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]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  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
9. [9]
  Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang . Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting. Acta Physico-Chimica Sinica, 2024, 40(12): 2405005-. doi: 10.3866/PKU.WHXB202405005
10. [10]
  Kaihui Huang , Dejun Chen , Xin Zhang , Rongchen Shen , Peng Zhang , Difa Xu , Xin Li . Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu₂O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(12): 2407020-. doi: 10.3866/PKU.WHXB202407020
11. [11]
  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
12. [12]
  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
13. [13]
  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
14. [14]
  Minna Ma , Yujin Ouyang , Yuan Wu , Mingwei Yuan , Lijuan Yang . Green Synthesis of Medical Chemiluminescence Reagents by Photocatalytic Oxidation. University Chemistry, 2024, 39(5): 134-143. doi: 10.3866/PKU.DXHX202310093
15. [15]
  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
16. [16]
  Tao Wen , Tao Zhang , Changguo Sun , Jinyu Liu . Preparation of Dess-Martin Reagent and Its Application in Oxidizing Cyclohexanol. University Chemistry, 2024, 39(5): 20-26. doi: 10.3866/PKU.DXHX202309055
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]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
19. [19]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(1803)
HTML views(788)

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