Citation: Li Sujia, Lü Jian, Luo Sanzhong. Enantioselective Indium(I)/Chiral Phosphoric Acid-catalyzed[4+2] Cycloaddition of Simple Olefin and β, γ-Unsaturated α-Keto Esters[J]. Acta Chimica Sinica, ;2018, 76(11): 869-873. doi: 10.6023/A18060227 shu

Enantioselective Indium(I)/Chiral Phosphoric Acid-catalyzed[4+2] Cycloaddition of Simple Olefin and β, γ-Unsaturated α-Keto Esters

Key Laboratory of Molecular Recognition and Functions, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190

Corresponding author: Lü Jian, lvjian@iccas.ac.cn Luo Sanzhong, luosz@iccas.ac.cn
Received Date: 8 June 2018
Available Online: 26 November 2018
Fund Project: the National Natural Science Foundation of China 21472193the National Natural Science Foundation of China 21521002the Chinese Academy of Sciences QYZDJ-SSW-SLU023the National Natural Science Foundation of China 21390400Project supported by the National Natural Science Foundation of China (Nos. 21390400, 21521002, 21472193) and the Chinese Academy of Sciences (No. QYZDJ-SSW-SLU023)

Figures(2)

Compared with indium(Ⅲ), indium(I) has both vacant p-orbitals and an electron lone pair, showing distinctive catalytic behaviors. However, chiral indium(I) catalysis has been rarely reported. Previously, we have developed asymmetric binary acid catalysis with indium(Ⅲ) and chiral phosphoric acid for a number of enantioselective transformations. Asymmetric binary-acid catalysis in[4+2] cycloaddition of β, γ-unsaturated α-keto esters with different olefins have been reported by our groups over the past five years. In 2013, we developed exo-selective and enantioselective[4+2] cycloaddition of simple industrial feedstock olefins, such as propene and isobutene, styrene and so on, catalyzed by In(BArF)₃/1a. However, the reaction with electron-rich olefins, such as 4-methoxylstyrene did not work very well by indium(Ⅲ) catalysis due to uncontrolled polymerization side pathway. Very recently, we developed a new binary acid system InCl/1a, which could catalyze enantioselective[4+2] annulation of β, γ-unsaturated α-keto esters with much more electron-rich alkoxyallenes. In this study, we reported that the binary acid InCl and 1a was an effective and exo-selective catalyst for the[4+2] cycloaddition of simple olefins. In the presence of InCl (10 mol%) and chiral phosphoric acid 1a (10 mol%), the reaction occurred smoothly to afford the desired cycloadducts in moderate to good yields (20%~93%), with excellent diastereoselectivity (>95:5, exo/endo) and enantioselectivity (up to 99% ee) under the room temperature in CHCl₃. Different olefins, such as styrenes 2, ring-strained norbornene 5a, norbornadiene 5b, and cyclopentadiene dimer 5c all worked well with excellent stereoselectivity under the optimal reaction conditions. More importantly, when 4-methoxylstyrene is used, the reaction can proceeded smoothly to afford[4+2] adduct 4k in 70% yield and good stereoselectivity (>95:5 dr, and 88% ee). The typical procedure for asymmetric[4+2] cycloaddition is as follows:To a dry reaction tube was added chiral phosphoric acid 1a (0.005 mmol, 5 mol%), InCl (0.005 mmol, 5 mol%), 4 MS (10 mg), 3 (0.1 mmol), then CHCl₃ (0.5 mL) and 2 or 5 (0.5 mmol) was added to the mixture. The mixture was stirred for 24 h at room temperature. The mixture was purified by column chromatography to give the desired cycloaddition products 4 or 6.
- asymmetric catalysis,
- [4+2]cycloaddition,
- binary-acid catalysis,
- InCl,
- chiral phosphoric acid
1. [1]
  (a) Gewali, M. B.; Tezuka, Y.; Banskota, A. H.; Ali, M. S.; Saiki, I.; Dong, H.; Kadota, S. Org. Lett. 1999, 1, 1733. (b) Tezuka, Y.; Gewali, M. B.; Ali, M. S.; Banskota, A. H.; Kadota, S. J. Nat. Prod. 2001, 64, 208. (c) Whiting, D. A. Nat. Prod. Rep. 1987, 4, 499.
2. [2]
  (a) Fehr, C.; Galindo, J.; Ohloff, G. Helv. Chim. Acta 1981, 64, 1247. (b) Sera, A.; Ohara, M.; Yamada, H.; Egashira, E.; Ueda, N.; Setsune, J.-I. Chem. Lett. 1990, 19, 2043. (c) Dujardin, G.; Maudet, M.; Brown, E. Tetrahedron Lett. 1994, 35, 8619. (d) Leconte, S.; Dujardin, G.; Brown, E. Eur. J. Org. Chem. 2000, 639. (e) Maingot, L.; Leconte, S.; Chataigner, I.; Martel, A.; Dujardin, G. Org. Lett. 2009, 11, 1619. (f) Brown, E.; Dujardin, G.; Maudet, M. Tetrahedron 1997, 53, 9679.
3. [3]
  (a) Lv, J.; Zhang, L.; Luo, S.; Cheng, J.-P. Angew. Chem., Int. Ed. 2013, 52, 9786; (b) Matumura, Y.; Suzuki, T.; Sakakura, A.; Ishihara, K. Angew. Chem., Int. Ed. 2014, 53, 6131.
4. [4]
5. [5]
6. [6]
7. [7]
  For reviews on indium (Ⅲ) as a Lewis acid, see (a) Ranu, B. C.; Eur. J. Org. Chem. 2000, 2347. (b) Ghosh, R. Maiti, S. J. Mol. Catal. A: Chem. 2007, 264, 1. (c) Osten, K. M.; Mehrkhodavandi, P. Acc. Chem. Res. 2017, 50, 2861.
8. [8]
  For recent selected examples of chiral indium(Ⅲ) Lewis acid- catalysis, see: (a) Zhao, J.-F.; Tsui, H.-Y.; Wu, P.-J.; Lu, J.; Loh, T.-P. J. Am. Chem. Soc. 2008, 130, 16492. (b) Yu, Z.; Liu, X.; Dong, Z.; Xie, M.; Feng, X. Angew. Chem. Int. Ed. 2008, 47, 1308. (c) Lin, L.; Kuang, Y.; Liu, X.; Feng, X. Org. Lett. 2011, 13, 3868. (d) Zhao, J.-F.; Tan, B.-H.; Loh, T.-P. Chem. Sci. 2011, 2, 349. (e) Zhao, B. Loh, T.-P. Org. Lett. 2013, 15, 2914. (f) Praveen, C.; Montaignac, B.; Vitale, M. R.; Ratovelomanana-Vidal, V.; Michelet, V. ChemCatChem 2013, 5, 2395. (g) Zhang, X.; Wang, M.; Ding, R.; Xu, Y.-H.; Loh, T.-P. Org. Lett. 2015, 17, 2736. (h) Wang, L.; Lv, J.; Zhang, L.; Luo, S. Angew. Chem., Int. Ed. 2017, 56, 10867.
9. [9]
  (a) Schneider, U.; Kobayashi, S. Acc. Chem. Res. 2012, 45, 1331. (b) Tuck, D. G. Chem. Soc. Rev. 1993, 22, 269. (c) Andrews, C. G. Macdonald, C. L. B. Angew. Chem., Int. Ed. 2005, 44, 7453. (d) Cooper, B. F. T.; Andrews, C. G.; Macdonald, C. L. B. J. Organmet. Chem. 2007, 692, 2843. (e) Allan, C. J.; Cooper, B. F. T.; Cowley, H. J.; Rawson, J. M.; Macdonald, C. L. B. Chem. Eur. J. 2013, 19, 14470.
10. [10]
  (a) Chakrabarti, A.; Konishi, H.; Yamaguchi, M.; Schneider, U.; Kobayashi, S. Angew. Chem., Int. Ed. 2010, 49, 1838. (b) Huang, Y.-Y.; Chakrabarti, A.; Morita, N.; Schneider, U.; Kobayashi, S. Angew. Chem., Int. Ed. 2011, 50, 11121. (c) Li, S.; Lv, J.; Luo, S. Org. Chem. Front. 2018, 5, 1787.
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]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
9. [9]
  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
10. [10]
  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
11. [11]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
12. [12]
  Xueting Cao , Shuangshuang Cha , Ming Gong . 电催化反应中的界面双电层：理论、表征与应用. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-. doi: 10.1016/j.actphy.2024.100041
13. [13]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
14. [14]
  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
15. [15]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
16. [16]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
17. [17]
  Qiuting Zhang , Fan Wu , Jin Liu , Zian Lin . Chromatographic Stationary Phase and Chiral Separation Using Frame Materials. University Chemistry, 2025, 40(4): 291-298. doi: 10.12461/PKU.DXHX202405174
18. [18]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
19. [19]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
20. [20]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(956)
HTML views(164)

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