Citation: Zhao Yong, Li Shihong, Zhang Miaomiao, Liu Feng. ynthesis of β, γ-Unsaturated Esters and γ-Ketone Esters with Amino Acid Ester-Derived Katritzky Salts[J]. Acta Chimica Sinica, ;2019, 77(9): 916-921. doi: 10.6023/A19040121 shu

ynthesis of β, γ-Unsaturated Esters and γ-Ketone Esters with Amino Acid Ester-Derived Katritzky Salts

Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, Suzhou 215123

Corresponding author: Liu Feng, fliu2@suda.edu.cn
Received Date: 8 April 2019
Available Online: 22 September 2019
Fund Project: Project supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No. 18KJA350001)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China 18KJA350001

Figures(3)

β, γ-Unsaturated ester and γ-ketone ester are important synthons, which can be used to convert into various heterocyclic compounds, natural products and pharmaceuticals. The development of efficient methods for the synthesis of β, γ-unsaturated ester and γ-ketone ester compounds has attracted much attention from synthetic chemists. By using Katritzky pyridinium salts as radical precursors, commercially available Ru(bpy)₃Cl₂•6H₂O as photocatalyst, K₂CO₃ as base, and dichloromethane (DCM) as solvent, we developed a simple and efficient method for the synthesis of a series of β, γ-unsaturated esters and γ-ketone esters by C-N bond activation. Bench-stable and easily handled redox-active Katritzky pyridinium salts derived from abundant amino acids were used as radical precursors for the alkylation of 1, 1-diarylethylene and aryl enol silyl ether species upon irradiation with household blue LEDs. The reaction displays an excellent functional group tolerance and a potential utility for amino acids functionalization, allowing to access desired products in moderate to good yields. Moreover, under air conditions, the reaction has moderate compatibility. Scaling up the reaction in grams, the yield was higher and the target product was obtained with 91% yield. Control experiments demonstrated that the photocatalyst and visible light were both essential for the success of the reaction. Performing the reaction in the presence of radical scavenger TEMPO, did lead to no desired product 3a formation. Moreover, a TEMPO-trapped product was determined by MS analysis and NMR, indicating a radical-type mechanism of this reaction. It is of note that this protocol could offer a powerful complementary strategy for the use of amino acids that were also employed in photoredox-catalyzed decarboxylative reactions. A representative procedure for this reaction is as following:A 10 mL oven-dried Schlenk-tube was charged with 1a (111.5 mg, 0.20 mmol), Ru(bpy)₃Cl₂•6H₂O (3.0 mg, 2 mol%), K₂CO₃ (55.2 mg, 0.40 mmol) and a magnetic stirring bar. The tube was evacuated and back-filled three times with argon. A solution of 2a (53 μL, 0.30 mmol) in DCM (2 mL) was injected into the tube by syringe. The resulting mixture was stirred at room temperature upon irradiation with blue LEDs (22 W) and monitored by thin-layer chromatography (TLC). After completion, the solvent was then removed under reduced pressure and the residue was purified by flash column chromatography on silica gel to give 3a as an off-white solid (42.7 mg, 65% yield).
- Katritzky salt,
- β, γ-unsaturated ester,
- γ-ketone ester,
- free radical reaction,
- photocatalysis,
- C-N bond activation
1. [1]
2. [2]
3. [3]
  For selected recent examples, see: (a) Kautzky, J. A.; Wang, T.; Evans, R. W.; MacMillan, D. W. C. J. Am. Chem. Soc. 2018, 140, 6522; (b) Bloom, S.; Liu, C.; K lmel, D. K.; Qiao, J.-X.; Zhang, Y.; Poss, M. A.; Ewing, W. R.; MacMillan, D. W. C. Nature Chem. 2018, 10, 205; (c) Zhao, Y.; Chen, J.-R.; Xiao, W.-J. Org. Lett. 2018, 20, 224; (d) Cheng, W.-M.; Shang, R.; Fu, M.-C.; Fu, Y. Chem. Eur. J. 2017, 23, 2537; (e) Wang, D.; Zhu, N.; Chen, P.; Lin, Z.; Liu, G. J. Am. Chem. Soc. 2017, 139, 15632; (f) Fawcett, A.; Pradeilles, J.; Wang, Y.; Mutsuga, T.; Myers, E. L.; Aggarwal, V. K. Science 2017, 357, 283; (g) Garza-Sanchez, R. A.; Tlahuext-Aca, A.; Tavakoli, G.; Glorius, F. ACS Catal. 2017, 7, 4057; (h) Cheng, W.-M.; Shang, R.; Fu, Y. ACS Catal. 2017, 7, 907; (i) McCarver, S. J.; Qiao, J.-X.; Carpenter, J.; Borzilleri, R. M.; Poss, M. A.; Eastgate, M. D.; Miller, M.; MacMillan, D. W. C. Angew. Chem., Int. Ed. 2017, 56, 728; (j) Johnston, C. P.; Smith, R.; Allmendinger, T. S.; MacMillan, D. W. C. Nature 2016, 536, 322; (k) Müller, D. S.; Untiedt, N. L.; Dieskau, A. P.; Lackner, G. L.; Overman, L. E. J. Am. Chem. Soc. 2015, 137, 660.
4. [4]
  For selected recent examples, see: (a) Zhou, W.-J.; Cao, G.-M.; Shen, G.; Zhu, X.-Y.; Gui, Y.-Y.; Ye, J.-H.; Sun, L.; Liao, L.-L.; Li, J.; Yu, D.-G. Angew. Chem., Int. Ed. 2017, 56, 15683; (b) Nuhant, P.; Oderinde, M. S.; Genovino, J.; Juneau, A.; Gagné, Y.; Allais, C.; Chinigo, G. M.; Choi, C.; Sach, N. W.; Bernier, L.; Fobian, Y. M.; Bundesmann, M. W.; Khunte, B.; Frenette, M.; Fadeyi, O. O. Angew. Chem., Int. Ed. 2017, 56, 15309; (c) Zhang, P.; Le, C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2016, 138, 8084; (d) Feng, Z.; Min, Q.-Q.; Zhao, H.-Y.; Gu, J.-W.; Zhang, X. Angew. Chem., Int. Ed. 2015, 54, 1270; (e) Iqbal, N.; Choi, S.; Kim, E.; Cho, E. J. J. Org. Chem. 2012, 77, 11383.
5. [5]
  For selected recent examples, see: (a) Lima, F.; Sharma, U. K.; Grunenberg, L.; Saha, D.; Johannsen, S.; Sedelmeier, J.; Van der Eycken, E. V.; Ley, S. V. Angew. Chem., Int. Ed. 2017, 56, 15136; (b) Matsui, J. K.; Primer, D. N.; Molander, G. A. Chem. Sci. 2017, 8, 3512; (c) Amani, J.; Molander, G. A. Org. Lett. 2017, 19, 3612; (d) Primer, D. N.; Molander, G. A. J. Am. Chem. Soc. 2017, 139, 9847; (e) Lima, F.; Kabeshov, M. A.; Tran, D. N.; Battilocchio, C.; Sedelmeier, J.; Sedelmeier, G.; Schenkel, B.; Ley, S. V. Angew. Chem., Int. Ed. 2016, 55, 14085; (f) Huo, H.; Harms, K.; Meggers, E. J. Am. Chem. Soc. 2016, 138, 6936; (g) El Khatib, M.; Serafim, R. A. M.; Molander, G. A. Angew. Chem., Int. Ed. 2016, 55, 254; (h) Primer, D. N.; Karakaya, I.; Tellis, J. C.; Molander, G. A. J. Am. Chem. Soc. 2015, 137, 2195.
6. [6]
  For selected recent examples, see: (a) Lang, S. B.; Wiles, R. J.; Kelly, C. B.; Molander, G. A. Angew. Chem., Int. Ed. 2017, 56, 15073; (b) Zheng, S.; Primer, D. N.; Molander, G. A. ACS Catal. 2017, 7, 7957; (c) Remeur, C.; Kelly, C. B.; Patel, N. R.; Molander, G. A. ACS Catal. 2017, 7, 6065; (d) Lin, K.; Wiles, R. J.; Kelly, C. B.; Davies, G. H. M.; Molander, G. A. ACS Catal. 2017, 7, 5129; (e) Patel, N. R.; Kelly, C. B.; Siegenfeld, A. P.; Molander, G. A. ACS Catal. 2017, 7, 1766; (f) Deng, Y.; Liu, Q. Smith, A. B. J. Am. Chem. Soc. 2017, 139, 9487; (g) Jouffroy, M.; Primer, D. N.; Molander, G. A. J. Am. Chem. Soc. 2016, 138, 475; (h) Corc, V.; Chamoreau, L.-M.; Derat, E.; Goddard, J.-P.; Ollivier, C.; Fen-sterbank, L. Angew. Chem., Int. Ed. 2015, 54, 11414.
7. [7]
  For selected recent examples, see: (a) Slutskyy, Y.; Jamison, C. R.; Zhao, P.; Lee, J.; Rhee, Y. H.; Overman, L. E. J. Am. Chem. Soc. 2017, 139, 7192; (b) Zhang, X.; MacMillan, D. W. C. J. Am. Chem. Soc. 2016, 138, 13862; (c) Lackner, G. L.; Quasdorf, K. W.; Pratsch, G.; Overman, L. E. J. Org. Chem. 2015, 80, 6012; (d) Nawrat, C. C.; Jamison, C. R.; Slutskyy, Y.; MacMillan, D. W. C.; Overman, L. E. J. Am. Chem. Soc. 2015, 137, 11270.
8. [8]
  The Generation of Aryl Radicals Can be Achieved via the Reductive Cleavage of C(sp²)-N Bonds of the Aryl Diazonium Salts, For a review, see: Ghosh, I.; Marzo, L.; Das, A.; Shaikh, R.; König, B. Acc. Chem. Res. 2016, 49, 1566.
9. [9]
  (a) Eds.: Pollegioni, L.; Servi, S. Nonnatural Amino Acids: Methods and Protocols, Springer, New York, 2012, pp. 1~249; (b) Ager, D. J. Amino Acids, Peptides and Proteins in Organic Chemistry, Ed.: Hughes, A. B., Wiley-VCH, Weinheim, 2009, Vol. 1, pp. 495~526.
10. [10]
  Katritzky, A. R.; Gruntz, U.; Kenny, D. H.; Rezende, M. C.; Sheikh, H. J. Chem. Soc. Perkin Trans. 1 1979, 430.
11. [11]
  Ouyang, K.; Hao, W.; Zhang, W.-X.; Xi, Z. Chem. Rev. 2015, 115, 12045. doi: 10.1021/acs.chemrev.5b00386
12. [12]
  (a) Basch, C. H.; Liao, J.; Xu, J.; Piane, J. J.; Watson, M. P. J. Am. Chem. Soc. 2017, 139, 5313; (b) Liao, J.; Guan, W.; Boscoe, B. P.; Tucker, J. W.; Tomlin, J. W.; Garnsey, M. R.; Watson, M. P. Org. Lett. 2018, 20, 3030; (c) Guan, W.; Liao, J.; Watson, M. P. Synthesis 2018, 50, 3231.
13. [13]
  Grimshaw, J.; Moore, S.; Grimshaw, J. T. Acta Chem. Scand. Ser. B 1983, 37, 485.
14. [14]
  (a) Klauck, F. J. R.; James, M. J.; Glorius, F. Angew. Chem., Int. Ed. 2017, 56, 12336; (b) Klauck, F. J. R.; Yoon, H.; James, M. J.; Lautens, M.; Glorius, F. ACS Catal. 2019, 9, 236; (c) Sandfort, F.; Strieth-Kalthoff, F.; Klauck, F. J. R.; James, M. J.; Glorius, F. Chem. Eur. J. 2018, 24, 17210.
15. [15]
  (a) Wu, J.-J.; He, L.; Noble, A.; Aggarwal, V. K. J. Am. Chem. Soc. 2018, 140, 10700; (b) Wu, J.-J.; Grant, P. S.; Li, X.-B.; Noble, A.; Aggarwal, V. K. Angew. Chem., Int. Ed. 2019, 58, 10.1002/anie.201814452.
16. [16]
  Hu, J.; Wang, G.; Li, S.; Shi, Z. Angew. Chem., Int. Ed. 2018, 57, 15227. doi: 10.1002/anie.201809608
17. [17]
  Ociepa, M.; Turkowska, J.; Gryko, D. ACS Catal. 2018, 8, 11362. doi: 10.1021/acscatal.8b03437
18. [18]
  (a) Zhu, Z.-F.; Zhang, M.-M.; Liu, F. Org. Biomol. Chem. 2019, 17, 1531; (b) Zhang, M.-M.; Liu, F. Org. Chem. Front. 2018, 5, 3443.
19. [19]
  Brase, S.; Waegell, B.; de Meijere, A. Synthesis 1998, 2, 148.
20. [20]
  Ikeda, Y.; Nakamura, T.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2002, 124, 6514. doi: 10.1021/ja026296l
21. [21]
  Tang, S.; Liu, K.; Liu, C.; Lei, A.-W. Chem. Soc. Rev. 2015, 44, 1070. doi: 10.1039/C4CS00347K
22. [22]
  For selected recent examples with aliphatic carboxylic acids, see: (a) Cao, H.; Jiang, H.; Feng, H.; Kwan, J. M. C.; Liu, X.; Wu, J. J. Am. Chem. Soc. 2018, 140, 16360; (b) Zhou, H.; Ge, L.; Song, J.; Jian, W.; Li, Y.; Li, C.; Bao, H. iScience 2018, 3, 255; (c) Wang, G.-Z.; Shang, R.; Fu, Y. Org. Lett. 2018, 20, 888; (d) Koy, M.; Sandfort, F.; Tlahuext-Aca, A.; Quach, L.; Daniliuc, C. G.; Glorius, F. Chem. Eur. J. 2018, 24, 4552; (e) Zhu, N.; Zhao, J.; Bao, H. Chem. Sci. 2017, 8, 2081.
23. [23]
  For selected examples with alkyl halides, see: (a) Xiong, H.; Li, Y.; Qian, B.; Wei, R.; Van der Eycken, E. V.; Bao, H. Org. Lett., 2019, 21, 776; (b) Kurandina, D.; Rivas, M.; Radzhabov, M.; Gevorgyan, V. Org. Lett. 2018, 20, 357; (c) Wang, G.-Z.; Shang, R.; Cheng, W.-M.; Fu, Y. J. Am. Chem. Soc. 2017, 139, 18307; (d) Kurandina, D.; Parasram, M.; Gevorgyan, V. Angew. Chem., Int. Ed. 2017, 56, 14212; (e) Liu, W.; Li, L.; Chen, Z.; Li, C.-J. Org. Biomol. Chem. 2015, 13, 6170; (f) Weiss, M. E.; Kreis, L. M.; Lauber, A.; Carreira, E. M. Angew. Chem., Int. Ed. 2011, 50, 11125; (g) Affo, W. H.; Fujioka, T.; Ikeda, Y.; Nakamura, T.; Yorimitsu, H.; Oshima, K.; Imamura, Y.; Mizuta, T.; Miyoshi, K. J. Am. Chem. Soc. 2006, 128, 8068; (h) Na, Y. G.; Park, S. Y.; Han, S. B.; Han, H.; Ko, S. W.; Chang, S. J. Am. Chem. Soc. 2004, 126, 250.
24. [24]
  (a) Liu, C.; Tang, S.; Liu, D.; Yuan, J.; Zheng, L.; Meng, L.; Lei, A.-W. Angew. Chem., Int. Ed. 2012, 51, 3638; (b) Nishikata, T.; Noda, Y.; Fujimoto, R.; Sakashita, T. J. Am. Chem. Soc. 2013, 135, 16372; (c) Liu, Q.; Yi, H.; Liu, J.; Yang, Y.-H.; Zhang, X.; Zeng, Z.-Q.; Lei, A.-W. Chem. Eur. J. 2013, 19, 5120.
25. [25]
  Jiang, X.; Zhang, M.-M.; Xiong, W.; Lu, L.-Q.; Xiao, W.-J. Angew. Chem., Int. Ed. 2019, 58, 2402. doi: 10.1002/anie.201813689
1. [1]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
2. [2]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
3. [3]
  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
4. [4]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
5. [5]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
6. [6]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
7. [7]
  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
8. [8]
  Xin Zhou , Zhi Zhang , Yun Yang , Shuijin Yang . A Study on the Enhancement of Photocatalytic Performance in C/Bi/Bi₂MoO₆ Composites by Ferroelectric Polarization: A Recommended Comprehensive Chemical Experiment. University Chemistry, 2024, 39(4): 296-304. doi: 10.3866/PKU.DXHX202310008
9. [9]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . 两步焙烧法制备大比表面积和结晶性增强超薄g-C₃N₄纳米片及其高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-. doi: 10.3866/PKU.WHXB202406019
10. [10]
  Changjun You , Chunchun Wang , Mingjie Cai , Yanping Liu , Baikang Zhu , Shijie Li . 引入内建电场强化BiOBr/C₃N₅ S型异质结中光载流子分离以实现高效催化降解微污染物. Acta Physico-Chimica Sinica, 2024, 40(11): 2407014-. doi: 10.3866/PKU.WHXB202407014
11. [11]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
12. [12]
  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
13. [13]
  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
14. [14]
  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
15. [15]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . ZnCoP/CdLa₂S₄肖特基异质结的构建促进光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-. doi: 10.3866/PKU.WHXB202404030
16. [16]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
17. [17]
  Zijian Jiang , Yuang Liu , Yijian Zong , Yong Fan , Wanchun Zhu , Yupeng Guo . Preparation of Nano Zinc Oxide by Microemulsion Method and Study on Its Photocatalytic Activity. University Chemistry, 2024, 39(5): 266-273. doi: 10.3866/PKU.DXHX202311101
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]
  Jingyu Cai , Xiaoyu Miao , Yulai Zhao , Longqiang Xiao . Exploratory Teaching Experiment Design of FeOOH-RGO Aerogel for Photocatalytic Benzene to Phenol. University Chemistry, 2024, 39(4): 169-177. doi: 10.3866/PKU.DXHX202311028
20. [20]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . 钛酸铋/氮化碳无机有机复合S型异质结纯水光催化产过氧化氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-. doi: 10.3866/PKU.WHXB202403009

Get Citation

PDF

XML

Metrics

PDF Downloads(27)
Abstract views(2120)
HTML views(576)

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