Citation: Zhang Ronghua, Xu Bing, Zhang Zhanming, Zhang Junliang. Ming-Phos/Copper(I)-Catalyzed Asymmetric[3+2] Cycloaddition of Azomethine Ylides with Nitroalkenes[J]. Acta Chimica Sinica, ;2020, 78(3): 245-249. doi: 10.6023/A20010019 shu

Ming-Phos/Copper(I)-Catalyzed Asymmetric[3+2] Cycloaddition of Azomethine Ylides with Nitroalkenes

a.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062
b.
Department of Chemistry, Fudan University, Shanghai 200438

Corresponding author: Zhang Zhanming, zhangzhanming12@163.com Zhang Junliang, jlzhang@chem.ecnu.edu.cn; junliangzhang@fudan.edu.cn
Received Date: 21 January 2020
Available Online: 9 March 2020
Fund Project: the Program of Eastern Scholar at Shanghai Institutions of Higher Learning and the China Postdoctoral Science Foundation 2019M650071the National Natural Science Foundation of China 21801078the Program of Eastern Scholar at Shanghai Institutions of Higher Learning and the China Postdoctoral Science Foundation 2019M661418the National Natural Science Foundation of China 21425205973 Program 2015CB856600Project supported by the National Natural Science Foundation of China (Nos. 21425205, 21672067, 21801078), 973 Program (No. 2015CB856600), and the Program of Eastern Scholar at Shanghai Institutions of Higher Learning and the China Postdoctoral Science Foundation (Nos. 2019M650071, 2019M661418)the National Natural Science Foundation of China 21672067

Figures(1)

Optically pure pyrrolidine ring systems are core structural motifs found in a range of bioactive compounds, natural products, pharmaceuticals and catalysts. The synthesis of optically pure pyrrolidine ring systems is no longer mysterious as a great number of studies concerning the catalytic asymmetric 1, 3-dipolar cycloaddition of iminoesters have been reported. Overall, the transition-metal-catalyzed asymmetric 1, 3-dipolar cycloaddition of iminoesters with electron-deficient alkenes is one of the most powerful and straightforward synthetic tools for the optically pure pyrrolidines. However, high diastereo-and enantioselectivities are requested simultaneously during the synthesis of chiral substituted pyrrolidine and it still remains a big challenge to develop an efficient way to achieve both of them. Recently, we developed a novel chiral sulfinamide mono-phosphine (Ming-Phos) which performed well in copper-catalyzed intermolecular cycloaddition of iminoesters with β-trifluoromethyl β, β-disubstituted enones or α-trifluoromethyl α, β-unsaturated esters. Encouraged by the satisfying results, herein we report the Ming-Phos/Cu-catalyzed asymmetric intermolecular[3+2] cycloaddition of azomethine ylides with nitroalkenes. To our delight, a new Ming-Phos M3 bearing a trifluoromethyl showed good performance in this type of inter-molecular cycloaddition with high diastereo-and enantioselectivities (up to 13:1 dr, 98% ee and 95% yield). High efficiency, high diastereo-and enantioselectivity, a novel ligand, an inexpensive copper catalyst, and good functional group tolerance make it worth to be considered as an efficient, reliable and atom-economic strategy for the synthesis of optically pyrrolidines. The general procedure is as following:the solution of M3 (5.5 mol%) and Cu(CH₃CN)₄BF₄ (5 mol%) in methyl tert-butyl ether (MTBE, 6 mL) was stirred at room temperature for 2 h. After the reaction temperature was dropped to -30℃, azomethine ylides 2 (0.6 mmol), Cs₂CO₃ (0.15 mmol) and nitroalkene 1 (0.3 mmol) were added sequentially. After the nitroalkene 1 was consumed completely, the solvent was removed under reduced pressure. The crude product was analyzed with ¹H NMR to determine the diastereomeric ratio. Then the crude product was then purified by flash column chromatography on silica gel to afford the desired product.
- copper catalysis,
- phosphine ligand,
- cycloaddition,
- enantioselectivity,
- ylides
1. [1]
  For recent reviews and selected examples on the application of pyrrolidines in the natural products and biologically molecules, see: (a) Pyne, S. G.; Davis, A. S.; Gates, N. J.; Hartley, J. P.; Lindsay, K. B.; Machan, T.; Tang, M. Synlett 2004, 2670. (b) Michael, J. P. Nat. Prod. Rep. 2008, 25, 139. (c) Enders, D.; Thiebes, C. Pure Appl. Chem. 2001, 73, 573. (d) Narayan, R.; Potowski, M.; Jia, Z. J.; Antonchick, A. P.; Waldmann, H. Acc. Chem. Res. 2014, 47, 1296. (e) Kumar, I. RSC Adv. 2014, 4, 16397. (f) Randjelovic, J.; Simic, M.; Tasic, G.; Husinec, S.; Savic, V. Curr. Org. Chem. 2014, 18, 1073. (g) Álvarez-Corral, M.; Muñoz-Dorado, M.; Rodriguez-Garcı́a, I. Chem. Rev. 2008, 108, 3174, and references therein.
2. [2]
3. [3]
  For recent reviews about 1, 3-dipolar cycloadditions of iminoesters, see: (a) Nair, V.; Suja, T. D. Tetrahedron 2007, 63, 12247. (b) Stanley, L. M.; Sibi, M. P. Chem. Rev. 2008, 108, 2887. (c) Álvarez-Corral, M.; Muñoz-Dorado, M.; Rodríguez-García, I. Chem. Rev. 2008, 108, 3174. (d) Naodovic, M.; Yamamoto, H. Chem. Rev. 2008, 108, 3132. (e) Engels, B.; Christl, M. Angew. Chem., Int. Ed. 2009, 48, 7968. (f) Adrio, J.; Carretero, J. C. Chem. Commun. 2011, 47, 6784. (g) Moyano, A.; Rios, R. Chem. Rev. 2011, 111, 4703. (h) Albrecht, Ł.; Jiang, H.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2011, 50, 8492. (i) Maroto, E. E.; Izquierdo, M.; Reboredo, S.; Marco-Martínez, J.; Filippone, S.; Martín, N. Acc. Chem. Res. 2014, 47, 2660. (j) Hashimoto, T.; Maruoka, K. Chem. Rev. 2015, 115, 5366. (k) Taggi, A. E.; Hafez, A. M.; Lectka, T. Acc. Chem. Res. 2003, 36, 10. (l) Dickstein, J. S.; Kozlowski, M. C. Chem. Soc. Rev. 2008, 37, 1166. (m) Kobayashi, S.; Mori, Y.; Fossey, J. S.; Salter, M. M. Chem. Rev. 2011, 111, 2626. (n) Fang, X.; Wang, C.-J. Org. Biomol. Chem. 2018, 16, 2591.
4. [4]
5. [5]
  Allway, P.; Grigg, R. Tetrahedron Lett. 1991, 32, 5817. doi: 10.1016/S0040-4039(00)93563-9
6. [6]
  Longmire, J. M.; Wang, B.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 13400. doi: 10.1021/ja025969x
7. [7]
  (a) Yan, X.-X.; Peng, Q.; Zhang, Y.; Zhang, K.; Hong, W.; Hou, X.-L.; Wu, Y.-D. Angew. Chem., Int. Ed. 2006, 45, 1979. (b) Arai, T.; Yokoyama, N.; Mishiro, A.; Sato, H. Angew. Chem., Int. Ed. 2010, 49, 7895. (c) Bai, X.-F.; Song, T.; Xu, Z.; Xia, C.-G.; Huang, W.-S.; Xu, L.-W. Angew. Chem., Int. Ed. 2015, 54, 5255. (d) Feng, B.; Chen, J.-R.; Yang, Y.-F.; Lu, B.; Xiao, W. J. Chem. Eur. J. 2018, 24, 1714.
8. [8]
  For applications of Ming-Phos in asymmetric catalysis, see: (a) Zhang, Z.-M.; Chen, P.; Li, W.; Niu, Y.; Zhao, X. L.; Zhang, J. Angew. Chem., Int. Ed. 2014, 53, 4350. (b) Chen, M.; Zhang, Z.-M.; Yu, Z.; Qiu, H.; Ma, B.; Wu, H.-H.; Zhang, J. ACS Catal. 2015, 5, 7488. (c) Zhang, Z.-M.; Xu, B.; Xu, S.; Wu, H.-H.; Zhang, J. Angew. Chem., Int. Ed. 2016, 55, 6324. (d) Xu, B.; Zhang, Z.-M.; Xu, S.; Liu, B.; Xiao, Y.; Zhang, J. ACS Catal. 2017, 7, 210. (e) Wang, Y.; Zhang, Z.-M.; Liu, F.; He, Y.; Zhang, J. Org. Lett. 2018, 20, 6403. (f) Di, X.; Wang, Y.; Wu, L.; Zhang, Z.-M.; Dai, Q.; Li, W.; Zhang, J. Org. Lett. 2019, 21, 3018. (g) Wu, Y.; Xu, B.; Liu, B.; Zhang, Z. M.; Liu, Y. Org. Biomol. Chem. 2019, 17, 1395. (h) Zhou, L.; Li, S.; Xu, B.; Ji, D.; Wu, L.; Liu, Y.; Zhang Z.-M.; Zhang, J. Angew. Chem., Int. Ed. 2020, 59, 2769. (i) Zhou, L.; Xu, B.; Ji, D.; Zhang, Z.-M.; Zhang, J. Chin. J. Chem. DOI: 10.1002/cjoc.202000034.
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
6. [6]
  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
7. [7]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
8. [8]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
9. [9]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
10. [10]
  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
11. [11]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
12. [12]
  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
13. [13]
  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
14. [14]
  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
15. [15]
  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
16. [16]
  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
17. [17]
  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
18. [18]
  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
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(21)
Abstract views(2385)
HTML views(376)

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