过渡金属催化1,1-二取代烯烃的不对称硼氢化反应研究进展

doi:10.6023/cjoc202603032

摘要/Abstract

烯烃的不对称硼氢化反应是高效构建手性含硼化合物的重要方法之一. 几十年以来, 随着一系列优势配体被开发, 过渡金属催化1,1-二取代烯烃的不对称硼氢化研究取得了显著进展. 系统总结了该领域的研究现状, 着重归纳了现有催化体系与反应机理, 指出了该领域当前面临的挑战, 并对未来的发展前景进行了展望.

关键词: 硼氢化, 1,1-二取代烯烃, 过渡金属催化, 不对称催化

Asymmetric hydroboration of alkenes is one of the important methods for the efficient construction of chiral boron- containing compounds. Over the past few decades, with the development of a series of privileged ligands, significant progress has been made in the transition metal catalyzed asymmetric hydroboration of 1,1-disubstituted alkenes. This review systematically summarizes the current research status of this field, with a focus on the existing catalytic systems and reaction mechanisms, identifies the current challenges, and provides an outlook on future development prospects.

Key words: hydroboration, 1,1-disubstituted alkenes, transition metal catalysis, asymmetric catalysis

引用此文

熊康宇, 陆展. 过渡金属催化1,1-二取代烯烃的不对称硼氢化反应研究进展[J]. 有机化学, 2026, 46(7): 2493-2510.

Kangyu Xiong, Zhan Lu. Research Progress in Transition Metal-Catalyzed Asymmetric Hydroboration of 1,1-Disubstituted Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2493-2510.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 19

图式1. 1,1-二取代烯烃不对称硼氢化的对映选择性控制

Scheme 1. Enantioselective control of asymmetric hydroboration of 1,1-disubstituted alkenes

图式2. 铑催化1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 2. Rhodium-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

图式3. 铑催化导向官能团取代的1,1-二取代烯烃的不对称硼氢化

Scheme 3. Rhodium-catalyzed asymmetric hydroboration of directing group-substituted 1,1-disubstituted alkenes

图式4. 铱催化1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 4. Iridium-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

图式5. 铜催化1,1-二取代芳基烯烃的不对称质子硼化

Scheme 5. Copper-catalyzed asymmetric protoboration of 1,1-disubstituted aryl alkenes

图式6. 铜催化1,3-共轭二烯的不对称1,2-硼氢化

Scheme 6. Copper-catalyzed asymmetric 1,2-hydroboration of 1,3-dienes

图式7. 钴催化1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 7. Cobalt-catalyzed asymmetric hydroboration of 1,1-disubstituted aryl alkenes

图式8. 钴催化1,1-二取代大位阻芳基烯烃的不对称硼氢化反应

Scheme 8. Cobalt-catalyzed asymmetric hydroboration of 1,1-disubstituted sterically hindered aryl alkenes

图式9. 钴催化1,3-二烯的不对称1,2-硼氢化反应

Scheme 9. Cobalt-catalyzed asymmetric 1,2-hydroboration of 1,3-dienes

图式10. 钴催化远程烯炔的不对称硼氢化成环反应

Scheme 10. Cobalt-catalyzed asymmetric hydroboration/cyclization of remote enynes

图式11. 钴催化酯基取代的1,1-二取代烯烃的不对称硼氢化反应

Scheme 11. Cobalt-catalyzed asymmetric hydroboration of ester-substituted 1,1-disubstituted alkenes

图式12. 钴催化硅基取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 12. Cobalt-catalyzed asymmetric hydroboration of silyl-substituted 1,1-disubstituted aryl alkenes

图式13. 钴催化硅醚取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 13. Cobalt-catalyzed asymmetric hydroboration of silyl ether-substituted 1,1-disubstituted aryl alkenes

图式14. 钴催化环丙基取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 14. Cobalt-catalyzed asymmetric hydroboration of cyclopropyl-substituted 1,1-disubstituted aryl alkenes

图式15. 钴催化三氟甲基取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 15. Cobalt-catalyzed asymmetric hydroboration of trifluoromethyl-substituted 1,1-disubstituted aryl alkenes

图式16. 钴催化非张力环醚取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 16. Cobalt-catalyzed asymmetric hydroboration of unstrained cyclic ether-substituted 1,1-disubstituted aryl alkenes

图式17. 铁催化环丙基取代的1,1-二取代芳基烯烃的不对称硼氢化反应

Scheme 17. Iron-catalyzed asymmetric hydroboration of cyclopropyl-substituted 1,1-disubstituted aryl alkenes

图式18. 非活化型1,1-二取代烯烃的不对称硼氢化反应

Scheme 18. Asymmetric hydroboration of unactivated 1,1-disubstituted alkenes

Metal	Catalytically active species	Chirality-controlling step	C—B bond formation step	Representative references
Rh	B-Rh-H	Alkene migratory insertion into Rh-H	B-Rh-C reductive elimination	[18], [27], [29-30]
Ir	B-Ir-H	Alkene migratory insertion into Ir-H	B-Ir-C reductive elimination	[32]
Cu	Cu-H	Alkene migratory insertion into Cu-H	σ-Bond metathesis between the Cu-C species and pinacol borane	[55-56]
Cu	Cu-B	Alkene migratory insertion into Cu-B and enantioselective Cu-C protonation	Alkene migratory insertion into Cu-B	[34]
Co	Co-H	Alkene migratory insertion into Co-H Alkene migratory insertion into Co-C'	σ-Bond metathesis between the Co-C species and pinacol borane	[39-41] [45]
	B-Co-H	Alkene migratory insertion into Co-H	B-Co-C reductive elimination	[43]
	B-Co-H	Alkene migratory insertion into Co-B	Alkene migratory insertion into Co-B	[47]
Fe	Fe-H	Alkene migratory insertion into Fe-H β-C Elimination of the Fe-C species	σ-Bond metathesis between the Fe-C species and pinacol borane	[53] [54]

表1. 过渡金属催化的1,1-二取代烯烃的不对称硼氢化催化模式

Table 1. Transition metal-catalyzed asymmetric hydroboration modes of 1,1-disubstituted alkenes

参考文献 60

[1]	Selected examples: (a) Brown, H. C.; Rao, B. C. S. J. Am. Chem. Soc. 1956, 78, 5694. doi: 10.1021/ja01602a063
	(b) Brown, H. C.; Jadhav, P. K.; Mandal, A. K. Tetrahedron 1981, 37, 3547. doi: 10.1016/S0040-4020(01)98886-6
	(c) Burgess, K.; Ohlmeyer, M. J. Chem. Rev. 1991, 91, 1179. doi: 10.1021/cr00006a003
[2]	Selected examples: (a) Zhang, F.-H.; Zhang, F.-J.; Li, M.-L.; Xie, J.-H.; Zhou, Q.-L. Nat. Catal. 2020, 3, 621. doi: 10.1038/s41929-020-0474-5
	(b) Zhou, H.; Zhou, Y.; Bae, H. Y.; Leutzsch, M.; Li, Y.; De, C. K.; Cheng, G.-J.; List, B. Nature 2022, 605, 84. doi: 10.1038/s41586-022-04531-5
	(c) Wang, M.; Liu, S.; Liu, H.; Wang, Y.; Lan, Y.; Liu, Q. Nature 2024, 631, 556. doi: 10.1038/s41586-024-07581-z
	(d) Liu, W.; Guo, J.; Xing, S.; Lu, Z. Org. Lett. 2020, 22, 2532. doi: 10.1021/acs.orglett.0c00293
[3]	Liu, W.; Lu, Z. Chin. J. Org. Chem. 2020, 40, 3596 (in Chinese). doi: 10.6023/cjoc202008039
	(刘文伯, 陆展, 有机化学, 2020, 40, 3596.) doi: 10.6023/cjoc202008039
[4]	Selected examples: (a) Gonzalez, A. Z.; Román, J. G.; Gonzalez, E.; Martinez, J.; Medina, J. R.; Matos, K.; Soderquist, J. A. J. Am. Chem. Soc. 2008, 130, 9218. doi: 10.1021/ja803119p pmid: 18582063
	(b) Thomas, S. P.; Aggarwal, V. K. Angew. Chem., Int. Ed. 2009, 48, 1896. doi: 10.1002/anie.v48:11 pmid: 18582063
[5]	Collins, B. S. L.; Wilson, C. M.; Myers, E. L.; Aggarwal, V. K. Angew. Chem., Int. Ed. 2017, 56, 11700. doi: 10.1002/anie.v56.39
[6]	Selected examples for transition-metal-free hydroboration of 1,1-disubstituted alkenes: (a) Huninik, P.; Szyling, J.; Czapik, A.; Walkowiak, J. Green Chem. 2023, 25, 3715. doi: 10.1039/D2GC04163D
	(b) Huninik, P.; Im, H.; Szyling, J.; Baik, M.-H.; Walkowiak, J. J. Am. Chem. Soc. 2025, 147, 44152. doi: 10.1021/jacs.5c13555
[7]	Selected reviews for asymmetric hydroboration of 1,1-disubstituted alkenes: (a) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. doi: 10.1016/S0040-4020(97)00001-X
	(b) Zuo, Z.; Wen, H.; Liu, G.; Huang, Z. Synlett 2018, 29, 1421. doi: 10.1055/s-0037-1609682
	(c) Chen, J.; Guo, J.; Lu, Z. Chin. J. Chem. 2018, 36, 1075. doi: 10.1002/cjoc.v36.11
	(d) Guo, J.; Cheng, Z.; Chen, J.; Chen, X.; Lu, Z. Acc. Chem. Res. 2021, 54, 2701. doi: 10.1021/acs.accounts.1c00212
	(e) Sun, Y.; Guan, R.; Liu, Z.; Wang, Y. Chin. J. Org. Chem. 2020, 40, 899 (in Chinese). doi: 10.6023/cjoc201909035
	(孙越, 关瑞, 刘兆洪, 王也铭, 有机化学, 2020, 40, 899.) doi: 10.6023/cjoc201909035
[8]	Selected reviews for asymmetric hydroboration of other alkenes: (a) Brösamlen, D.; Oestreich, M. ACS Catal. 2026, 16, 6198. doi: 10.1021/acscatal.6c00700
	(b) Lu, H.; Li, B. Chin. J. Org. Chem. 2022, 42, 3167 (in Chinese). doi: 10.6023/cjoc202207040
	(陆候祥, 李必杰, 有机化学, 2022, 42, 3167.) doi: 10.6023/cjoc202207040
	(c) Li, S.; Shu, X.; Wu, L. Chin. J. Org. Chem. 2023, 43, 1751 (in Chinese). doi: 10.6023/cjoc202212022
	(李思达, 舒兴中, 吴立朋, 有机化学, 2023, 43, 1751.) doi: 10.6023/cjoc202212022
	(d) Wang, Z.-X.; Bai, X.-Y.; Li, B.-J. Chin. J. Chem. 2019, 37, 1174. doi: 10.1002/cjoc.v37.11
[9]	Selected examples for asymmetric hydroboration of other alkenes: (a) Chen, X.; Cheng, Z.; Guo, J.; Lu, Z. Nat. Commun. 2018, 9, 3939. doi: 10.1038/s41467-018-06240-y pmid: 30258070
	(b) Ren, X.; Lu, Z. Org. Lett. 2021, 23, 8370. doi: 10.1021/acs.orglett.1c03110 pmid: 30258070
	(c) Bao, Y.; Zheng, C.; Xiong, K.; Hu, C.; Lu, P.; Wang, Y.; Lu, Z. J. Am. Chem. Soc. 2024, 146, 21089. doi: 10.1021/jacs.4c06585 pmid: 30258070
[10]	Li, L.-J.; He, Y.; Yang, Y.; Guo, J.; Lu, Z.; Wang, C.; Zhu, S.; Zhu, S.-F. CCS Chem. 2023, 6, 537. doi: 10.31635/ccschem.023.202303412
[11]	Zhu, Y.-S.; Li, J.-X.; Zhao, H.-T.; Su, B. Chin. J. Chem. 2024, 42, 3588. doi: 10.1002/cjoc.v42.24
[12]	Lian, C.; Zhang, J.; Qiu, D.; Mo, F. Chin. J. Chem. 2025, 43, 104. doi: 10.1002/cjoc.v43.1
[13]	Li, Y.; Cheng, Y.; Shan, C.; Zhang, J.; Xu, D.; Bai, R.; Qu, L.; Lan, Y. Chin. J. Org. Chem. 2018, 38, 1885 (in Chinese). doi: 10.6023/cjoc201804031
	(李园园, 程玉华, 单春晖, 张敬, 徐冬冬, 白若鹏, 屈凌波, 蓝宇, 有机化学, 2018, 38, 1885.) doi: 10.6023/cjoc201804031
[14]	Zheng, C.; Liu, J.; Wang, Y.; Li, H.; Wang, Y.; Lu, Z. Chem. Sci. 2026, 17, 492. doi: 10.1039/D5SC06683B
[15]	Chen, J.; Cao, M.; Cheng, B.; Lu, Z. Synlett 2015, 26, 2332. doi: 10.1055/s-00000083
[16]	Tan, Y.; Ying, J.; Yu, B.; Lu, Z. Chin. J. Org. Chem. 2025, 45, 1684 (in Chinese). doi: 10.6023/cjoc202409002
	(谭燕, 应佳乐, 於兵, 陆展, 有机化学, 2025, 45, 1684.) doi: 10.6023/cjoc202409002
[17]	Selected examples for asymmetric hydrogenation and hydrofunctionalization of 1,1-disubstituted alkenes: (a) Wang, L.; Li, M.; Yan, H.; Cheng, Z.; Lu, Z. Chin. J. Chem. 2025, 43, 3496. doi: 10.1002/cjoc.v43.24
	(b) Lu, P.; Ren, X.; Xu, H.; Lu, D.; Sun, Y.; Lu, Z. J. Am. Chem. Soc. 2021, 143, 12433. doi: 10.1021/jacs.1c04773
[18]	Burgess, K.; Ohlmeyer, M. J. J. Org. Chem. 1988, 53, 5178. doi: 10.1021/jo00256a059
[19]	Burgess, K.; Ohlmeyer, M. J. Tetrahedron Lett. 1989, 30, 395. doi: 10.1016/S0040-4039(00)95210-9
[20]	Burgess, K.; Ohlmeyer, M. J. Tetrahedron Lett. 1989, 30, 5857. doi: 10.1016/S0040-4039(01)93489-6
[21]	Burgess, K.; van der Donk, W. A.; Ohlmeyer, M. J. Tetrahedron: Asymmetry 1991, 2, 613.
[22]	Sato, M.; Miyaura, N.; Suzuki, A. Tetrahedron Lett. 1990, 31, 231.
[23]	Hayashi, T.; Matsumoto, Y.; lto, Y. Tetrahedron: Asymmetry 1991, 2, 601.
[24]	Männig, D.; Nöth, H. Angew. Chem., Int. Ed. 1985, 24, 878. doi: 10.1002/anie.v24:10
[25]	Widauer, C.; Grützmacher, H.; Ziegler, T. Organometallics 2000, 19, 2097. doi: 10.1021/om9909946
[26]	Smith, S. M.; Hoang, G. L.; Pal, R.; Khaled, M. O. B.; Pelter, L. S. W.; Zeng, X. C.; Takacs, J. M. Chem. Commun. 2012, 48, 12180. doi: 10.1039/c2cc36199j
[27]	Hu, N.; Zhao, G.; Zhang, Y.; Liu, X.; Li, G.; Tang, W. J. Am. Chem. Soc. 2015, 137, 6746. doi: 10.1021/jacs.5b03760
[28]	Shoba, V. M.; Thacker, N. C.; Bochat, A. J.; Takacs, J. M. Angew. Chem., Int. Ed. 2016, 55, 1465. doi: 10.1002/anie.v55.4
[29]	Chakrabarty, S.; Takacs, J. M. ACS Catal. 2018, 8, 10530. doi: 10.1021/acscatal.8b03591 pmid: 31134137
[30]	Shao, H.; Chakrabarty, S.; Qi, X.; Takacs, J. M.; Liu, P. J. Am. Chem. Soc. 2021, 143, 4801. doi: 10.1021/jacs.1c01303
[31]	Bochat, A. J.; Shoba, V. M.; Takacs, J. M. Angew. Chem., Int. Ed. 2019, 58, 9434. doi: 10.1002/anie.v58.28
[32]	Mazet, C.; Gérard, D. Chem. Commun. 2011, 47, 298. doi: 10.1039/C0CC01547D
[33]	Magre, M.; Biosca, M.; Pàmies, O.; Diéguez, M. ChemCatChem 2015, 7, 114. doi: 10.1002/cctc.v7.1
[34]	Corberán, R.; Mszar, N. W.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2011, 50, 7079. doi: 10.1002/anie.v50.31
[35]	Wang, Z.; He, X.; Zhang, R.; Zhang, G.; Xu, G.; Zhang, Q.; Xiong, T.; Zhang, Q. Org. Lett. 2017, 19, 3067. doi: 10.1021/acs.orglett.7b01135
[36]	Wen, L.; Cheng, F.; Li, H.; Zhang, S.; Hong, X.; Meng, F. Asian J. Org. Chem. 2018, 7, 103. doi: 10.1002/ajoc.v7.1
[37]	Liu, Y.; Fiorito, D.; Mazet, C. Chem. Sci. 2018, 9, 5284. doi: 10.1039/C8SC01538D
[38]	Wu, J.; Wu, H.; Li, X.; Liu, X.; Zhao, Q.; Huang, G.; Zhang, C. Angew. Chem., Int. Ed. 2021, 60, 20376. doi: 10.1002/anie.v60.37
[39]	Zhang, L.; Zuo, Z.; Wan, X.; Huang, Z. J. Am. Chem. Soc. 2014, 136, 15501. doi: 10.1021/ja5093908 pmid: 25325782
[40]	Chen, J.; Xi, T.; Ren, X.; Cheng, B.; Guo, J.; Lu, Z. Org. Chem. Front. 2014, 1, 1306. doi: 10.1039/C4QO00295D
[41]	Zhang, H.; Lu, Z. ACS Catal. 2016, 6, 6596. doi: 10.1021/acscatal.6b02278
[42]	Obligacion, J. V.; Chirik, P. J. J. Am. Chem. Soc. 2013, 135, 19107. doi: 10.1021/ja4108148 pmid: 24328236
[43]	Duvvuri, K.; Dewese, K. R.; Parsutkar, M. M.; Jing, S. M.; Mehta, M. M.; Gallucci, J. C.; RajanBabu, T. V. J. Am. Chem. Soc. 2019, 141, 7365. doi: 10.1021/jacs.8b13812
[44]	Ma, H.; Dong, W.; Zhao, W. Angew. Chem., Int. Ed. 2025, 64, e202501767. doi: 10.1002/anie.v64.37
[45]	Wang, C.; Ge, S. J. Am. Chem. Soc. 2018, 140, 10687. doi: 10.1021/jacs.8b06814
[46]	Wu, C.; Liao, J.; Ge, S. Angew. Chem., Int. Ed. 2019, 58, 8882. doi: 10.1002/anie.v58.26
[47]	Patil, M. D.; Ghosh, K. K.; RajanBabu, T. V. J. Am. Chem. Soc. 2024, 146, 6604. doi: 10.1021/jacs.3c12020
[48]	Guo, J.; Lu, Z. Angew. Chem., Int. Ed. 2016, 55, 10835. doi: 10.1002/anie.v55.36
[49]	Dong, W.; Ye, Z.; Zhao, W. Angew. Chem., Int. Ed. 2022, 61, e202117413. doi: 10.1002/anie.v61.29
[50]	Chen, C.; Wang, H.; Li, T.; Lu, D.; Li, J.; Zhang, X.; Hong, X.; Lu, Z. Angew. Chem., Int. Ed. 2022, 61, e202205619. doi: 10.1002/anie.v61.30
[51]	Hu, M.; Tan, B. B.; Ge, S. J. Am. Chem. Soc. 2022, 144, 15333. doi: 10.1021/jacs.2c06488
[52]	Xiong, K.; Lu, Z. CCS Chem. 2026, 8, 2299. doi: 10.31635/ccschem.026.202507003
[53]	Chen, J.; Xi, T.; Lu, Z. Org. Lett. 2014, 16, 6452. doi: 10.1021/ol503282r
[54]	Chen, C.; Shen, X.; Chen, J.; Hong, X.; Lu, Z. Org. Lett. 2017, 19, 5422. doi: 10.1021/acs.orglett.7b02691
[55]	Jang, W. J.; Song, S. M.; Moon, J. H.; Lee, J. Y.; Yun, J. J. Am. Chem. Soc. 2017, 139, 13660. doi: 10.1021/jacs.7b08379 pmid: 28899086
[56]	Xi, Y.; Su, B.; Qi, X.; Pedram, S.; Liu, P.; Hartwig, J. F. J. Am. Chem. Soc. 2020, 142, 18213. doi: 10.1021/jacs.0c08746
[57]	Selected examples of Markovnikov-type hydrofunctionalization of terminal alkynes: (a) Han, L.-B.; Tanaka, M. J. Am. Chem. Soc. 1996, 118, 1571. doi: 10.1021/ja953690t
	(b) Gao, F.; Hoveyda, A. H. J. Am. Chem. Soc. 2010, 132, 10961. doi: 10.1021/ja104896b
	(c) Jang, H.; Zhugralin, A. R.; Lee, Y.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 7859. doi: 10.1021/ja2007643
	(d) Dérien, S.; Klein, H.; Bruneau, C. Angew. Chem., Int. Ed. 2015, 54, 12112. doi: 10.1002/anie.v54.41
	(e) Zhang, X.; Xie, X.; Liu, Y. J. Am. Chem. Soc. 2018, 140, 7385. doi: 10.1021/jacs.8b02542
	(f) Chen, J.; Shen, X.; Lu, Z. Angew. Chem., Int. Ed. 2021, 60, 690. doi: 10.1002/anie.v60.2
	(g) Ying, J.; Tan, Y.; Lu, Z. Nat. Commun. 2024, 15, 8057. doi: 10.1038/s41467-024-52249-x
	(h) Ye, Z.; Ying, J.; Zhang, X.; Zhang, X.; Lu, Z. ACS Catal. 2025, 15, 14268. doi: 10.1021/acscatal.5c03532
	(i) Li, M.; Lv, X.; Wang, L.; Yan, H.; Zhang, Z.; Zhang, X.; Wang, M.; Lu, Z. J. Am. Chem. Soc. 2026, 148, 2617. doi: 10.1021/jacs.5c18484
	(j) Sun, Y.; Wang, B.; Wang, C.; Li, J.; Chen, J.; Hong, X.; Lu, Z. Sci. China Chem. 2025, 68, 2491. doi: 10.1007/s11426-024-2362-4
[58]	Chen, J.; Wei, W.-T.; Li, Z.; Lu, Z. Chem. Soc. Rev. 2024, 53, 7566. doi: 10.1039/D4CS00167B
[59]	Li, Z.; Ying, J.; Lu, Z. Chin. J. Chem. 2026, 44, 553. doi: 10.1002/cjoc.v44.4
[60]	Lu, J.-M.; Wang, H.-F.; Guo, Q.-H.; Wang, J.-W.; Li, T.-T.; Chen, K.-X.; Zhang, M.-T.; Chen, J.-B.; Shi, Q.-N.; Huang, Y.; Shi, S.-W.; Chen, G.-Y.; Pan, J.-Z.; Lu, Z.; Fang, Q. Nat. Commun. 2024, 15, 8826. doi: 10.1038/s41467-024-53204-6