Citation: Zhang Yongling, Wang Min, Cao Peng, Liao Jian. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand[J]. Acta Chimica Sinica, ;2017, 75(8): 794-797. doi: 10.6023/A17040144 shu

Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand

Zhang Yongling ^a,b ,
Wang Min ^a ,
Cao Peng ^a ,
Liao Jian ^a,b,,

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

Corresponding author: Liao Jian, jliao@cib.ac.cn
Received Date: 12 April 2017
Available Online: 9 August 2017
Fund Project: Project supported by the National Natural Science Foundation of China (Nos.21472184, 21572218 and 21402186)the National Natural Science Foundation of China 21402186the National Natural Science Foundation of China 21472184the National Natural Science Foundation of China 21572218

Figures(1)

To date, copper catalysis has become an attractive approach to access multifunctional alkylborons through borylative coupling processes, many important protocols such as carboboration, stannylboration and aminoboration were developed. Among these methods, however, there is no report involving enantioselective aminoboration of simple styrene substrates, which can generate a class of useful chiral compounds. In this work, an enantioselective Cu-catalyzed aminoboration of styrenes by using a chiral sulfoxide-phosphine (SOP) ligand was developed, chiral β-aminoalkylboranes were obtained in satisfied yields and ee values, and these products can be readily converted to a class of valuable β-hydroxylalkylamines. A general procedure for the aminoboration of styrenes is as following:in glove box, CuCl (0.02 mmol), chiral sulfoxide phosphine L1 (0.022 mmol) and 2.0 mL of dried tetrahydrofuran were added into a flame-dried tube, the resolved solution was stirred for 30 min at room temperature, then bis(pinacolato)diboron (B₂pin₂) (0.3 mmol), t-BuOLi (0.6 mmol) and styrene (0.2 mmol) were added. The tube was taken out of the glove box and cooled to 0℃. Electrophilic amination reagent, O-benzoyl-N, N-dibenzylhydroxylamine (2a, 0.3 mmol), was dissolved in 1.0 mL of ethyl acetate and added to the mixture, the resolved mixture was stirred at 0℃ for 24 h. The crude product was filtered through a celite pad, concentrated and oxidized by NaBO₃·4H₂O. The mixture was extracted three times with ethyl acetate, concentrated and purified with silica gel chromatography to give the desired β-hydroxylalkylamines, the enantioselective excess of products were determined by chiral HPLC analysis. Broad substrate scope which related to steric and electronic effect were compatible in this catalysis under the standard conditions. To demonstrate the utility of this method, a gram scale experiment was performed and the desired product was obtained in 92% isolated yield and 90% ee. The benzyl group of products can be readily removed via a Pd/C-catalyzed hydrogenation process and the corresponding product with a free amino group in excellent yield (95%).
- Cu-catalyzed,
- chiral sulfoxide phosphine,
- styrenes,
- enantioselective aminoboration,
- β-hydroxylalkylamines
1. [1]
  (a) Pelter, A.; Smith, K.; Brown, H. C. Borane Reagents, Academic Press, London, 1988; (b) Miyaura, N.; Suzuki, A. Chem. Rev.1995, 95, 2457; (c) Davison, M.; Hughes, A. K.; Marder, T. B.; Wade, K. Contemporary Boron Chemistry, RSC, Cambridge, U. K., 2000; (d) Boronic Acids, 2nd ed.; Ed.: Hall, D. G., Wiley-VCH, Weinheim, Germany, 2011.
2. [2]
  (a) Ishiyama, T.; Matsuda, N.; Miyaura, N.; Suzuki, A. J. Am.Chem. Soc. 1993, 115, 11018; (b) Ishiyama, T.; Matsuda, N.; Murata, M.; Ozawa, F.; Suzuki, A.; Miyaura, N. Organometallics 1996, 15, 713; (c) Lesley, G.; Nguyen, P.; Taylor, N. J.; Marder, T. B. Organometallics 1996, 15, 5137; (d) Ishiyama, T.; Yamamoto, M.; Miyaura, N. Chem.Commun. 1996, 2073; (e) Ishiyama, T.; Yamamoto, M.; Miyaura, N. Chem.Commun. 1997, 689; (f) Thomas, R. L.; Souza, F. E. S.; Marder, T. B. J. Chem. Soc., Dalton Trans. 2001, 1650; (g) Yang, F.-Y.; Cheng, C.-H. J. Am. Chem. Soc. 2001, 123, 761; (h) Burks, H. E.; Kliman, L. T.; Morken, J. P. J. Am.Chem. Soc. 2009, 131, 9134; (i) Kliman, L. T.; Mlynarski, S. N.; Morken, J. P. J. Am. Chem. Soc. 2009, 131, 13210; (j) Iwadate, N.; Suginome, M. J. Am. Chem. Soc. 2010, 132, 2548; (k) Coombs, J. R.; Haeffner, F.; Kliman, L. T.; Morken, J. P. J. Am. Chem. Soc. 2013, 135, 11222; (l) Coombs, J. R.; Zhang, L.; Morken, J. P. J. Am.Chem. Soc. 2014, 136, 16140; For review, see: Ishiyama, T.; Ishida, K.; Miyaura, N. Tetrahedron 2001, 57, 9813 and references therein.
3. [3]
4. [4]
  Selected examples, see: (a) Adams, C. J.; Baber, R. A.; Batsanov, A. S.; Bramham, G.; Charmant, J. P.; Haddow, M. F.; Howard, J. A.; Lam, W. H.; Lin, Z.; Marder, T. B.; Norman, N. C.; Orpen, A. G. Dalton Trans. 2006, 1370; (b) Obligacion, J. V.; Chirik, P. J. Org. Lett.2013, 15, 2680; (c) Obligacion, J. V.; Chirik, P. J. J. Am.Chem. Soc. 2013, 135, 19107. (d) Zhang, L.; Peng, D.; Leng, X.; Huang, Z. Angew. Chem., Int. Ed. 2013, 52, 3676; (e) Cao, Y.; Zhang, Y.; Zhang, L.; Zhang, D.; Leng, X.; Huang, Z. Org. Chem. Front.2014, 1, 1101; (f) Chen, J.; Xi, T.; Lu, Z.Org. Lett. 2014, 16, 6452; (g) Chen, J.; Xi, T.; Ren, X.; Cheng, B.; Guo, J.; Lu, Z. Org. Chem. Front. 2014, 1, 1306; (h) Zhang, L.; Zuo, Z.; Leng, X.; Huang, Z. Angew. Chem., Int. Ed. 2014, 53, 2696; (i) Zhang, L.; Zuo, Z.; Wan, X.; Huang, Z. J. Am. Chem. Soc. 2014, 136, 15501; (j) Guo, J.; Chen, J.; Lu, Z. Chem. Commun. 2015, 51, 5725; (k) Zhang, L.; Huang, Z. J. Am. Chem. Soc. 2015, 137, 15600; (l) Zhang, H.; Lu, Z. ACS Catal. 2016, 6, 6596; (m) Zuo, Z.; Huang, Z. Org. Chem. Front. 2016, 3, 434; (n) Zuo, Z.; Yang, J.; Huang, Z. Angew. Chem., Int.Ed. 2016, 55, 10839; (o) Xi, T.; Lu, Z. ACS Catal. 2017, 7, 1181.
5. [5]
  (a) Suginome, M.; Matsuda, T.; Yoshimoto, T.; Ito, Y. Org. Lett.1999, 1, 1567; (b) Suginome, M.; Shirakura, M.; Yamamoto, A. J.Am. Chem. Soc. 2006, 128, 14438; (c) Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534.
6. [6]
7. [7]
  (a) Bloch, R. Chem. Rev. 1998, 98, 1407; (b) Ramadhar, T. R.; Batey, R. A. Synthesis 2011, 1321; (c) Yus, M.; González-Gómez, J. C.; Foubelo, F. Chem. Rev. 2013, 113, 5595.
8. [8]
  (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) Shi, M. Chem. Commun. 2016, 52, 5273.
9. [9]
  (a) Chen, B.; Cao, P.; Yin, X.; Liao, Y.; Jiang, L.; Ye, J.; Wang, M.; Liao, J. ACS Catal. 2017, 7, 2425; (b) Jia, T.; Cao, P.; Wang, B.; Lou, Y.; Yin, X.; Wang, M.; Liao, J. J. Am.Chem. Soc. 2015, 137, 13760; (c) Jia, T.; Cao, P.; Wang, D.; Lou, Y.; Liao, J. Chem. Eur. J.2015, 21, 4918.
10. [10]
  Metro, T. X.; Appenzeller, J.; Pardo, D. G.; Cossy, J. Org. Lett. 2006, 8, 3509. doi: 10.1021/ol061133d
1. [1]
  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
2. [2]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
3. [3]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
4. [4]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
5. [5]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
6. [6]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
7. [7]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
8. [8]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
9. [9]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
10. [10]
  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
11. [11]
  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
12. [12]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
13. [13]
  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
14. [14]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
15. [15]
  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
16. [16]
  Qin Hou , Jiayi Hou , Aiju Shi , Xingliang Xu , Yuanhong Zhang , Yijing Li , Juying Hou , Yanfang Wang . Preparation of Cuprous Iodide Coordination Polymer and Fluorescent Detection of Nitrite: A Comprehensive Chemical Design Experiment. University Chemistry, 2024, 39(8): 221-229. doi: 10.3866/PKU.DXHX202312056
17. [17]
  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
18. [18]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(1459)
HTML views(217)

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