Citation:
Sun Guofeng, Su Min, Fang Jie, Borzov Maxim, Nie Wanli. Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C6F5)3/Ammonium Chloride Systems with Terminal Alkyne[J]. Acta Chimica Sinica,
;2017, 75(8): 824-830.
doi:
10.6023/A17040141
-
Stereoselective hydroboration reaction of alkynes has been considered as one of the most important organic reaction. To date a handful of metal-catalyzed systems have been demonstrated to achieve trans-hydroboration of alkynes. This paper describes the first non-metal-catalyzed systems which could stereoselectively hydroborate the terminal alkynes in a trans-configuration. The Lewis acid B(C6F5)3 and ammonium chloride have been used as the reaction substrates, and phenylsilane as the hydride source. The hydroboration reaction could be performed in a one-pot procedure by mixing of B(C6F5)3, ammonium chloride and silane together in an equivalent amount. But this one-pot reaction is not so nice since there is always mixed with the ammonium hydroborate[R2NH2]+[H-B(C6F5)3]- intermediates products. A series of ammonium hydroborates prepared from the corresponding primary, secondary, tertiary and quaternary amine hydrochlorides have been isolated, and used in the directly hydroboration with terminal alkynes. To our surprise the ammonium hydroborate[R2NH2]+[H-B(C6F5)3]- could not react with the alkynes alone. When using[R2NH2]+[H-B(C6F5)3]- to react with alkynes, trace amount of catalytic Lewis acid B(C6F5)3 is necessary to firstly activate the carbon-carbon triple bonds and form the crucial zwitterionic σ-complexes. The mechanism study has shown that different from the typical Lewis acid/Lewis base FLPs system reacted with alkynes, in this B(C6F5)3/ammonium chloride system the ammonium chloride plays an important role on the stereoselective control of the reaction. The week interaction between the Cl ion and B(C6F5)3 in the σ-complexes has not only slowed down the unfavorite 1, 1-carboboration reaction, but also stabilized the σ-complexes which has offer the chance for the nucleophilic reagent to attack the reaction center in a cis-or trans-mode. In our experiment the bulky ion[H-B(C6F5)3]-could only attach the active alkynes from the trans-side and form the Z-hydroboration product. This work demonstrates that the combination of the ammonium halides with the Lewis acid B(C6F5)3 could act as a novel "frustrated Lewis pair" to activate alkynes, and will enable the development of even more sophisticated FLP and related catalyzed reactions.
-
Keywords:
- ammonium chloride,
- B(C6F5)3,
- silane,
- alkyne,
- hydroboration
-
-
-
[1]
Kropp, M. A.; Baillargeon, M.; Park, K. M.; Ahamidapaty, K.; Schuster, G. B. J. Am. Chem. Soc. 1991, 113, 2155. doi: 10.1021/ja00006a038
-
[2]
Ohmura, T.; Yamamoto, Y.; Miyaura, N. J. Am. Chem. Soc. 2000, 122, 4990. doi: 10.1021/ja0002823
-
[3]
Gunanathan, C.; Hoelscher, M.; Pan, F.; Leitner, W. J. Am. Chem. Soc. 2012, 134, 14349. doi: 10.1021/ja307233p
-
[4]
Obligacion, J. V.; Neely, J. M.; Yazdani, A. N.; Pappas, I.; Chirik, P. J. J. Am. Chem. Soc. 2015, 137, 5855. doi: 10.1021/jacs.5b00936
-
[5]
-
[6]
Xu, S.-M.; Zhang, Y.-Z.; Li, B.; Liu, S. H.-Y. J. Am. Chem. Soc. 2016, 138(44), 14566. doi: 10.1021/jacs.6b09759
-
[7]
-
[8]
Bismuto, A.; Thomas, S. P.; Cowley, M. J. Angew. Chem., Int. Ed. 2016, 55, 15356. doi: 10.1002/anie.v55.49
-
[9]
Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science 2006, 314, 1124. doi: 10.1126/science.1134230
-
[10]
Welch, G. C.; Stephan, D. W. J. Am. Chem. Soc. 2007, 129, 1880. doi: 10.1021/ja067961j
-
[11]
Chen, D.-J.; Wang, Y.; Klankermayer, J. Angew. Chem., Int. Ed. 2010, 49, 9475. doi: 10.1002/anie.201004525
-
[12]
Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2010, 49, 46. doi: 10.1002/anie.200903708
-
[13]
Stephan, D. W. Acc. Chem. Res. 2015, 48, 306. doi: 10.1021/ar500375j
-
[14]
Chen, C.; Kehr, G..; Fröhlich, R.; Erker, G. J. Am. Chem. Soc. 2010, 132, 13594. doi: 10.1021/ja106365j
-
[15]
Chen, C.; Voss, T.; Fröhlich, R.; Kehr, G.; Erker, G. Org. Lett. 2011, 13, 62. doi: 10.1021/ol102544x
-
[16]
Jiang, C.; Blacque, O.; Berke, H. Organometallics 2010, 29, 125. doi: 10.1021/om9008636
-
[17]
Reddy, J. S.; Xu, B.-H.; Mahdi, T.; Fröhlich, R.; Kehr, G.; Stephan, D. W.; Erker, G. Organometallics 2012, 31, 5638. doi: 10.1021/om3006068
-
[18]
Nie, W.-L.; Klare, H. F. T.; Oestreich, M.; FrÖhlich, R.; Kehr, G.; Erker, G. Z. Naturforsch. 2012, 67b, 987.
-
[19]
Xu, Y.-Y.; Li, Z.; Borzov, M.; Nie, W.-L. Chem. Prog. 2012, 24(8), 1526.
-
[20]
Tian, C.; Jiang, Y.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2015, 73, 1203.
-
[21]
Hu, X.; Tian, C.; Jiang, Y.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2015, 73, 1025. doi: 10.3866/PKU.WHXB201504141
-
[22]
Wen, Z.-G.; Tian, C.; Jiang, Y.; Borzov, M.; Nie, W.-L. Acta Chim. Sinica 2016, 74, 498
-
[23]
-
[24]
Nie, W.-L.; Sun, G.-F.; Tian, C.; Borzov, M. Naturforsch. 2016, 71(10) b, 1029.
-
[25]
-
[1]
-
-
-
[1]
Daojuan Cheng , Fang Fang . Exploration and Implementation of Science-Education Integration in Organic Chemistry Teaching for Pharmacy Majors: A Case Study on Nucleophilic Substitution Reactions of Alkyl Halides. University Chemistry, 2024, 39(11): 72-78. doi: 10.12461/PKU.DXHX202403105
-
[2]
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
-
[3]
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
-
[4]
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
-
[5]
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
-
[6]
Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
-
[7]
Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce4ⅢCe6Ⅳ(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
-
[8]
Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
-
[9]
Houjin Li , Wenjian Lan . Name Reactions in University Organic Chemistry Laboratory. University Chemistry, 2024, 39(4): 268-279. doi: 10.3866/PKU.DXHX202310016
-
[10]
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
-
[11]
Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
-
[12]
Aidang Lu , Yunting Liu , Yanjun Jiang . Comprehensive Organic Chemistry Experiment: Synthesis and Characterization of Triazolopyrimidine Compounds. University Chemistry, 2024, 39(8): 241-246. doi: 10.3866/PKU.DXHX202401029
-
[13]
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
-
[14]
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
-
[15]
Aiai WANG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress of bimetallic organic framework in tumor diagnosis and treatment. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1825-1839. doi: 10.11862/CJIC.20240225
-
[16]
Feng Sha , Xinyan Wu , Ping Hu , Wenqing Zhang , Xiaoyang Luan , Yunfei Ma . Design of Course Ideology and Politics for the Comprehensive Organic Synthesis Experiment of Benzocaine. University Chemistry, 2024, 39(2): 110-115. doi: 10.3866/PKU.DXHX202307082
-
[17]
Xinyu Zhu , Meili Pang . Application of Functional Group Addition Strategy in Organic Synthesis. University Chemistry, 2024, 39(3): 218-230. doi: 10.3866/PKU.DXHX202308106
-
[18]
Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
-
[19]
Shicheng Yan . Experimental Teaching Design for the Integration of Scientific Research and Teaching: A Case Study on Organic Electrooxidation. University Chemistry, 2024, 39(11): 350-358. doi: 10.12461/PKU.DXHX202408036
-
[20]
Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
-
[1]
Metrics
- PDF Downloads(10)
- Abstract views(2823)
- HTML views(695)