025, 13, 2402531. doi: 10.1002/adom.v13.6
	(e) Chen, K.; Wu, X.; Yao, J.; Liao, H.; Ran, Q. Chem. Eng. J. 2025, 518, 164613. doi: 10.1016/j.cej.2025.164613
[2]	(a) Franz, A. K.; Wilson, S. O. J. Med. Chem. 2013, 56, 388. doi: 10.1021/jm3010114
	(b) Ye, T. T.; Wang, Q. Y.; Shen, L. H.; Cao, D.; Wu, H. L.; Yin, X. P. J. Hangzhou Norm. Univ. (Nat. Sci.) 2013, 12, 555 (in Chinese).
	(叶婷婷, 王秋岩, 沈凌宏, 曹丹, 吴慧丽, 殷晓浦, 杭州师范大学学报(自然科学版), 2013, 12, 555.)
	(c) Fujii, S.; Hashimoto, Y. Future Med. Chem. 2017, 9, 485. doi: 10.4155/fmc-2016-0193
	(d) Panayides, J.-L.; Riley, D. L.; Hasenmaile, F.; van Otterlo, W. A. L. RSC Med. Chem. 2024, 15, 3286. doi: 10.1039/D4MD00169A
[3]	(a) Matsumoto, K.; Huang, J.; Naganawa, Y.; Guo, H.; Beppu, T.; Sato, K.; Shimada, S.; Nakajima, Y. Org. Lett. 2018, 20, 2481. doi: 10.1021/acs.orglett.8b00847 pmid: 29617139
	(b) Pang, X.; Shu, X.-Z. Chem.-Eur. J. 2023, 29, e202203362. doi: 10.1002/chem.v29.11 pmid: 29617139
	(c) Zhang, Y.-F.; Li, L.; Tang, Y.; Zhou, Y.-Y. Org. Lett. 2025, 27, 4032. doi: 10.1021/acs.orglett.5c01015 pmid: 29617139
[4]	(a) Tobisu, M.; Kita, Y.; Ano, Y.; Chatani, N. J. Am. Chem. Soc. 2008, 130, 15982. doi: 10.1021/ja804992n
	(b) Chu, C. K.; Liang, Y.; Fu, G. C. J. Am. Chem. Soc. 2016, 138, 6404. doi: 10.1021/jacs.6b03465
	(c) Xue, W.; Oestreich, M. Angew. Chem., Int. Ed. 2017, 56, 11649. doi: 10.1002/anie.v56.38
	(d) Xue, W.; Shishido, R.; Oestreich, M. Angew. Chem., Int. Ed. 2018, 57, 12141. doi: 10.1002/anie.v57.37
[5]	(a) Yamamoto, E.; Ukigai, S.; Ito, H. Synlett 2017, 28, 2460. doi: 10.1055/s-0036-1590835
	(b) Cai, Y.; Zhao, W.; Wang, S.; Liang, Y.; Yao, Z.-J. Org. Lett. 2019, 21, 9836. doi: 10.1021/acs.orglett.9b03679
	(c) Denker, L.; Wullschläger, D.; Martínez, J. P.; Świerczewski, S.; Trzaskowski, B.; Tamm, M.; Frank, R. ACS Catal. 2023, 13, 2586. doi: 10.1021/acscatal.2c06259
	(d) Li, Z.; Liu, J.-G.; Zhang, W.-P.; Xu, M.-H. Adv. Synth. Catal. 2024, 366, 2514. doi: 10.1002/adsc.v366.11
	(e) Chen, S.-H.; Zhang, S.; Chen, Z.-Y.; Wu, Y.; Wang, P. J. Am. Chem. Soc. 2025, 147, 15666. doi: 10.1021/jacs.5c02996
[6]	(a) Guseva, M. A.; Alentiev, D. A.; Bermesheva, E. V.; Zamilatskov, I. A.; Bermeshev, M. V. RSC Adv. 2019, 9, 33029. doi: 10.1039/C9RA06784A
	(b) Hu, M.-Y.; He, P.; Qiao, T.-J.; Sun, W.; Li, W.-T.; Lian, J.; Li, J.-H.; Zhu, S.-F. J. Am. Chem. Soc. 2020, 142, 16894. doi: 10.1021/jacs.0c09083
	(c) Wei, D.; Buhaibeh, Y.; Canac, Y.; Sortais, J.-B. Molecules 2021, 26, 2598. doi: 10.3390/molecules26092598
	(d) Zhang, S.; Findlater, M. ACS Catal. 2023, 13, 8731. doi: 10.1021/acscatal.3c01221
	(e) Yang, C.; Chen, J.; Li, X.; Meng, L.; Wang, K.; Sun, W.; Fan, B. Acta Chim. Sinica 2023, 81, 1 (in Chinese). doi: 10.6023/A22110454
	(杨春晖, 陈景超, 李新汉, 孟丽, 王凯民, 孙蔚青, 樊保敏, 化学学报, 2023, 81, 1.)
	(f) Coschigano, M. G.; Gregory, S. L.; Catazaro, J.; Rossini, A. J.; Klausen, R. S. Macromolecules 2024, 57, 4095. doi: 10.1021/acs.macromol.3c02110
[7]	(a) Zhang, L.; An, K.; Wang, Y.; Wu, Y.-D.; Zhang, X.; Yu, Z.-X.; He, W. J. Am. Chem. Soc. 2021, 143, 3571. doi: 10.1021/jacs.0c13335
	(b) Kong, Y.; Mu, D. Chem. - Asian J. 2022, 71, e202200104.
	(c) Empel, C.; Jana, S.; Langletz, T.; Koenigs, R. M. Chem.-Eur. J. 2022, 28, e202104321. doi: 10.1002/chem.v28.12
	(d) Thorwart, T.; Greb, L. Chem. Sci. 2023, 14, 11237. doi: 10.1039/D3SC03488G
	(e) Deng, S.; Peng, C.; Niu, Y.; Xu, Y.; Zhang, Y.; Chen, X.; Wang, H.; Liu, S.; Shen, X. Acta Chim. Sinica 2024, 82, 119 (in Chinese). doi: 10.6023/A23110487
	(邓沈娜, 彭常春, 牛云宏, 许云, 张云霄, 陈祥, 王红敏, 刘珊珊, 沈晓, 化学学报, 2024, 82, 119.)
[8]	(a) You, Q.; Zhang, J.; Zhou, X. Chem.-Eur. J. 2020, 34, 7702.
	(b) You, L.; Yuan, W.; He, C. Eur. J. Org. Chem. 2021, 3079.
	(c) Ge, Y.; Ke, J.; He, C. Acc. Chem. Res. 2025, 58, 375. doi: 10.1021/acs.accounts.4c00667
[9]	(a) Hsieh, S.-Y.; Bode, J. W. Org. Lett. 2016, 18, 2098. doi: 10.1021/acs.orglett.6b00722 pmid: 36749888
	(b) Yang, X.; Wang, X. Chem.-Asian. J. 2018, 13, 2307. doi: 10.1002/asia.v13.17 pmid: 36749888
	(c) Yepes, P.; Suárez-Sobrino, Á. L.; Rodríguez, M. A.; Ballesteros, A. Org. Lett. 2023, 25, 1020. doi: 10.1021/acs.orglett.3c00221 pmid: 36749888
	(d) Zhang, X.; Lu, K.; Chen, X.; Su, G.; Rong, X.; Ma, M. Org. Biomol. Chem. 2024, 22, 5353. doi: 10.1039/D4OB00745J pmid: 36749888
	(e) Hansjacob, P.; Schwoerer, C.; Leroux, F. R.; Donnard, M. Org. Biomol. Chem. 2024, 22, 70. doi: 10.1039/D3OB01787G pmid: 36749888
[10]	Motokura, K.; Baba, T. Green Chem. 2012, 14, 565. doi: 10.1039/c2gc16291a
[11]	Shang, X.; Liu, Z.-Q. Org. Biomol. Chem. 2016, 14, 7829. doi: 10.1039/C6OB00797J
[12]	Wang, M.; Yu, M.; Wang, W.; Lin, W.; Luo, F. Chin. J. Org. Chem. 2019, 39, 3145 (in Chinese). doi: 10.6023/cjoc201904024
	(王明凤, 余茂栋, 王文蜀, 林伟立, 罗斐贤, 有机化学, 2019, 39, 3145.)
[13]	Ghosh, S.; Lai, D.; Hajra, A. Org. Biomol. Chem. 2021, 19, 2399. doi: 10.1039/D1OB00082A
[14]	Pal, P. P.; Ghosh, S.; Hajra, A. Org. Biomol. Chem. 2023, 21, 2272. doi: 10.1039/D3OB00230F
[15]	Wu, M.-Y.; Yang, F.-Y.; Cheng, C.-H. J. Org. Chem. 1999, 64, 2471. doi: 10.1021/jo982307a
[16]	Liu, Z.; Chen, J.; Lu, H.-X.; Li, X.; Gao, Y.; Coombs, J. R.; Goldfogel, M. J.; Engle, K. M. Angew. Chem., Int. Ed. 2019, 58, 2. doi: 10.1002/anie.v58.1
[17]	(a) Ackerman, L. K. G.; Lovell, M. M.; Weix, D. J. Nature 2015, 524, 454. doi: 10.1038/nature14676 pmid: 39711236
	(b) Vázquez-Galiñanes, N.; Fañanás-Mastral, M. ChemCatChem 2018, 10, 4817. doi: 10.1002/cctc.v10.21 pmid: 39711236
	(c) Olivares, A. M.; Weix, D. J. J. Am. Chem. Soc. 2018, 140, 2446. doi: 10.1021/jacs.7b13601 pmid: 39711236
	(d) Xu, W.-Y.; Li, Y.-J.; Gong, T.-J.; Fu, Y. Org. Lett. 2022, 24, 5884. doi: 10.1021/acs.orglett.2c01875 pmid: 39711236
	(e) Navrátil, R.; Kellovská, K.; Baszczyňski, O. Green Chem. 2023, 25, 9779. doi: 10.1039/D3GC02735J pmid: 39711236
	(f) Serrano-Díez, E.; Pita-Milleiro, A.; Rangel-García, J.; Moreno, J. J.; Roselló-Merino, M.; Campos, J. J. Am. Chem. Soc. 2025, 147, 1271. doi: 10.1021/jacs.4c15359 pmid: 39711236
[18]	Zhao, B.; Li, Y.; Li, H.; Belal, M.; Zhu, L.; Yin, G. Sci. Bull. 2021, 66, 570. doi: 10.1016/j.scib.2020.10.001
[19]	Neogi, S.; Bhunya, S.; Ghosh, A. K.; Sarkar, B.; Roy, L.; Hajra, A. ACS Catal. 2024, 14, 4510. doi: 10.1021/acscatal.4c00034
[20]	(a) Huang, Q.; Hu, M.-Y.; Zhu, S.-F. Org. Lett. 2019, 21, 7883. doi: 10.1021/acs.orglett.9b02873
	(b) Xu, G.-L.; Liu, C.-Y.; Pang, X.; Liu, X.-Y.; Shu, X.-Z. CCS Chem. 2021, 3, 1147.
	(c) Cook, A.; St. Onge, P.; Newman, S. G. Nat. Synth. 2023, 2, 663. doi: 10.1038/s44160-023-00275-w
	(d) Chen, R.; Intermaggio, N. E.; Xie, J.; Rossi-Ashton, J. A.; Gould, C. A.; Martin, R. T.; Alcázar, J.; MacMillan, D. W. C. Science 2024, 383, 1350. doi: 10.1126/science.adl5890
	(e) Qi, L.; Xu, S.; Pang, X.; Wu, Y.-K.; Wang, X.; Shu, X.-Z. Angew. Chem., Int. Ed. 2025, e202509961.
[21]	Pan, Q.-Q.; Qi, L.; Pang, X.; Shu, X.-Z. Angew. Chem., Int. Ed. 2023, 62, e202215703. doi: 10.1002/anie.v62.4
[22]	Zhang, L.; Liu, D.; Liu, Z.-Q. Org. Lett. 2015, 17, 2534. doi: 10.1021/acs.orglett.5b01067
[23]	Peng, H.; Yu, J.-T.; Jiang, Y.; Cheng, J. Org. Biomol. Chem. 2015, 13, 10299. doi: 10.1039/C5OB01855B
[24]	Zhou, J.; Jiang, B.; Fujihira, Y.; Zhao, Z.; Imai, T.; Shibata, N. Nat. Commun. 2021, 12, 3749. doi: 10.1038/s41467-021-24031-w pmid: 34145264
[25]	Cui, B.; Jia, S.; Tokunaga, E.; Shibata, N. Nat. Commun. 2018, 9, 4393. doi: 10.1038/s41467-018-06830-w
[26]	(a) Jiao, L.; Zhou, F.-Y. Synlett 2021, 32, 159. doi: 10.1055/s-0040-1706552 pmid: 40169259
	(b) Xu, P.; Wang, Z.; Guo, S.-M.; Studer, A. Nat. Commun. 2024, 4121. pmid: 40169259
	(c) Bouchard, J. L.; Chang, S.; Krishnan, S.; Presley, C. C.; Boutaud, O.; Schley, N. D.; Engers, D. W.; Engers, J. L.; Lindsley, C. W.; Bender, A. M. J. Nat. Prod. 2025, 88, 996. doi: 10.1021/acs.jnatprod.5c00104 pmid: 40169259
	(d) Hart, M. A.; Uhlenbruck, B. J. H.; Levy, J. N.; McNally, A. J. Am. Chem. Soc. 2025, 147, 18406. doi: 10.1021/jacs.5c03091 pmid: 40169259
[27]	(a) Hara, F. O.; Blackmond, D. G.; Baran, P. S. J. Am. Chem. Soc. 2013, 135, 12122. doi: 10.1021/ja406223k pmid: 34318659
	(b) Cuthberson, J. D.; MacMillan, D. W. C. Nature 2015, 519, 74. doi: 10.1038/nature14255 pmid: 34318659
	(c) Koniarczyk, J. L.; Greenwood, J. W.; Alegre-Requena, J. V.; Paton, R. S.; McNally, A. Angew. Chem., Int. Ed. 2019, 58, 14882. doi: 10.1002/anie.201906267 pmid: 34318659
	(d) Lee, W.; Jung, S.; Kim, M.; Hong, S. J. Am. Chem. Soc. 2021, 143, 3003. doi: 10.1021/jacs.1c00549 pmid: 34318659
	(e) Choi, J.; Laudadio, G.; Godineau, E.; Baran, P. S. J. Am. Chem. Soc. 2021, 143, 11927. doi: 10.1021/jacs.1c05278 pmid: 34318659
[28]	Gao, L.; Liu, X.; Li, G.; Chen, S.; Cao, J.; Wang, G.; Li, S. Org. Lett. 2022, 24, 5698. doi: 10.1021/acs.orglett.2c02074
[29]	(a) Blackwell, J. H.; Harris, G. R.; Smith, M. A.; Gaunt, M. J. J. Am. Chem. Soc. 2021, 143, 15946. doi: 10.1021/jacs.1c07402 pmid: 34551248
	(b) Zhang, H.; Chen, J.-X.; Qu, J.-P.; Kang, Y.-B. Nature 2024, 635, 610. doi: 10.1038/s41586-024-08179-1 pmid: 34551248
[30]	Zhang, Z.; Hu, X. ACS Catal. 2020, 10, 777. doi: 10.1021/acscatal.9b04916
[31]	Neogi, S.; Ghosh, A. K.; Mandal, S.; Ghosh, D.; Ghosh, S.; Hajra, A. Org. Lett. 2021, 23, 6510. doi: 10.1021/acs.orglett.1c02322
[32]	Zheng, W.; Xu, Y.; Luo, H.; Feng, Y.; Zhang, J.; Lin, L. Org. Lett. 2022, 24, 7145. doi: 10.1021/acs.orglett.2c02835
[33]	(a) Álvarez, R.; Vaz, B.; Gronemeyer, H.; de Lera, Á. R. Chem. Rev. 2014, 114, 1. doi: 10.1021/cr400126u pmid: 24266866
	(b) Zweig, J. E.; Kim, D. E.; Newhouse, T. R. Chem. Rev. 2017, 117, 11680. doi: 10.1021/acs.chemrev.6b00833 pmid: 24266866
[34]	(a) Huang, E.; Bunel, E.; Faul, M. F. Org. Lett. 2007, 9, 4343. doi: 10.1021/ol7019839 pmid: 25032503
	(b) Grigalunas, M.; Ankner, T.; Norrby, P.-O.; Wiest, O.; Helquist, P. Org. Lett. 2014, 16, 3970. doi: 10.1021/ol5017965 pmid: 25032503
[35]	Obora, Y.; Tsuji, Y.; Kawamura, T. J. Am. Chem. Soc. 1993, 115, 10414. doi: 10.1021/ja00075a089
[36]	Nii, S.; Terao, J.; Kambe, N. J. Org. Chem. 2000, 65, 5291. pmid: 10993358
[37]	Jiang, S.; Zhang, T.; Luo, X.-Y.; Dong, S.; Ma, J.-T.; Xiao, L.-J. Angew. Chem., Int. Ed. 2025, 64, e202504494. doi: 10.1002/anie.v64.24
[38]	Sun, J.; Zhou, Y.; Gu, R.; Li, X.; Liu, A.; Zhang, X. Nat. Commun. 2022, 13, 7093. doi: 10.1038/s41467-022-34901-6
[39]	Wang, J.; Duan, Z.; Liu, X.; Dong, S.; Chen, K.; Li, J. Angew. Chem., Int. Ed. 2022, e202202379.
[40]	Tani, Y.; Fujihara, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2014, 136, 17706. doi: 10.1021/ja512040c
[41]	Han, S.-M.; Wang, X.; Miao, S.; Yuab, Z.-Y.; Liu, T. RSC Adv. 2017, 7, 29035. doi: 10.1039/C7RA03723F
[42]	Hou, J.; Ee, A.; Cao, H.; Ong, H.-W.; Xu, J.-H.; Wu, J. Angew. Chem., Int. Ed. 2018, 57, 17220. doi: 10.1002/anie.v57.52
[43]	Liu, L.; Liu, W.; Cui, D.-M.; Zeng, M. Chin. J. Org. Chem. 2021, 41, 4289 (in Chinese). doi: 10.6023/cjoc202104049
	(刘亮, 刘文波, 崔冬梅, 曾明, 有机化学, 2021, 41, 4289.)
[44]	Ni, D.; Brown, M. K. ACS Catal. 2021, 11, 1858. doi: 10.1021/acscatal.0c05449
[45]	Wang, L.; Huo, X.; He, X.; Ackermann, L.; Wang, D. Green Chem. 2024, 26, 8315. doi: 10.1039/D3GC04109C
[46]	Inagaki, T.; Sakurai, S.; Yamanaka, M.; Tobisu, M. Angew. Chem., Int. Ed. 2022, 61, e202202387. doi: 10.1002/anie.v61.21
[47]	He, T.; Qu, Z.-W.; Klare, H. F. T.; Grimme, S.; Oestreich, M. Angew. Chem., Int. Ed. 2022, 61, e202203347. doi: 10.1002/anie.v61.24