Citation: Huang Hao, Lin Huaxin, Wang Min, Liao Jian. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with 1, 2-Benzisoxazole as Nitrogen Source[J]. Acta Chimica Sinica, ;2020, 78(11): 1229-1234. doi: 10.6023/A20090424 shu

Copper-Catalyzed Enantioselective Aminoboration of Styrenes with 1, 2-Benzisoxazole as Nitrogen Source

Huang Hao ^a,b ,
Lin Huaxin ^a,b ,
Wang Min ^a ,
Liao Jian ^a,b,,

a.
Natural Products Research Center, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Liao Jian, jliao@cib.ac.cn
Received Date: 14 September 2020
Available Online: 28 October 2020
Fund Project: the Biological Resources Programme, Chinese Academy of Sciences KFJ-BRP-008the National Nature Science Foundation of China 21871251Project supported by the National Nature Science Foundation of China (No. 21871251) and the Biological Resources Programme, Chinese Academy of Sciences (No. KFJ-BRP-008)

Figures(4)

Organoboron compounds are important intermediates in organic synthesis because of their high utilities for C—C and C—X bond formations. Transition metal-catalyzed borylative difunctionalization of alkenes, which can simultaneously introduce C—B, C—C or C—X bonds, could directly construct highly functionalized organoboron in one step. Among these reactions, copper catalyzed enantioselective aminoboration of styrenes is an efficient approach to generate enantioriched β-aminoboronate which is a class of useful chiral compounds. In this work, employing styrenes as substrates, 1, 2-benzisoxazole as an electrophilic primary amine source, bis(pinacolato)diboron (B₂pin₂) as boron source and LiOCH₃ as base, an enantioselective Cu-catalyzed aminoboration of styrenes by using a chiral sulfoxide-phosphine (SOP) ligand was developed, and a board range of chiral β-aminoalkylboranes, which could be readily converted to a class of valuable β-hydroxylalkylamines, were accessed with high yields and ee values. A general procedure for this aminoboration of styrenes is described in the following: in a glove box, CuI (0.05 mmol), chiral sulfoxide phosphine ligand L1 (0.06 mmol), and 2 mL of anhydrous tetrahydrofuran were added into a flame-dried tube. The resulting mixture was stirred at room temperature for 30 min. Then bis(pinacolato)diboron (B₂pin₂) (0.75 mmol), LiOCH₃ (1.25 mmol), styrene 1 (0.5 mmol), 1, 2-benzisoxazole (0.75 mmol) and another 2 mL of THF were added into the reaction system in sequence. The reaction tube was removed out from the glove box and stirred at 20 ℃ for 12 h. After the reaction was finished, the NMR yield was firstly determined with dimethyl terephthalate (9.7 mg, 0.05 mmol) as internal standard, then, the crude product was recovered and purified with a preparative TLC which was alkalized with triethylamine to give the desired β-aminoboronates in moderate to good yields (47%~84%) and enantioselectivities (81%~99%). To demonstrate the utility of this reaction, β-boronate primary amine could be easily obtained by removing the Schiff base group of β-aminoboronate 3 under the methanol solution of hydroxylamine hydrochloride, which could be further oxidized to give corresponding chiral β-amino alcohol in moderate yield (48%).
- Cu-catalyzed,
- styrenes,
- 1, 2-benzisoxazole,
- enantioselective aminoboration,
- β-boronate primary amine
1. [1]
2. [2]
  (a) Gorovoy, A. S.; Gozhina, O.; Svendsen, J.-S.; Tetz, G. V.; Domorad, A.; Tetz, V. V.; Lejon, T. J. Pept. Sci. 2013, 19, 613. (b) Gorovoy, A. S.; Gozhina, O. V.; Svendsen, J. S.; Domorad, A. A.; Tetz, G. V.; Tetz, V. V.; Lejon, T. Chem. Biol. Drug Des. 2013, 81, 408.
3. [3]
  (a) Solé, G.; Gulyás, H.; Fernández, E. Chem. Commun. 2012, 48, 3769. (b) He, Z. T.; Zhao, Y. S.; Tian, P.; Wang, C. C.; Dong, H. Q.; Lin, G. Q. Org. Lett. 2014, 16, 1426. (c) Takeda, Y.; Kuroda, A.; Sameera, W. M. C.; Morokuma, K.; Minakata, S. Chem. Sci. 2016, 7, 6141. (d) Park, J.; Lee, Y.; Kim, J.; Cho, S. H. Org. Lett. 2016, 18, 1210. (e) Kim, J.; Ko, K.; Cho, S. H. Angew. Chem., Int. Ed. 2017, 56, 11584. (f) Li, X.; Hall, D. G. Angew. Chem., Int. Ed. 2018, 57, 10304. (g) Kim, J.; Hwang, C.; Kim, Y.; Cho, S. H. Org. Process Res. Dev. 2019, 23, 1663. (h) Kim, J.; Shin, M.; Cho, S. H. ACS Catal. 2019, 9, 8503. (i) Li, X.; Hall, D. G. J. Am. Chem. Soc. 2020, 142, 9063.
4. [4]
5. [5]
  (a) Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. J. Am. Chem. Soc. 2013, 135, 4934. (b) Sakae, R.; Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16, 1228. (c) Parra, A.; Amenos, L.; Guisan-Ceinos, M.; Lopez, A.; Garcia Ruano, J. L.; Tortosa, M. J. Am. Chem. Soc. 2014, 136, 15833. (d) Sakae, R.; Hirano, K.; Miura, M. J. Am. Chem. Soc. 2015, 137, 6460. (e) Sakae, R.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2015, 54, 613. (f) Kato, K.; Hirano, K.; Miura, M. Angew. Chem., Int. Ed. 2016, 55, 14400. (g) Nishikawa, D.; Hirano, K.; Miura, M. Org. Lett. 2016, 18, 4856. (h) Jiang, H. C.; Tang, X. Y.; Shi, M. Chem. Commun. 2016, 52, 5273. (i) Huo, J.; Xue, Y.; Wang, J. Chem. Commun. 2018, 54, 12266. (j) Kato, K.; Hirano, K.; Miura, M. Chem. Eur. J. 2018, 24, 5775.
6. [6]
  (a) Guo, S.; Yang, J. C.; Buchwald, S. L. J. Am. Chem. Soc. 2018, 140, 15976. (b) Feng, S.; Hao, H.; Liu, P.; Buchwald, S. L. ACS Catal. 2019, 10, 282. (c) Guo, S.; Zhu, J.; Buchwald, S. L. Angew. Chem., Int. Ed. 2020, 59, 20841.
7. [7]
  (a) Casey, M. L.; Kemp, D. S.; Paul, K. G.; Cox, D. J. Org. Chem. 1973, 38, 2294.
8. [8]
9. [9]
  (a) Noshita, M.; Shimizu, Y.; Morimoto, H.; Ohshima, T. Org. Lett. 2016, 18, 6062.
10. [10]
  (a) Laitar, D. S.; Tsui, E. Y.; Sadighi, J. P. Organometallics 2006, 25, 2405. (b) Jiang, L.; Cao, P.; Wang, M.; Chen, B.; Wang, B.; Liao, J. Angew. Chem., Int. Ed. 2016, 55, 13854. (c) Tobisch, S. Chem. Eur. J. 2017, 23, 17800.
1. [1]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
2. [2]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
3. [3]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
4. [4]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
5. [5]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
6. [6]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
7. [7]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
8. [8]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
9. [9]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
10. [10]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
11. [11]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
12. [12]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
13. [13]
  Xiuyun Wang , Jiashuo Cheng , Yiming Wang , Haoyu Wu , Yan Su , Yuzhuo Gao , Xiaoyu Liu , Mingyu Zhao , Chunyan Wang , Miao Cui , Wenfeng Jiang . Improvement of Sodium Ferric Ethylenediaminetetraacetate (NaFeEDTA) Iron Supplement Preparation Experiment. University Chemistry, 2024, 39(2): 340-346. doi: 10.3866/PKU.DXHX202308067
14. [14]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
15. [15]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
16. [16]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
17. [17]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
18. [18]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
19. [19]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
20. [20]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(723)
HTML views(80)

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