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]
  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
2. [2]
  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
3. [3]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
4. [4]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
5. [5]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
6. [6]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
7. [7]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
8. [8]
  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
9. [9]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
10. [10]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
11. [11]
  Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C₃N₄/Ti₃C₂T_x Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477
12. [12]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
13. [13]
  Siyu HOU , Weiyao LI , Jiadong LIU , Fei WANG , Wensi LIU , Jing YANG , Ying ZHANG . Preparation and catalytic performance of magnetic nano iron oxide by oxidation co-precipitation method. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1577-1582. doi: 10.11862/CJIC.20230469
14. [14]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
15. [15]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
16. [16]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
17. [17]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
18. [18]
  Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO₂/Bi₂MoO₆ Microsphere Heterojunction for Efficient Photocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
19. [19]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
20. [20]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(765)
HTML views(110)

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