Citation: Zhang Luwen, Wen Zhiguo, Borzov Maxim, Nie Wanli. Research of B(C₆F₅)₃/Aromatic Ammonium Chloride Systems Catalyzed Hydroamination/Reduction Reaction[J]. Acta Chimica Sinica, ;2017, 75(8): 819-823. doi: 10.6023/A17040142 shu

Research of B(C₆F₅)₃/Aromatic Ammonium Chloride Systems Catalyzed Hydroamination/Reduction Reaction

Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department of Leshan Normal University, Leshan 614000

Corresponding author: Nie Wanli, niewl126@126.com
Received Date: 6 April 2017
Available Online: 23 August 2017
Fund Project: Project supported by the National Natural Science Foundation of China (No.21542011) and Scientific Research Fund of Leshan Normal University (Nos.Z1414, Z1308)the National Natural Science Foundation of China 21542011Scientific Research Fund of Leshan Normal University Z1308Scientific Research Fund of Leshan Normal University Z1414

Figures(4)

Although in recent years the frustrated Lewis pairs (FLPs) reactivity towards small molecule activation has been widely concerned, the reports on the FLPs derived from aromatic amines are few. This paper describes a new method of an one-pot hydroamination/reduction reaction of terminal alkynes with aromatic amines catalyzed by the B(C₆F₅)₃/aromatic ammonium chloride systems with a hydridosilane as a source of the hydride. We consider that the active intermediate[Ar₂NH₂]⁺[H-B(C₆F₅)₃]^-which formed by the aromatic ammonium chloride/B(C₆F₅)₃ reaction with silanes plays a very important role on the formation and reduction of the mediate product imines. The hydroamination reaction is firstly induced by the trace amount amines produced by the dissociation of the borohydride aromatic amine salt, which then reacts with the alkynes and forms the imines. Then the borohydride intermediate[Ar₂NH₂]⁺[H-B(C₆F₅)₃]^- reduces the imines to amines. It has been proved that the borohydride intermediate[Ar₂NH₂]⁺[H-B(C₆F₅)₃]^-could successfully reduce the corresponding imines to amines in an in-situ reaction condition. However it has been found that the usually most active mono-substituted hydridosilane, such as PhSiH₃ shows the poorest reactivity in this case. And the less active trisubstituted silanes such as Et₃SiH or Ph₃SiH exhibit the highest reactivity. To explain this abnormal phenomenon the different reaction speeds of the cascade hydroamination/reduction reaction and the dissociation of the borohydride aromatic amine salt should be concerned. Since the dissociation of[Ar₂NH₂]⁺[H-B(C₆F₅)₃]^-to H₂ is comparably quicker than the hydroamination reaction. By reacting with the less active trisubstituted silanes could not only slow down the formation and dissociation of[Ar₂NH₂]⁺[H-B(C₆F₅)₃]^-, but could also let the hydroamination and reduction steps proceeded completely. Moreover by slowly adding the diluted hydrosilanes to the reaction systems could also improve the reaction. The reaction yield is affected by the substituent on the terminal alkynes, too. The alkynes with the electron withdrawn group show comparably higher reactivity than with the electron donating ones.
- frustrated Lewis pairs,
- aromatic ammonium chloride,
- B(C₆F₅)₃,
- silanes,
- hydroamination/reduction reaction
1. [1]
  Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795. doi: 10.1021/cr0306788
2. [2]
  Severin, R.; Doye, S. Chem. Soc. Rev. 2007, 36, 1407. doi: 10.1039/b600981f
3. [3]
  Nishina, N.; Yamamoto, Y. Top. Organomet. Chem. 2013, 43, 115.
4. [4]
  (a) Sun, Q.; Wang, Y.-R.; Yuan, D.; Yao, Y.-M.; Shen, Q. Organometallics 2014, 33, 994. (b) Liang, S.-Z.; Hammond, L.; Xu, B.; Hammond, G. B. Adv. Synth. Catal. 2016, 358(20), 3313. (c) Sakai, N.; Takahashi, N.; Ogiwara, Y. Eur. J. Org. Chem. 2014, 5078.
5. [5]
  Wang, J.; Cui, D.-M. Chin. J. Org. Chem. 2016, 36(6), 1163
6. [6]
  Bian, R.-J.; Bao, X.-G. Chin. J. Org. Chem. 2017, 37(1), 190
7. [7]
  McCahill, J. S. J.; Welch, G. C.; Stephan, D. W. Angew. Chem., Int. Ed. 2007, 46, 4968. doi: 10.1002/(ISSN)1521-3773
8. [8]
  Dureen, M. A.; Brown, C. C.; Stephan, D. W. Organometallics 2010, 29, 6594. doi: 10.1021/om1009044
9. [9]
  Sajid, M.; Elmer, L.-M.; Rosorius, C.; Daniliuc, C. G.; Grimme, S.; Kehr, G.; Erker, G. Angew. Chem., Int. Ed. 2013, 52, 2243. doi: 10.1002/anie.201208750
10. [10]
  Mçmming, C. M.; Otten, E.; Kehr, G.; Frçhlich, R.; Grimme, S.; Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2009, 48, 6643. doi: 10.1002/anie.v48:36
11. [11]
  Cardenas, A. J. P.; Culotta, B. J.; Warren, T. H.; Grimme, S.; Stute, A.; Froehlich, R.; Kehr, G.; Erker, G. Angew. Chem., Int. Ed. 2011, 50, 7567. doi: 10.1002/anie.201101622
12. [12]
  Otten, E.; Neu, R. C.; Stephan, D. W. J. Am. Chem. Soc. 2009, 131, 9918. doi: 10.1021/ja904377v
13. [13]
  Sajid, M.; Klose, A.; Birkmann, B.; Liang, L.; Schirmer, B.; Wiegand, T.; Eckert, H.; Lough, A. J.; Froehlich, R.; Daniliuc, C. G.; Grimme, S.; Stephan, D. W.; Kehr, G.; Erker, G. Chem. Sci. 2013, 4, 213. doi: 10.1039/C2SC21161K
14. [14]
  Mahdi, T.; Stephan, D. W. Angew. Chem., Int. Ed. 2013, 52, 12418. doi: 10.1002/anie.201307254
15. [15]
  Mahdi, T.; Stephan, D. W. Chem. Eur. J. 2015, 21, 11134. doi: 10.1002/chem.v21.31
16. [16]
  Wen, Z.-G.; Tian, C.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2016, 74, 498.
17. [17]
  Hu, X.; Tian, C.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2015, 73, 1025. doi: 10.3866/PKU.WHXB201504141
18. [18]
  Nie, W.-L.; Sun, G.-F.; Tian, C.; Borzov, M. V. Z. Naturforsch. 2016, 71(10) b, 1029.
19. [19]
  Tian, C.; Jiang, Y.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2015, 73, 1203.
20. [20]
  Li, L.; Huang, G.; Chen, Z.; Liu, W.; Wang, X.; Chen, Y.; Yang, L.; Li, W.; Li, Y. Eur. J. Org. Chem. 2012, 28, 5564.
1. [1]
  Mengxiu Li , Jiahui Mao , Jiangfeng Ni , Liang Li . Three birds with one stone: modification of Li₅FeO₄ with thermal induction of Lewis acid. Acta Physico-Chimica Sinica, 2026, 42(4): 100189-0. doi: 10.1016/j.actphy.2025.100189
2. [2]
  Baitong Wei , Rongxiu Zhu , Zhenghu Xu . Thalidomide: Defeating the Three Evils. University Chemistry, 2026, 41(2): 273-278. doi: 10.12461/PKU.DXHX202502020
3. [3]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
4. [4]
  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
5. [5]
  Haiping Wang . A Streamlined Method for Drawing Lewis Structures Using the Valence State of Outer Atoms. University Chemistry, 2024, 39(8): 383-388. doi: 10.12461/PKU.DXHX202401073
6. [6]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017
7. [7]
  Chengxiao Zhao , Zhaolin Li , Dongfang Wu , Xiaofei Yang . SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production. Acta Physico-Chimica Sinica, 2026, 42(1): 100149-0. doi: 10.1016/j.actphy.2025.100149
8. [8]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
9. [9]
  Weikang Wang , Yadong Wu , Jianjun Zhang , Kai Meng , Jinhe Li , Lele Wang , Qinqin Liu . Green H₂O₂ synthesis via melamine-foam supported S-scheme Cd_0.5Zn_0.5In₂S₄/S-doped carbon nitride heterojunction: synergistic interfacial charge transfer and local photothermal effect. Acta Physico-Chimica Sinica, 2025, 41(8): 100093-0. doi: 10.1016/j.actphy.2025.100093
10. [10]
  Xin Feng , Kexin Guo , Chunguang Jia , Bowen Liu , Suqin Ci , Junxiang Chen , Zhenhai Wen . Hydrogen Generation Coupling with High-Selectivity Electrocatalytic Glycerol Valorization into Formate in an Acid-Alkali Dual-Electrolyte Flow Electrolyzer. Acta Physico-Chimica Sinica, 2024, 40(5): 2303050-0. doi: 10.3866/PKU.WHXB202303050
11. [11]
  Dawei Zhang , Lei Zhang , Yibo Zhou , Yajie Li , YuPeng Guo . Developing a “One Core, Three Dimensions, Five Integrations” Chemistry Curriculum System for Non-Chemistry Majors at Jilin University. University Chemistry, 2025, 40(12): 147-156. doi: 10.12461/PKU.DXHX202510089
12. [12]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
13. [13]
  Xiuyun Wang , Jiashuo Cheng , Yiming Wang , Haoyu Wu , Yan Su , Yuzhuo Gao , Xiaoyu Liu , Mingyu Zhao , Chunyan Wang , Miao Cui , Wenfeng Jiang . Improvement of Sodium Ferric Ethylenediaminetetraacetate (NaFeEDTA) Iron Supplement Preparation Experiment. University Chemistry, 2024, 39(2): 340-346. doi: 10.3866/PKU.DXHX202308067
14. [14]
  Xiaofei Zhang , Shanhao Xu , Zhiyuan Wang , Long He , Tiangcheng Huang , Yongming Xu , Yucui Bian , Yike Li , Haijun Chen , Zhongjun Li . Surface doping of graphene into BiOCl for efficient photocatalytic amine coupling under visible light. Acta Physico-Chimica Sinica, 2026, 42(5): 100202-0. doi: 10.1016/j.actphy.2025.100202
15. [15]
  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
16. [16]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
17. [17]
  Zongsheng LI , Yichao WANG , Yujie WANG , Wenhao ZHU , Xiaoyao YIN , Wudan YANG , Songzhi ZHENG , Weihai SUN . Preparation of CsPbBr₃ perovskite solar cells via bottom interface modification with methylammonium chloride. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1805-1816. doi: 10.11862/CJIC.20250066
18. [18]
  Chenyang WANG , Yiyan BAI , Wei ZHANG , Zhaorong LIU , Yuchun WANG . Performance of photo-assisted copper oxide catalyzed hydrolysis of ammonia borane to produce hydrogen. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 97-110. doi: 10.11862/CJIC.20250116
19. [19]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
20. [20]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(2283)
HTML views(625)

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

Research of B(C6F5)3/Aromatic Ammonium Chloride Systems Catalyzed Hydroamination/Reduction Reaction

Metrics

通讯作者: 陈斌, bchen63@163.com

Research of B(C₆F₅)₃/Aromatic Ammonium Chloride Systems Catalyzed Hydroamination/Reduction Reaction