Citation: Zhang Shuo, Lou Jianfang, Wang Jiarui, Song Zihe, Peng Dan, Wang Feng, Yan Zhiwang, Cui Shiqi, Liu Yifan, Mu Qiuhong, Li Jinhui. Zn/Y Bimetallic Relay Catalysis: One Pot Intramolecular Cyclo-isomerization/Intermolecular Alder-Ene Reaction toward Oxazole α-Hydroxy Amide Derivatives[J]. Chinese Journal of Organic Chemistry, ;2020, 40(3): 704-713. doi: 10.6023/cjoc201909002 shu

Zn/Y Bimetallic Relay Catalysis: One Pot Intramolecular Cyclo-isomerization/Intermolecular Alder-Ene Reaction toward Oxazole α-Hydroxy Amide Derivatives

Zhang Shuo ^a ,
Lou Jianfang ^b,, ,
Wang Jiarui ^c ,
Song Zihe ^b ,
Peng Dan ^a ,
Wang Feng ^a ,
Yan Zhiwang ^b ,
Cui Shiqi ^b ,
Liu Yifan ^b ,
Mu Qiuhong ^a ,
Li Jinhui ^a

a.
Shandong Provincial Key Laboratory for Special Silicone-Containing Materials, Advanced Materials Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014
b.
School of Chemistry and Pharmaceutical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353
c.
College of Food Science and Engineering, Shandong Agricultural University, Taian 271018

Corresponding author: Lou Jianfang, wangma@cau.edu.cn
Received Date: 2 September 2019
Revised Date: 23 October 2019
Available Online: 7 November 2019
Fund Project: the National Natural Science Foundation of China 51503118the Youth Science Funds of Shandong Academy of Sciences 2018QN0030the Shandong Provincial Natural Science Foundation ZR2017BB033Project supported by the Shandong Provincial Natural Science Foundation (No. ZR2017BB033), the Youth Science Funds of Shandong Academy of Sciences (No. 2018QN0030) and the National Natural Science Foundation of China (No. 51503118)

Figures(1)

A novel tandem metal relay catalytic system of Zn/Y has been successfully developed. By using this unprecedented Zn(OTf)₂/Y(OTf)₃ bimetallic relay catalytic system, a variety of oxazole α-hydroxy amides derivatives were obtained from easily available N-(propargyl)-arylamides and various 1-benzylindoline-2, 3-dione derivatives through intramolecular cycloisomerization/intermolecular Alder-ene reaction under mild conditions. The first step of the one-pot procedure is that Zn(OTf)₂ acts as a π acid to activate the triple bond of N-(propargyl)-arylamides, and a subsequent intramolecular 5-exo-dig cyclization forms the oxazoline intermediate. Separately, Y(OTf)₃ acts as Lewis acid, then oxazoline intermediate and 1-benzylindoline-2, 3-dione derivatives are transformed to the oxazole α-hydroxy amide derivatives in good to excellent yields in an intermolecular Alder-ene reaction. Control experiments in the optimization section disclose the fact that Zn(OTf)₂ and Y(OTf)₃ are both indispensable for this intramolecular cycloisomerization/intermolecular Alder-ene reaction. Generally, the synthetic reactions run under air atmosphere by heating all the substrates and reagents in one-pot at 100℃. The present method benefits from the distinctive features of simple reaction conditions, high atom economy and broad substrate tolerance. It is of great significance for the synthesis of oxazole derivatives.
- relay catalysis,
- cycloisomerization,
- Alder-Ene reaction,
- oxazole derivatives
1. [1]
  (a) Wipf, P.; Venkatraman, S. J. Org. Chem. 1996, 61, 6517.
  (b) David, N.; Pasceri, R.; Kitson, R. R. A.; Pradal, A.; Moody, C. Chem.-Eur. J. 2016, 22, 10867.
  (c) Turchi, I. J.; Dewar, M. J. S. Chem. Rev. 1975, 75, 389.
  (d) Meyers, A. I.; Mihelich, E. D. Angew. Chem., Int. Ed. 1976, 15, 270.
  (e) Desimoni, G.; Quadrelli, G. F. P. Chem. Rev. 2003, 103, 3119.
  (f) Onishi, H. R.; Pelak, B. A.; Gerckens, L. S.; Silver, L. L.; Kahan, F. M.; Chen, M.-H.; Patchett, A. A.; Galloway, S. M.; Hyland, S. A.; Anderson, M. S.; Raetz, C. R. H. Science 1996, 274, 980.
  (g) Bergeron, R. J.; Xin, M. G.; Weimar, W. R.; Smith, R. E.; Wiegand, J. J. Med. Chem. 2001, 44, 2469.
  (h) Genet, J. P.; Thorimbert, S.; Touzin, A. M. Tetrahedron Lett. 1993, 34, 1159.
  (Ⅰ) Zhou, Q.; Zheng, D. D.; Shi, Y. J.; Yao, W.; Qian, H. W.; Ding, Y.; Wei, Z. H.; Shen, A. B.; Feng, X.; Shi, J.; Dai, H. Chin. J. Org. Chem. 2018, 38, 3318(in Chinese).
  (周钱, 郑丹丹, 石玉军, 姚炜, 钱宏炜, 丁颖, 魏中昊, 沈爱宝, 冯霞, 石健, 戴红, 有机化学, 2018, 38, 3318.)
  (j) Zhou, J. H.; Dai, H.; Qian, H. W.; Du, X. C.; Mao, X. Y.; Shi, Y. J.; Feng, H.; Shi, J.; Yao, Y. Chin. J. Org. Chem. 2018, 38, 2122(in Chinese).
  (周家华, 戴红, 钱宏炜, 杜显超, 茅心宇, 石玉军, 冯浩, 石健, 姚勇, 有机化学, 2018, 38, 2122.)
  (k) Dai, H.; Ding, Y.; Du, X. C.; Yao, W.; Chen, Q. W.; Wang, X. L.; Zhong, S. L.; Cao, X. F.; Shi, Y. J. Chin. J. Org. Chem. 2018, 38, 1755(in Chinese).
  (戴红, 丁颖, 杜显超, 姚炜, 陈庆文, 王祥龙, 仲苏林, 曹雄飞, 石玉军, 有机化学, 2018, 38, 1755.)
  (l) Shi, Y. J.; Du, X. C.; Wang, X. L.; Chen, Q. W.; Li, L.; Dai, H.; Xu, C. Q.; Zhang, J. Y.; Ling, Y. Chin. J. Org. Chem. 2018, 38, 1772(in Chinese).
  (石玉军, 杜显超, 王祥龙, 陈庆文, 李玲, 戴红, 徐蔡芹, 张敬远, 凌勇, 有机化学, 2018, 38, 1772.)
2. [2]
  (a) Haidukewych, D.; Meyers, A. I. Tetrahedron Lett. 1972, 13, 3031.
  (b) Meyers, A. I.; Temple, D. L. J. Am. Chem. Soc. 1970, 92, 6644.
  (c) Nelson, T. D.; Meyers, A. I. J. Org. Chem. 1994, 59, 2577.
3. [3]
  Lahm, G.; Opatz, T. Org. Lett. 2014, 16, 4201.
  (b) Wang, H. L.; Shang, M.; Sun, S. Z.; Zhou, Z. L.; Laforteza, N.; Dai, H. X.; Yu, J. Q. Org. Lett. 2015, 17, 1228.
  (c) Ling, P. X.; Fang, S. L.; Yin, X. S.; Chen, K.; Sun, B. Z.; Shi, B. F. Chem.-Eur. J. 2015, 21, 17503;
4. [4]
  (a) Desimoni, G.; Faita, G.; Jorgensen, K. A. Chem. Rev. 2006, 106, 3561.
  (b) McManus, H. A.; Guiry, P. J. Chem. Rev. 2004, 104, 4151.
  (c) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109, 2505.
  (d) Gade, L. H.; Bellemin-Laponnaz, S. Coord. Chem. Rev. 2007, 251, 718.
5. [5]
  (a) Peng, H.; Akhmedov, N. G.; Liang, Y. F.; Jiao, N.; Shi, X. J. Am. Chem. Soc. 2015, 137, 8912.
  (b) Hashmi, A. S. K.; Weyrauch, J. P.; Frey, W.; Bats, J. W. Org. Lett. 2004, 6, 4391.
  (c) Doherty, S.; Knight, J. G.; Hashmi, A. S. K.; Smyth, C. H.; Ward, N. A. B.; Robson, K. J.; Tweedley, S.; Harrington R. W.; Clegg, W. Organometallics 2010, 29, 4139.
  (d) Hashmi, A. S. K.; Schuster, A. M.; Rominger, F. J. Org. Chem. 2012, 77, 6394.
  (e) Hashmi, A. S. K.; Schuster, A. M.; Schmuck, M.; Rominger, F. Eur. J. Org. Chem. 2011, 2011, 4595.
6. [6]
  (a) Saito, A.; Iimura, K.; Hanzawa, Y. Tetrahedron Lett. 2010, 51, 1471.
  (b) Beccalli, E. M.; Borsini, E.; Broggini, G.; Palmisano, G.; Sottocornola, S. J. Org. Chem. 2008, 73, 4746.
  (c) Arcadi, A.; Cacchi, S.; Cascia, L.; Fabrizi, G.; Marinelli, F. Org. Lett., 2001, 3, 2501
7. [7]
  (a) Jin, C.; Burgess, J. P.; Kepler, J. A.; Cook, C. E. Org. Lett. 2007, 9, 1887.
  (b) Alhalib, A.; Moran, W. J. Org. Biomol. Chem., 2014, 12, 795.
  (c) Zhang, S.; Chen, Y.; Wang, J.; Pan, Y.; Xu, Z.; Tung, C.-H. Org. Chem. Front. 2015, 2, 578
8. [8]
  (a) Harmata, M.; Huang, C. Synlett 2008, 1399.
  (b) Wong, V. H. L.; White, A. J. P.; Hor, T. S.; Hii, K. K. Adv. Synth. Catal. 2015, 357, 3943.
  (c) Hu, Y.; Yi, R.; Wu, F.; Wan, B. J. Org. Chem. 2013, 78, 7714.
9. [9]
  (a) Gao, X. H.; Qian, P. C.; Zhang, X. G.; Deng, C. L. Synlett, 2016, 27, 1110;
10. [10]
  (a) Wang, B.; Chen, Y.; Zhou, L.; Wang, J.; Tung, C.-H.; Xu, Z. J. Org. Chem. 2015, 80, 12718.
  (b) Wang, B.; Chen, Y.; Zhou, L.; Wang, J.; Xu, Z. Org. Biomol. Chem. 2016, 14, 826.
11. [11]
  (a) Mikami, K.; Shimizu, M. Chem. Rev. 1992, 92, 1021.
  (b) Maruoka, K.; Hoshino, Y.; Shirasaka, T.; Yamamoto, H. Tetrahedron Lett. 1988, 29, 3967.
  (c) Whitesell, J. K.; Bhattacharya, A.; Buchanan, C. M.; Chen, H. H.; Deyo, D.; James, D.; Liu, C. L.; Minto, M. A. Tetrahedron 1986, 42, 2993.
  (d) Okachi, T.; Onaka, M. J. Am. Chem. Soc. 2004, 126, 2306.
  (e) Hutson, G. E.; Dave, A. H.; Rawal, V. H. Org. Lett. 2007, 9, 3869.
12. [12]
  Mikami, K. Pure Appl. Chem. 1996, 68, 639; doi: 10.1351/pac199668030639
13. [13]
  Zheng, K.; Shi, J.; Liu, X.; Feng, X. J. Am. Chem. Soc. 2008, 130, 15770. doi: 10.1021/ja808023y
14. [14]
  Mikami, K.; Terada, M.; Nakai, T. J. Am. Chem. Soc. 1990, 112, 3949. doi: 10.1021/ja00166a035
15. [15]
  Evans, D. A.; Burgey, C. S.; Paras, N. A.; Vojkovsky, T.; Tregay, S. W. J. Am. Chem. Soc. 1998, 120, 5824. doi: 10.1021/ja980549m
16. [16]
  (a) Trost, B. M.; Lee, D. C.; Rise, F. Tetrahedron Lett. 1989, 30, 651.
  (b) Trost, B. M.; Czeskis, B. A. Tetrahedron Lett. 1994, 35, 211.
17. [17]
  (a) Zhang, S.; Wei, F.; Song, C. L.; Jia, J.; Xu, Z. H. Chin. J. Chem. 2014, 32, 937.
  (b) Liang, M.; Zhang, S.; Jia, J.; Tung, C-H.; Wang, J. W.; Xu, Z. H. Org. Lett. 2017, 19, 2526.
  (c) Zhang, S.; Xu, Z. L.; Jia, J.; Tung, C-H.; Xu, Z. H. Chem. Commun. 2014, 50, 12084.
  (d) Wang, X. H.; Dong, S. L.; Yao, Z. L.; Feng, L.; Daka, P.; Wang, H.; Xu, Z. H. Org. Lett. 2014, 16, 22.
  (e) Thirupathi, N.; Wei, F.; Tung, C.-H., Xu, Z. Nat. Commun. 2019, 10, 3158.
  (f) Kong, L.; Thirupathi, N.; Jia, J., Xu, Z. Sci. China Chem. 2019, 62, 80.
  (f) Gupta, G. R.; Shah, J.; Vadagaonkar, K. S.; Lavekar, A. G.; Kapdi, A. R. Org. Biomol. Chem. 2019, 17, 7596.
  (g) Liang, Q. J.; Xu, Y. H.; Loh, T. P. Org. Chem. Front. 2018, 5, 2765.
1. [1]
  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
2. [2]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
3. [3]
  Zhongyan Cao , Shengnan Jin , Yuxia Wang , Yiyi Chen , Xianqiang Kong , Yuanqing Xu . Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186
4. [4]
  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
5. [5]
  Jianfeng Yan , Yating Xiao , Xin Zuo , Caixia Lin , Yaofeng Yuan . Comprehensive Chemistry Experimental Design of Ferrocenylphenyl Derivatives. University Chemistry, 2024, 39(4): 329-337. doi: 10.3866/PKU.DXHX202310005
6. [6]
  Siran Wang , Yinuo Wang , Yilong Zhao , Dazhen Xu . Advances in the Application and Preparation of Rhodanine and Its Derivatives. University Chemistry, 2025, 40(5): 318-327. doi: 10.12461/PKU.DXHX202407033
7. [7]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
8. [8]
  Jia-He Li , Yu-Ze Liu , Jia-Hui Ma , Qing-Xiao Tong , Jian-Ji Zhong , Jing-Xin Jian . 洛芬碱衍生物的合成、化学发光与重金属离子检测. University Chemistry, 2025, 40(6): 230-237. doi: 10.12461/PKU.DXHX202407080
9. [9]
  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
10. [10]
  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
11. [11]
  Xuanzhu Huo , Yixi Liu , Qiyu Wu , Zhiqiang Dong , Chanzi Ruan , Yanping Ren . Integrated Experiment of “Electrolytic Preparation of Cu₂O and Gasometric Determination of Avogadro’s Constant: Implementation, Results, and Discussion: A Micro-Experiment Recommended for Freshmen in Higher Education at Various Levels Across the Nation. University Chemistry, 2024, 39(3): 302-307. doi: 10.3866/PKU.DXHX202308095
12. [12]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
13. [13]
  Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo . 氰基修饰的苝二酰亚胺衍生物作为膜厚不敏感型阴极界面材料用于高效有机太阳能电池. Acta Physico-Chimica Sinica, 2025, 41(3): 2406007-. doi: 10.3866/PKU.WHXB202406007
14. [14]
  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
15. [15]
  Wenjiang LI , Pingli GUAN , Rui YU , Yuansheng CHENG , Xianwen WEI . C₆₀-MoP-C nanoflowers van der Waals heterojunctions and its electrocatalytic hydrogen evolution performance. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 771-781. doi: 10.11862/CJIC.20230289
16. [16]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
17. [17]
  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
18. [18]
  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
19. [19]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
20. [20]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(1197)
HTML views(228)

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