Citation: SHE Chuan, YU Pei, LUO Xingting, TIAN Zaiwen, ZHANG Wanxuan. Synthesis of Alkynyl Selenides by Gold Tribromide Catalyzed Reaction of Terminal Alkynes with Diaryl Diselenides[J]. Chinese Journal of Applied Chemistry, ;2017, 34(10): 1134-1139. doi: 10.11944/j.issn.1000-0518.2017.10.160513 shu

Synthesis of Alkynyl Selenides by Gold Tribromide Catalyzed Reaction of Terminal Alkynes with Diaryl Diselenides

Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Ministry of Education, Hubei Collaborative Innovation Center for Advanced Organic Chemical Material, Hubei University, Wuhan 430062, China

Corresponding author: ZHANG Wanxuan, zhangwx@hubu.edu.cn
Received Date: 19 December 2016
Revised Date: 13 February 2017
Accepted Date: 29 March 2017

Fund Project: Supported by the Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Ministry of Education, Hubei University and Stu-dent Innovation Training Program(No.201410512002)the Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Ministry of Education, Hubei University and Stu-dent Innovation Training Program 201410512002

Figures(3)

Alkynyl selenides are important starting materials for the synthesis of some organic selenides. In this paper, alkynyl selenides were synthesized by the reaction between terminal alkynes and diaryl diselenides catalyzed by gold tribromide(AuBr₃) in the presence of a base such as potassium carbonate in good to excellent yields(69%~98%). The reaction was performed at 80℃ in air, and all the selenium atoms of diaryl diselenides could be taken into use. Dimethyl sulfoxide is a proper solvent. The reaction does not occur when less polar tetrahydrofuran or toluene is used as the solvent. Aryl, alkenyl and alkyl alkynes can smoothly react with diaryl diselenides under the above conditions. Para-substituted phenylacetylene(such as 4-ethynyltoluene, 1-ethynyl-4-methoxybenzene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, etc.) gives rise to alkynyl selenides in good to excellent yields(78%~98%) whether the substituents are electron-donating or -withdrawing. Ortho-and meta-substituted phenylacetylene leads to relatively low yields(69%~82%). Non-aryl alkynes(such as 1-nonyne and 1-ethynylcyclohexene) also afford corresponding alkynyl selenides with high yields(95%).
- gold tribromide,
- terminal alkynes,
- diselenides,
- alkynyl selenides
1. [1]
  Lucas M A, Ngugen O T K, Schiesser C H. Preparation of 5-Selenopentopyranose Sugars from Pentose Starting Materials by Samarium(Ⅱ) Iodide or (Phenylseleno)formate Mediated Ring Closures[J]. Tetrahedron, 2000,56(26):3995-4000.
2. [2]
  Wirth T H. Organoselenium Chemistry in Stereoselective Reactions H[J]. Angew Chem Int Ed, 2000,39(21):3740-3749. doi: 10.1002/(ISSN)1521-3773
3. [3]
  Comasseto J V, Ling L W. Vinylic Selenides and Tellurides-Preparation, Reactivity and Synthetic Applications[J]. Synthesis, 1997,4(26):373-403.
4. [4]
  Chieffi A, Comasseto J V. Organoselenium Chemistry:A Practical Approach[M]. UK:Oxford University Press, 1999:131.
5. [5]
  Dabdoub M J, Begnini M L, Guerrero P G. Hydrozirconation of Lithium Alkynylselenolate Anions. Generation and Reactions of α-Zirconated Vinyl Selenide Intermediates[J]. J Org Chem, 2000,65(1):61-67. doi: 10.1021/jo991016e
6. [6]
  Xu W M, Tang E, Huang X H. Preparation of Isoxazol(in)yl Substituted Selenides and Their Further Deselenenylation Reaction to Synthesize 3, 5-Disubstituted Isoxazoles[J]. Tetrahedron, 2005,61(2):501-506. doi: 10.1016/j.tet.2004.10.071
7. [7]
  Bolzan R C, Folmer V, Farina M. δ-Aminolevulinate Dehydratase Inhibition by Phenyl Selenoacetylene:Effect of Reaction with Hydrogen Peroxide[J]. Pharmacol Toxicol, 2002,90(4):214-219. doi: 10.1034/j.1600-0773.2002.900408.x
8. [8]
  Ahammed S, Bhadra S, Kundu D. An Efficient and General Procedure for the Synthesis of Alkynyl Chalcogenides (Selenides and Tellurides) by Alumina-supported Cu(Ⅱ)-catalyzed Reaction of Alkynyl Bromides and Diphenyl Dichalcogenides[J]. Tetrahedron, 2012,68(51):10542-10549. doi: 10.1016/j.tet.2012.08.046
9. [9]
  Tingoli M, Tiecco M, Testaferri L. Reactions of Terminal Alkynes with Iodobenzene Diacetate and Diphenyl Diselenide:Synthesis of Phenyl Alkynyl Selenides[J]. Synlett, 1993,1993(3):211-212. doi: 10.1055/s-1993-22405
10. [10]
  Bieber L W, Margarete F, Menezes P H. Short and Efficient Preparation of Alkynyl Selenides, Sulfides and Tellurides from Terminal Alkynes[J]. Tetrahedron Lett, 2004,45(13):2735-2737. doi: 10.1016/j.tetlet.2004.02.042
11. [11]
  Mohammadi E, Movassagh B. Cryptand-22 as an Efficient Ligand for the Copper-Catalyzed Cross-Coupling Reaction of Diorgano Dichalcogenides with Terminal Alkynes Leading to the Synthesis of Alkynyl Chalcogenides[J]. Tetrahedron Lett, 2014,55(9):1613-1615. doi: 10.1016/j.tetlet.2014.01.088
12. [12]
  Schneider P H, Merlo A A, Rampon D S. Chalcogenoacetylenes Obtained by Indium(Ⅲ) Catalysis:Dual Catalytic Activation of Diorgano Dichalcogenides and Csp-H Bonds[J]. Eur J Org Chem, 2011,2011(35):7066-7070. doi: 10.1002/ejoc.v2011.35
13. [13]
  Braga A L, Godoi M, Ricardo E W. An Efficient Synthesis of Alkynyl Selenides and Tellurides from Terminal Acetylenes and Diorganyl Diselenides or Ditellurides Catalyzed by Recyclable Copper Oxide Nanopowder[J]. Tetrahedron, 2012,68(51):10426-10430. doi: 10.1016/j.tet.2012.08.086
14. [14]
  Braga A L, Godoi M, Liz D G. Magnetite (Fe₃O₄) Nanoparticles:An Efficient and Recoverable Catalyst for the Synthesis of Alkynyl Chalcogenides (Selenides and Tellurides) from Terminal Acetylenes and Diorganyl Dichalcogenides[J]. Tetrahedron, 2014,70(20):3349-3354. doi: 10.1016/j.tet.2013.09.095
15. [15]
  Xu X H, Lu R, Zhang Q L. Atom-economic Reaction:Diselenides Reacted with Terminal Alkynes to Synthesize Alkynyl Selenides Catalyzed by Cesium Hydroxy and Promoted by Air[J]. Chem J Chinese Univ, 2005,26(2):267-269.
16. [16]
  Sharma A, Schwab R S, Braga A L. A Convenient Synthetic Route for Alkynylselenides from Alkynyl Bromides and Diaryl Diselenides Employing Copper(Ⅰ)/Imidazole as Novel Catalyst System[J]. Tetrahedron Lett, 2008,49(35):5172-5174. doi: 10.1016/j.tetlet.2008.06.071
17. [17]
  Movassagh B, Navidi M. A Simple and Effective Approach to the Synthesis of Alkynyl Selenides from Terminal Alkynes[J]. Chinese Chem Lett, 2012,23(9):1035-1038. doi: 10.1016/j.cclet.2012.06.036
18. [18]
  Perin G, Borges E L, Alves D. Highly Stereoselective Method to Prepare Bis-phenylchalcogen Alkenes via Addition of Chalcogenolate to Phenylseleno Alkynes[J]. Tetrahedron Lett, 2012,53(16):2066-2069. doi: 10.1016/j.tetlet.2012.02.028
19. [19]
  Lara R G, Rosa P C, Soares L K. A Simple and Stereoselective Synthesis of (Z)-1, 2-Bisarylselanyl Alkenes from Alkynes Using KF/Al₂O₃[J]. Tetrahedron, 2012,68(51):10414-10418. doi: 10.1016/j.tet.2012.08.055
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
5. [5]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
6. [6]
  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
7. [7]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
8. [8]
  Huayan Liu , Yifei Chen , Mengzhao Yang , Jiajun Gu . 二维材料基超级电容器的容量与倍率性能提升策略. Acta Physico-Chimica Sinica, 2025, 41(6): 100063-. doi: 10.1016/j.actphy.2025.100063
9. [9]
  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
10. [10]
  Linbao Zhang , Weisi Guo , Shuwen Wang , Ran Song , Ming Li . Electrochemical Oxidation of Sulfides to Sulfoxides. University Chemistry, 2024, 39(11): 204-209. doi: 10.3866/PKU.DXHX202401009
11. [11]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
12. [12]
  Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo . 氰基修饰的苝二酰亚胺衍生物作为膜厚不敏感型阴极界面材料用于高效有机太阳能电池. Acta Physico-Chimica Sinica, 2025, 41(3): 2406007-. doi: 10.3866/PKU.WHXB202406007
13. [13]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
14. [14]
  Yinwu Su , Xuanwen Zheng , Jianghui Du , Boda Li , Tao Wang , Zhiyan Huang . Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment. University Chemistry, 2024, 39(5): 307-314. doi: 10.3866/PKU.DXHX202311092
15. [15]
  Fei Liu , Dong-Yang Zhao , Kai Sun , Ting-Ting Yu , Xin Wang . Comprehensive Experimental Design for Photochemical Synthesis, Analysis, and Characterization of Seleno-Containing Medium-Sized N-Heterocycles. University Chemistry, 2024, 39(3): 369-375. doi: 10.3866/PKU.DXHX202309047
16. [16]
  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
17. [17]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
18. [18]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
19. [19]
  Cuicui Yang , Bo Shang , Xiaohua Chen , Weiquan Tian . Understanding the Wave-Particle Duality and Quantization of Confined Particles Starting from Classic Mechanics. University Chemistry, 2025, 40(3): 408-414. doi: 10.12461/PKU.DXHX202407066
20. [20]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(199)
HTML views(28)

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