Citation: Liu Wenbo, Lu Zhan. Application of Pinacolborane in Catalytic Enantioselective Hydroboration of Ketones and Imines[J]. Chinese Journal of Organic Chemistry, ;2020, 40(11): 3596-3604. doi: 10.6023/cjoc202008039 shu

Application of Pinacolborane in Catalytic Enantioselective Hydroboration of Ketones and Imines

Liu Wenbo ,
Lu Zhan ^,

Department of Chemistry, Zhejiang University, Hangzhou 310000

Corresponding author: Lu Zhan, luzhan@zju.edu.cn
Received Date: 21 August 2020
Revised Date: 8 September 2020
Available Online: 15 September 2020
Fund Project: National Natural Science Foundation of China 21922107Natural Science Foundation of Zhejiang Province LR19B020001Center of Chemistry for Frontier Technologies and the Fundamental Research Funds for the Central Universities 2019QNA3008Project supported by the National Natural Science Foundation of China (Nos. 21922107, 21772171), the Natural Science Foundation of Zhejiang Province (No. LR19B020001), the Center of Chemistry for Frontier Technologies and the Fundamental Research Funds for the Central Universities (No. 2019QNA3008)National Natural Science Foundation of China 21772771

Figures(18)

Enantioselective hydroboration of ketones and imines provides a powerful method to access valuable chiral alcohols and amines which are widely used in organic synthesis, materials science, pharmaceutical, agrochemistry and fine chemical industry. After invented in 1991, pinacolborane (HBpin) as a stable, commercially available and measurably simple reductive reagent has been widely applied in hydroboration of carbonyl derivatives, imines and nitriles and relevant mechanistic investigation. In the past 5 years, HBpin has also been employed for asymmetric catalytic hydroboration (CHB) to access chiral alcohols and amines. The enantioselective CHB reactions of ketones and imines using HBpin are outlined according to the classification of different catalysts, such as earth abundant transition metals, main group elements, and rare-earth metals.
- pinacolborane,
- asymmetric hydroboration,
- earth abundant transition metal,
- ketone,
- imine
1. [1]
  Marsden, S. Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, Vols. 1 and 2, Ed.: Hall, D. G., Wiley-VCH, Weinheim, 2011.
2. [2]
  Chong, C. C.; Kinjo, R. ACS Catal. 2015, 5, 3238. doi: 10.1021/acscatal.5b00428
3. [3]
  Brown, H. C.; Schlesinger, H. I.; Burg, A. B. J. Am. Chem. Soc. 1939, 61, 673. doi: 10.1021/ja01872a041
4. [4]
  Wang, Z. In Comprehensive Organic Name Reactions and Reagents, Ed.: Wang, Z., John Wiley & Sons, New Jersey, 2010, pp. 536~543.
5. [5]
  Corey, E. J.; Helal, C. J. Angew. Chem., Int. Ed. 1998, 37, 1986. doi: 10.1002/(SICI)1521-3773(19980817)37:15<1986::AID-ANIE1986>3.0.CO;2-Z
6. [6]
  Tucker, C. E.; Davidson, J.; Knochel, P. J. Org. Chem. 1992, 57, 3482. doi: 10.1021/jo00038a044
7. [7]
  Shegavi, M. L.; Bose, S. K. Catal. Sci. Technol. 2019, 9, 3307. doi: 10.1039/C9CY00807A
8. [8]
  Koren-Selfridge, L.; Londino, H. N.; Vellucci, J. K.; Simmons, B. J.; Casey, C. P.; Clark, T. B. Organometallics 2009, 28, 2085. doi: 10.1021/om801228m
9. [9]
  Query, I. P.; Squier, P. A.; Larson, E. M.; Isley, N. A.; Clark, T. B. J. Org. Chem. 2011, 76, 6452. doi: 10.1021/jo201142g
10. [10]
  Wu, Y.; Shan, C.; Ying, J.; Su, J.; Zhu, J.; Liu, L. L.; Zhao, Y. Green Chem. 2017, 19, 4169. doi: 10.1039/C7GC01632H
11. [11]
  Guo, J.; Chen, J.; Lu, Z. Chem. Commun. 2015, 51, 5725. doi: 10.1039/C5CC01084E
12. [12]
  Adams, M. R.; Tien, C.-H.; McDonald, R.; Speed, A. W. H. Angew. Chem., Int. Ed. 2017, 56, 16660. doi: 10.1002/anie.201709926
13. [13]
  Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed., 2001, 40, 40. doi: 10.1002/1521-3773(20010105)40:1<40::AID-ANIE40>3.0.CO;2-5
14. [14]
  Liu, W.; Guo, J.; Xing, S.; Lu, Z. Org. Lett. 2020, 22, 2532. doi: 10.1021/acs.orglett.0c00293
15. [15]
  Chen, F.; Zhang, Y.; Yu, L.; Zhu, S. Angew. Chem., Int. Ed. 2017, 56, 2022. doi: 10.1002/anie.201610990
16. [16]
  Vasilenko, V.; Blasius, C. K.; Wadepohl, H.; Gade, L. H. Angew. Chem., Int. Ed. 2017, 56, 8393. doi: 10.1002/anie.201704184
17. [17]
  Vasilenko, V.; Blasius, C. K.; Gade, L. H. J. Am. Chem. Soc. 2018, 140, 9244. doi: 10.1021/jacs.8b05340
18. [18]
  Blasius, C. K.; Vasilenko, V.; Gade, L. H. Angew. Chem., Int. Ed. 2018, 57, 10231. doi: 10.1002/anie.201806196
19. [19]
  Blasius, C. K.; Heinrich, N. F.; Vasilenko, V. Gade, L. H. Angew. Chem., Int. Ed. 2020, 59, 15974. doi: 10.1002/anie.202006557
20. [20]
  Agarwal, R.; Liao, Y.; Lin, D.-J.; Yang, Z.-X.; Lai, C.-F.; Chen, C.-T. Org. Chem. Front. 2020, 7, 2505. doi: 10.1039/C9QO01304K
21. [21]
  Mukherjee, D.; Osseili, H.; Spaniol, T. P.; Okuda, J. J. Am. Chem. Soc. 2016, 138, 10790. doi: 10.1021/jacs.6b06319
22. [22]
  Willcox, D.; Carden, J. L.; Ruddy, A. J.; Newman, P. D.; Melen, R. L. Dalton Trans. 2020, 49, 2417. doi: 10.1039/D0DT00232A
23. [23]
  Falconnet, A.; Magre, M.; Maity, B.; Cavallo, L.; Rueping, M. Angew. Chem., Int. Ed. 2019, 58, 17567. doi: 10.1002/anie.201908012
24. [24]
  Vasilenko, V.; Blasius, C. K.; Wadepohl, H.; Gade, L. H. Chem. Commun. 2020, 56, 1203. doi: 10.1039/C9CC09111D
25. [25]
  Lebedev, Y.; Polishchuk, I.; Maity, B.; Guerreiro, M. D. V.; Cavallo, L.; Rueping, M. J. Am. Chem. Soc. 2019, 141, 19415. doi: 10.1021/jacs.9b10364
26. [26]
  Lundrigan, T.; Welsh, E. N.; Hynes, T.; Tien, C.-H.; Adams, M. R.; Roy, K. R.; Robertson, K. N.; Speed, A. W. H. J. Am. Chem. Soc. 2019, 141, 14083. doi: 10.1021/jacs.9b07293
27. [27]
  Tian, J.-J.; Yang, Z.-Y.; Liang, X.-S.; Liu, N.; Hu, C.-Y.; Tu, X.-S.; Li, X.; Wang, X.-C. Angew. Chem., Int. Ed. 2020, 59, 18452. doi: 10.1002/anie.202007352
28. [28]
  Song, P.; Lu, C.; Fei, Z.; Zhao, B.; Yao, Y. J. Org. Chem. 2018, 83, 6093. doi: 10.1021/acs.joc.8b00783
29. [29]
  Sun, Y.; Lu, C.; Zhao, B.; Xue, M. J. Org. Chem. 2020, 85, 10504. doi: 10.1021/acs.joc.0c00877
30. [30]
  Zhang, F.-H.; Zhang, F.-G.; Li, M.-L.; Xie, J.-H.; Zhou, Q.-L. Nat. Catal. 2020, 3, 621. doi: 10.1038/s41929-020-0474-5
31. [31]
  For recent reactions with other boranes:
  (a) Taniguchi, T.; Curran, D. P. Angew. Chem., Int. Ed. 2014, 53, 13150.
  (b) Zhou, N.; Yuan, X.-A.; Zhao, Y.; Xie, J.; Zhu, C. Angew. Chem., Int. Ed. 2018, 57, 3990.
  (c) Shimoi, M.; Watanabe, T.; Maeda, K.; Curran, D. P.; Taniguchi, T. Angew. Chem., Int. Ed. 2018, 57, 9485.
  (d) Yamamoto, K.; Mohara, Y.; Mutoh, Y.; Saito, S. J. Am. Chem. Soc. 2019, 141, 17042.
  (e) Dai, W.; Geib, S. J.; Curran, D. P. J. Am. Chem. Soc. 2020, 142, 6261.
32. [32]
  For selected reviews:
  (a) Chen, J.; Lu, Z. Org. Chem. Front. 2018, 5, 260.
  (b) Chen, J.; Guo, J.; Lu, Z. Chin. J. Chem. 2018, 36, 1075.
  (c) Cheng, Z.; Guo, J.; Lu, Z. Chem. Commun. 2020, 56, 2229.
  (d) Li, Y. Y.; Cheng, Y. H.; Shan, C. H.; Zhang, J.; Xu, D. D.; Bai, R. P.; Qu, L. B.; Lan, Y. Chin. J. Org. Chem. 2018, 38, 1885(in Chinese).
  (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.)
  (e) Sun, Y.; Guan, R.; Liu, Z. H.; Wang, Y. M. Chin. J. Org. Chem. 2020, 40, 651(in Chinese).
  (孙越, 关瑞, 刘兆洪, 王也铭, 有机化学, 2020, 40, 651.)
1. [1]
  Jun Yan , Shenghao Jiang , Yin Wei , Min Shi . Palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone-vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs). Chinese Chemical Letters, 2026, 37(11): 112369-. doi: 10.1016/j.cclet.2026.112369
2. [2]
  Wen-Bo Wei , Qi-Long Zhu . Electrosynthesis of hydroxylamine from earth-abundant small molecules. Chinese Journal of Structural Chemistry, 2025, 44(1): 100383-100383. doi: 10.1016/j.cjsc.2024.100383
3. [3]
  Yadan SUN , Xinfeng LI , Qiang LIU , Oshio Hiroki , Yinshan MENG . Structures and magnetism of dinuclear Co complexes based on imine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2212-2220. doi: 10.11862/CJIC.20240131
4. [4]
  Yuexin Wang , Xianjun Lang . An imine detour to vinylene-linked covalent organic frameworks. Chinese Journal of Structural Chemistry, 2026, 45(6): 100911-100911. doi: 10.1016/j.cjsc.2026.100911
5. [5]
  Xiangwei Chen , Yunyun Liu , Jie-Ping Wan . Disclosing α-trichloromethyl ketone—secondary amine combination as peptide coupling reagent based on the three-component access to β-acyloxyl alkenyl amides. Chinese Chemical Letters, 2026, 37(12): 112469-. doi: 10.1016/j.cclet.2026.112469
6. [6]
  Hang Chen , Chengzhi Cui , Hebo Ye , Hanxun Zou , Lei You . Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups. Chinese Chemical Letters, 2024, 35(5): 109145-. doi: 10.1016/j.cclet.2023.109145
7. [7]
  Yan-Li Li , Zhi-Ming Li , Kai-Kai Wang , Xiao-Long He . Beyond 1,4-addition of in-situ generated (aza-)quinone methides and indole imine methides. Chinese Chemical Letters, 2024, 35(7): 109322-. doi: 10.1016/j.cclet.2023.109322
8. [8]
  Xiaxia Xing , Xiaoyu Chen , Zhenxu Li , Xinhua Zhao , Yingying Tian , Xiaoyan Lang , Dachi Yang . Polyethylene imine functionalized porous carbon framework for selective nitrogen dioxide sensing with smartphone communication. Chinese Chemical Letters, 2024, 35(9): 109230-. doi: 10.1016/j.cclet.2023.109230
9. [9]
  Lulu He , Le Wang , Zhen He , Yiqian Yang , Cheng Heng Pang , Aiguo Wu , Bencan Tang , Juan Li . An imine-linked covalent organic framework with intrinsic photo-induced mitochondrial regulation for breast cancer therapy. Chinese Chemical Letters, 2025, 36(9): 110717-. doi: 10.1016/j.cclet.2024.110717
10. [10]
  Teng Long , Haiqing Wang . Super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS₂ nanosheet/Ni₃S₄ nanoparticle with abundant plane- and edge-type active interfaces for robust all-pH hydrogen evolution. Chinese Chemical Letters, 2026, 37(3): 110623-. doi: 10.1016/j.cclet.2024.110623
11. [11]
  Hui Lei , Yingying Jiang , Jiayu Liu , Weifeng Zhang , Fanbo Meng , Jun Mou , Wenyi Liu , Pengcheng Lei , Rui Xiong , Zan Xu , Hang Zhang , Yanjun Wang , Guo-Bo Li , Lingling Yang , Hua-Li Wang . Structure-activity relationship studies of 3,4-disubstitued indole-2-ketone derivatives identify a potent glutaminyl cyclase inhibitor with antitumor activity against breast cancer. Chinese Chemical Letters, 2026, 37(6): 111511-. doi: 10.1016/j.cclet.2025.111511
12. [12]
  Tsegaye Tadesse Tsega , Jiantao Zai , Chin Wei Lai , Xin-Hao Li , Xuefeng Qian . Earth-abundant CuFeS2 nanocrystals@graphite felt electrode for high performance aqueous polysulfide/iodide redox flow batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100192-100192. doi: 10.1016/j.cjsc.2023.100192
13. [13]
  Taiwen Chen , Baohua Wang , Lu Zhang , Wenbo Bi , Cong Lyu . Amine/imine-functionalized covalent organic frameworks with high selective capacity of perfluoroalkyl substances: Mechanism and potential application as anode in capacitive deionization. Chinese Chemical Letters, 2026, 37(7): 112297-. doi: 10.1016/j.cclet.2025.112297
14. [14]
  Yu Pang , Min Wang , Ning-Hua Yang , Min Xue , Yong Yang . One-pot synthesis of a giant twisted double-layer chiral macrocycle via [4 + 8] imine condensation and its X-ray structure. Chinese Chemical Letters, 2024, 35(10): 109575-. doi: 10.1016/j.cclet.2024.109575
15. [15]
  Pengfu Gao , Yuan Geng , Wei Gong . Homochiral metal-organic frameworks bearing privileged ligands for heterogeneous asymmetric catalysis. Chinese Journal of Structural Chemistry, 2025, 44(10): 100719-100719. doi: 10.1016/j.cjsc.2025.100719
16. [16]
  Yanrui Liu , Paramaguru Ganesan , Peng Gao . Harnessing d-f transition rare earth complexes for single layer white organic light emitting diodes. Chinese Journal of Structural Chemistry, 2024, 43(9): 100369-100369. doi: 10.1016/j.cjsc.2024.100369
17. [17]
  Teng-Fei Yao , Guo-Ping Yang , Yao-Yu Wang . Boosting efficient electrocatalytic CO2 reduction by two-dimensional polyoxometalate@metal-organic framework composites with asymmetric sites. Chinese Journal of Structural Chemistry, 2026, 45(8): 100948-100948. doi: 10.1016/j.cjsc.2026.100948
18. [18]
  Xue-Lu Ma , Jun-Bo Lu , Yuan Zhang , Ya-Fei Jiang , Jun Li . Dinitrogen fixation on transition metal complexes with flexible axial bonding. Chinese Journal of Structural Chemistry, 2026, 45(3): 100831-100831. doi: 10.1016/j.cjsc.2025.100831
19. [19]
  Xingyu Liu , Xiang Wu . Transition metal phosphide electrocatalysts for hydrogen generation from water. Chinese Chemical Letters, 2026, 37(8): 111801-. doi: 10.1016/j.cclet.2025.111801
20. [20]
  Yicheng Li , Qian Liu , Tianhao Li , Hao Bi , Zhurui Shen . Recent achievements in rare earth modified metal oxides for environmental and energy applications: A review. Chinese Chemical Letters, 2025, 36(9): 110698-. doi: 10.1016/j.cclet.2024.110698

Get Citation

PDF

XML

Metrics

PDF Downloads(47)
Abstract views(8949)
HTML views(1198)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142