Citation: Wang Leming, Wang Qian, Chen Jiean, Huang Yong. Switching Reaction Pathways by Cooperative Catalysis of N-Heterocyclic Carbene and Lewis Acids[J]. Acta Chimica Sinica, ;2018, 76(11): 850-856. doi: 10.6023/A18060244 shu

Switching Reaction Pathways by Cooperative Catalysis of N-Heterocyclic Carbene and Lewis Acids

State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, Peking University, Shenzhen Graduate School, Shenzhen 518055

Corresponding author: Chen Jiean, chenja@pkusz.edu Huang Yong, huangyong@pkusz.edu.cn
Received Date: 23 June 2018
Available Online: 17 November 2018
Fund Project: the National Natural Science Foundation of China 21572004Shenzhen Basic Research Program JCYJ20170818085510474Shenzhen Basic Research Program JCYJ20170818085438996the National Natural Science Foundation of China 21602007Project supported by the National Natural Science Foundation of China (Nos. 21602007, 21572004), Guangdong Science and Technology Program (No. 2013B090500009) and Shenzhen Basic Research Program (Nos. JCYJ20170818085510474, JCYJ20170818085438996)Guangdong Science and Technology Program 2013B090500009

Figures(3)

The combination of N-heterocyclic carbenes (NHCs) and Lewis acids (LA) have been occasionally employed in asymmetric annulation reactions. However, synergistic effect of LA on NHC-mediated reactions remains scarce. Herein, we demonstrate that by switching LA co-catalysts, two distinct active species, homoenolate and acyl azolium, can be accessed from the same set of substrates. NHC-catalyzed enantioselective hydroesterification is one of the most straightforward strategies to prepare β-chiral esters. Despite recent advances for this redox-neutral transformation, obtaining high enantioselectivity and yield remains challenging. We recently reported synergistic catalysis, combining an achiral NHC and a chiral phosphoric acid, enables highly enantioselective hydrothioesterification and hydroesterification of enals. However, both stereoselectivity and yield for hydroesterification are far from ideal. Specifically, sluggish reactions, accompanied with ee's in mid-80% are often obtained. Additionally, competing pathways for E/Z isomerization and oxidative esterification of enal are serious for a number of substrates. In order to address this issue, we propose a new cooperative catalytic system, consisting of a NHC, a LA and a proton-shuttling agent, might accelerate the pivotal asymmetric β-protonation process. We suspect that the choice of LA might provide complementary reaction pathways from the same enal substrates. Starting from β-alkyl cinnamaldehydes, highly enantioselective hydroesterification is accomplished via asymmetric β-protonation enabled by a magnesium co-catalyst. In sharp contrast, the same homoenolate intermediate can undergo aerobic oxidation, via single electron transfer (SET), in the presence of a ruthenium co-catalyst. Control experiments show distinct rate difference between the E-and Z-isomers of enal. Substrates with Z-configuration react significantly slower under the standard reactions. E/Z isomerization is also slow. Photoirradiation was applied to address the challenging issue of isomeric enals and both high yield and ee are obtained using start materials as E/Z mixtures. General procedure for the asymmetric β-protonation is as following:NHC pre-catalyst (0.01 mmol), MgCl₂ (0.01 mmol), DABCO (0.12 mmol), 4 Å MS (100 mg), alcohol (0.6 mmol) and enal substrate (0.1 mmol) were dissolved in toluene (1.0 mL). The resulted mixture was stirred at room temperature under Ar atmosphere for 15 h. Upon complete consumption of the enal, the mixture was concentrated and purified by flash column chromatography. For the aerobic oxidation, the reaction proceeded with RuCl₃ (0.01 mmol) under O₂ atmosphere.
- N-heterocyclic carbenes,
- Lewis acid,
- synergistic catalysis,
- asymmetric protonation,
- aerobic oxidation
1. [1]
  (a) Shao, Z.; Zhang, H. Chem. Soc. Rev. 2009, 38, 2745; (b) Zhong, C.; Shi, X. Eur. J. Org. Chem. 2010, 2999; (c) Allen, A. E.; Macmillan, D. W. Chem. Sci. 2012, 3, 633; (d) Du, Z.; Shao, Z. Chem. Soc. Rev. 2013, 42, 1337.
2. [2]
  (a) Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606; (b) Chiang, P.-C.; Bode, J. W. TCI MAIL 2011, 149, 2; (c) Nair, V.; Menon, R. S.; Biju, A. T.; Sinu, C. R.; Paul, R. R.; Jose, A.; Sreekumar, V. Chem. Soc. Rev. 2011, 40, 5336; (d) Bugaut, X.; Glorius, F. Chem. Soc. Rev. 2012, 41, 3511; (e) Grossmann, A.; Enders, D. Angew. Chem., Int. Ed. 2012, 51, 314; (f) Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. Nature 2014, 510, 485; (g) Mahatthananchai, J.; Bode, J. W. Acc. Chem. Res. 2014, 47, 696; (h) Flanigan, D. M.; Romanov-Michailidis, F.; White, N. A.; Rovis, T. Chem. Rev. 2015, 115, 9307; (i) Zhang, C.; Hooper, J. F.; Lupton, D. W. ACS Catal. 2017, 7, 2583.
3. [3]
4. [4]
  (a) Dugal-Tessier, J.; O'Bryan, E. A.; Schroeder, T. B.; Cohen, D. T.; Scheidt, K. A. Angew. Chem., Int. Ed. 2012, 51, 4963; (b) Raup, D. E.; Cardinal-David, B.; Holte, D.; Scheidt, K. A. Nat. Chem. 2010, 2, 766; (c) Cohen, D. T.; Scheidt, K. A. Chem. Sci. 2012, 3, 53; (d) Mo, J.; Chen, X.; Chi, Y. R. J. Am. Chem. Soc. 2012, 134, 8810; (e) Wang, M.; Rong, Z. Q.; Zhao, Y. Chem. Commun. 2014, 50, 15309; (f) Reddi, Y.; Sunoj, R. B. ACS Catal. 2017, 7, 530.
5. [5]
  Breslow, R. J. Am. Chem. Soc. 1958, 80, 3719. doi: 10.1021/ja01547a064
6. [6]
  (a) Maki, B. E.; Chan, A.; Scheidt, K. A. Synthesis 2008, 1306; (b) Maki, B. E.; Patterson, E. V.; Cramer, C. J.; Scheidt, K. A. Org. Lett. 2009, 11, 3942; (c) Wang, M. H.; Barsoum, D.; Schwamb, C. B.; Cohen, D. T.; Goess, B. C.; Riedrich, M.; Chan, A.; Maki, B. E.; Mishra, R. K.; Scheidt, K. A. J. Org. Chem. 2017, 82, 4689.
7. [7]
  (a) Diez-Gonzalez, S.; Marion, N.; Nolan, S. P. Chem. Rev. 2009, 109, 3612; (b) Fortman, G. C.; Nolan, S. P. Chem. Soc. Rev. 2011, 40, 5151; (c) Janssen-Muller, D.; Schlepphorst, C.; Glorius, F. Chem. Soc. Rev. 2017, 46, 4845.
8. [8]
  Wang, M. H.; Cohen, D. T.; Schwamb, C. B.; Mishra, R. K.; Scheidt, K. A. J. Am. Chem. Soc. 2015, 137, 5891. doi: 10.1021/jacs.5b02887
9. [9]
  (a) Chen, J.; Yuan, P.; Wang, L.; Huang, Y. J. Am. Chem. Soc. 2017, 139, 7045; (b) Zhang, L.; Yuan, P.; Chen, J.; Huang, Y. Chem. Commun. 2018, 54, 1473; (c) Yuan, P.; Chen, J.; Zhao, J.; Huang, Y. Angew. Chem., Int. Ed. 2018. DOI: 10.1002/anie.201803556.
10. [10]
  Zhao, J.; Mück-Lichtenfeld, C.; Studer, A. Adv. Synth. Catal. 2013, 355, 1098. doi: 10.1002/adsc.v355.6
11. [11]
  (a) Murahashi, S.; Komiya, N.; Terai, H.; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312; (b) North, M. Angew. Chem., Int. Ed. 2004, 43, 4126; (c) Murahashi, S.; Komiya, N.; Terai, H. Angew. Chem., Int. Ed. 2005, 44, 6931; (d) Murahashi, S.; Nakae, T.; Terai, H.; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005.
12. [12]
  (a) White, N. A.; Rovis, T. J. Am. Chem. Soc. 2014, 136, 14674; (b) Zhang, Y.; Du, Y.; Huang, Z.; Xu, J.; Wu, X.; Wang, Y.; Wang, M.; Yang, S.; Webster, R. D.; Chi, Y. R. J. Am. Chem. Soc. 2015, 137, 2416; (c) Yang, W.; Hu, W.; Dong, X.; Li, X.; Sun, J. Angew. Chem., Int. Ed. 2016, 55, 15783.
1. [1]
  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
2. [2]
  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
3. [3]
  Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu . Synergistic Effects of Internal Electric and Dipole Fields in SnNb₂O₆/Nitrogen-Enriched C₃N₅ S-Scheme Heterojunction for Boosting Photocatalytic Performance. Acta Physico-Chimica Sinica, 2024, 40(10): 2311016-. doi: 10.3866/PKU.WHXB202311016
4. [4]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
5. [5]
  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
6. [6]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
7. [7]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
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]
  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
10. [10]
  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
11. [11]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
12. [12]
  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
13. [13]
  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
14. [14]
  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
15. [15]
  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
16. [16]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
17. [17]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
18. [18]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(1721)
HTML views(748)

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