Citation: Qing-Han Li, Yong Ding, Xue-Jun Yang. Nickel-catalyzed cross-coupling reaction of alkynyl bromides with Grignard reagents[J]. Chinese Chemical Letters, ;2014, 25(9): 1296-1300. doi: 10.1016/j.cclet.2014.04.019 shu

Nickel-catalyzed cross-coupling reaction of alkynyl bromides with Grignard reagents

1.
College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities, Chengdu 610041, China

Corresponding author: Qing-Han Li,
Received Date: 31 January 2014
Available Online: 4 April 2014
Fund Project: This work was financially supported by the Fundamental Research Funds for the Central Universities, Southwest University for Nationalities (No. 12NZYTH03) (No. 12NZYTH03) and the Project of Postgraduate Degree Construction, Southwest University for Nationalities (No. 2013XWD-S0703) (No. 381010)

We describe a convenient method for the synthesis of 1,2-disubstituted acetylenes via a cross-coupling reaction of (bromoethynyl)benzene with Grignard reagents. The reaction of (bromoethynyl)benzene (1 mmol) with Grignard reagent (1.3 mmol) mediated by NiCl₂ (4 mol%) and (p-CH₃Ph)3P (8 mol%) in THF could produce 1,2-disubstituted acetylenes in good yields at room temperature.
- 1,2-Disubstituted acetylene,
- Nickel,
- (Bromoethynyl)benzene,
- Grignard reagent,
- Cross-coupling
1. [1]
  [1] J.B. Johnson, T. Rovis, More than bystanders: the effect of olefins on transitionmetal-catalyzed cross-coupling reactions, Angew. Chem. Int. Ed. 47 (2008) 840-871.
2. [2]
  [2] D.G. Yu, Z.J. Shi, Mutual activation: Suzuki-Miyaura coupling through direct cleavage of the sp² C-O bond of naphtholate, Angew. Chem. Int. Ed. 50 (2011) 7079-7100.
3. [3]
  [3] J.J. Hirner, S.A. Blum, Nickel-catalyzed cross-coupling of organogold reagents, Organometallics 30 (2011) 1299-1302.
4. [4]
  [4] M.A. Greene, I.M. Yonova, F.J. Williams, E.R. Jarvo, Traceless directing group for stereospecific nickel-catalyzed alkyl-alkyl cross-coupling reactions, Org. Lett. 14 (2012) 4293-4296.
5. [5]
  [5] X.Q. Zhang, Z.X. Wang, Amido pincer nickel catalyzed Kumada cross-coupling of aryl, heteroaryl, and vinyl chlorides, Synlett 24 (2013) 2081-2084.
6. [6]
  [6] D.A. Everson, J.A. Buonomo, D.J. Weix, Nickel-catalyzed cross-electrophile coupling of 2-chloropyridines with alkyl bromides, Synlett 25 (2014) 233-238.
7. [7]
  [7] K. Sonogashira, Y. Tohda, N. Hagihara, A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines, Tetrahedron Lett. 50 (1975) 4467-4470.
8. [8]
  [8] R. Chinchilla, C. Nájera, The Sonogashira reaction: a booming methodology in synthetic organic chemistry, Chem. Rev. 107 (2007) 874-922.
9. [9]
  [9] E.M. Beccalli, G. Broggini, M. Martinelli, S. Sottocornola, C-C, C-O, C-N bond formation on sp² carbon by Pd(II)-catalyzed reactions involving oxidant agents, Chem. Rev. 107 (2007) 5318-5365.
10. [10]
  [10] D. Doucet, J.C. Hierso, Palladium-based catalytic systems for the synthesis of conjugated enynes by Sonogashira reactions and related alkynylations, Angew. Chem. Int. Ed. 46 (2007) 834-871.
11. [11]
  [11] H. Plenio, Catalysts for the Sonogashira coupling -the crownless again shall be king, Angew. Chem. Int. Ed. 47 (2008) 6954-6956.
12. [12]
  [12] M.M. Heravi, S. Sadjadi, Recent advances in the application of the Sonogashira method in the synthesis of heterocyclic compounds, Tetrahedron 65 (2009) 7761-7775.
13. [13]
  [13] K.C. Nicolaou, W.M. Dai, Chemistry and biology of the enediyne anticancer antibiotics, Angew. Chem. Int. Ed. 30 (1991) 1387-1416.
14. [14]
  [14] J.W. Grissom, G.U. Gunawardena, D. Klingberg, D.H. Huang, The chemistry of enediynes, enyne allenes and related compounds, Tetrahedron 52 (1996) 6453-6518.
15. [15]
  [15] T. Haro, C. Nevado, Gold-catalyzed ethynylation of arenes, J. Am. Chem. Soc. 132 (2010) 1512-1513.
16. [16]
  [16] B. Panda, T.K. Sarkar, On the catalytic duo PdCl₂(PPh₃)₂/AuCl(PPh₃) that cannot effect a Sonogashira-type reaction: a correction, Tetrahedron Lett. 51 (2010) 301-305.
17. [17]
  [17] M. Carril, A. Correa, C. Bolm, Iron-catalyzed Sonogashira reactions, Angew. Chem. Int. Ed. 47 (2008) 4862-4865.
18. [18]
  [18] L. Brandsma, S.F. Vasilevsky, H.D. Verkruijsse, Application of Transition Metal Catalysts in Organic Synthesis, Springer-Verlag, Berlin, 1988, pp. 179-225.
19. [19]
  [19] K.C. Nicolau, E.J. Sorensen, Classics in Total Synthesis, Wiley-VCH, Weinheim, 1996, pp. 582-586.
20. [20]
  [20] U.H.F. Bunz, Poly(aryleneethynylene)s: syntheses, properties, structures, and applications, Chem. Rev. 100 (2000) 1605-1644.
21. [21]
  [21] L.M. Tan, Z.Y. Sem, W.Y. Chong, et al., Continuous flow Sonogashira C-C coupling using a heterogeneous palladium-copper dual reactor, Org. Lett. 15 (2013) 65-67.
22. [22]
  [22] R. Ciriminna, V. Pandarus, G. Gingras, et al., Heterogeneous Sonogashira coupling over nanostructured SiliaCat Pd(0), ACS Sustainable Chem. Eng. 1 (2013) 57-61.
23. [23]
  [23] D.S. Yang, B. Li, H.J. Yang, H. Fu, L.I. Hu, Efficient copper-catalyzed Sonogashira couplings of aryl halides with terminal alkynes in water, Synlett 5 (2011) 702-706.
24. [24]
  [24] T. Suzuka, Y. Okada, K. Ooshiro, Y. Uozumi, Copper-free Sonogashira coupling in water with an amphiphilic resin-supported palladium complex, Tetrahedron 66 (2010) 1064-1069.
25. [25]
  [25] R. Severin, J. Reimer, S. Doye, One-pot procedure for the synthesis of unsymmetrical diarylalkynes, J. Org. Chem. 75 (2010) 3518-3521.
26. [26]
  [26] Y.S. Feng, Z.Q. Xu, L. Mao, F.F. Zhang, H.J. Xu, Copper catalyzed decarboxylative alkynylation of quaternary α-cyano acetate salts, Org. Lett. 15 (2013) 1472-1475.
27. [27]
  [27] S.H. Wang, L. Yu, P.H. Li, L.G. Meng, L. Wang, Copper(I) iodide catalyzed crosscoupling reaction of terminal alkynes with 1-bromoalkynes: a simple synthesis of unsymmetrical buta-1,3-diynes, Synthesis 10 (2011) 1541-1546.
28. [28]
  [28] K. Tsuyoshi, M. Nato, H. Koji, S. Tetsuya, M. Masahiro, Room temperature direct alkynylation of 1,3,4-oxadiazoles with alkynyl bromides under copper catalysis, J. Org. Chem. 75 (2010) 1764-1766.
29. [29]
  [29] M. Nato, H. Koji, S. Tetsuya, M. Masahiro, Nickel-catalyzed direct alkynylation of azoles with alkynyl bromides, Org. Lett. 11 (2009) 4156-4159.
30. [30]
  [30] J. Breitenfeld, J. Ruiz, M.D. Wodrich, X.L. Hu, Bimetallic oxidative addition involving radical intermediates in nickel-catalyzed alkyl-alkyl Kumada coupling reactions, J. Am. Chem. Soc. 135 (2013) 12004-12012.
31. [31]
  [31] Q.H. Li, H.M. Gau, Synthesis of allenes via nickel-catalyzed cross-coupling reaction of propargylic bromide with Grignard reagent, Synlett 23 (2012) 747-750.
32. [32]
  [32] A.M. Lauer, F. Mahmud, J.M. Wu, Cu(I)-catalyzed, α-selective, allylic alkylation reactions between phosphorothioate esters and organomagnesium reagents, J. Am. Chem. Soc. 133 (2011) 9119-9123.
33. [33]
  [33] G. Cahiez, O. Gager, J. Buendia, Copper-catalyzed cross-coupling of alkyl and aryl Grignard reagents with alkynyl halides, Angew. Chem. Int. Ed. 49 (2010) 1278-1281.
34. [34]
  [34] D. Castagnolo, M. Botta, Iron-Catalyzed Cross-Coupling between 1-Bromoalkynes and Grignard-Derived Organocuprate Reagents, Eur. J.Org.Chem. 17 (2010) 3224-3228.
35. [35]
  [35] H. Hofmeister, K. Annen, H. Laurent, R. Wiechert, A novel entry to 17a-bromoand 17a-iodoethynyl steroids, Angew. Chem. Int. Ed. Engl. 23 (1984) 727-729.
36. [36]
  [36] A.D. Finke, E.C. Elleby, M.J. Boyd, H. Weissman, J.S. Moore, Zinc chloride-promoted aryl bromide-alkyne cross-coupling reactions at room temperature, J. Org. Chem. 74 (2009) 8897-8900.
37. [37]
  [37] J. Moon, M. Jeong, H. Nam, et al., One-pot synthesis of diarylalkynes using palladium-catalyzed Sonogashira reaction and decarboxylative coupling of sp carbon and sp² carbon, Org. Lett. 10 (2008) 945-948.
38. [38]
  [38] X.F. Wu, H. Neumann, M. Beller, Palladium-catalyzed Sonogashira reactions of aryl amines with alkynes via in situ formation of arenediazonium salts, Chem. Commun. 47 (2011) 7959-7961.
1. [1]
  Zhirong Yang , Shan Wang , Ming Jiang , Gengchen Li , Long Li , Fangzhi Peng , Zhihui Shao . One stone three birds: Ni-catalyzed asymmetric allenylic substitution of allenic ethers, hydroalkylation of 1,3-enynes and double alkylation of enynyl ethers. Chinese Chemical Letters, 2024, 35(8): 109518-. doi: 10.1016/j.cclet.2024.109518
2. [2]
  Peng Guo , Shicheng Dong , Xiang-Gui Zhang , Bing-Bin Yang , Jun Zhu , Ke-Yin Ye . Cobalt-catalyzed migratory carbon-carbon cross-coupling of borabicyclo[3.3.1]nonane (9-BBN) borates. Chinese Chemical Letters, 2025, 36(4): 110052-. doi: 10.1016/j.cclet.2024.110052
3. [3]
  Jiangping Chen , Hongju Ren , Kai Wu , Huihuang Fang , Chongqi Chen , Li Lin , Yu Luo , Lilong Jiang . Boosting hydrogen production of ammonia decomposition via the construction of metal-oxide interfaces. Chinese Journal of Structural Chemistry, 2024, 43(2): 100236-100236. doi: 10.1016/j.cjsc.2024.100236
4. [4]
  Zhenkang Ai , Hui Chen , Xuebin Liao . Nickel-catalyzed decarboxylative difluoromethylation and alkylation of alkenes. Chinese Chemical Letters, 2025, 36(3): 109954-. doi: 10.1016/j.cclet.2024.109954
5. [5]
  Xiao-Bo Liu , Ren-Ming Liu , Xiao-Di Bao , Hua-Jian Xu , Qi Zhang , Yu-Feng Liang . Nickel-catalyzed reductive formylation of aryl halides via formyl radical. Chinese Chemical Letters, 2024, 35(12): 109783-. doi: 10.1016/j.cclet.2024.109783
6. [6]
  Shaobin He , Xiaoyun Guo , Qionghua Zheng , Huanran Shen , Yuan Xu , Fenglin Lin , Jincheng Chen , Haohua Deng , Yiming Zeng , Wei Chen . Engineering nickel-supported osmium bimetallic nanozymes with specifically improved peroxidase-like activity for immunoassay. Chinese Chemical Letters, 2025, 36(4): 110096-. doi: 10.1016/j.cclet.2024.110096
7. [7]
  Wanmin Cheng , Juan Du , Peiwen Liu , Yiyun Jiang , Hong Jiang . Photoinitiated Grignard Reagent Synthesis and Experimental Improvement in Triphenylmethanol Preparation. University Chemistry, 2024, 39(5): 238-242. doi: 10.3866/PKU.DXHX202311066
8. [8]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
9. [9]
  Lang Gao , Cen Zhou , Rui Wang , Feng Lan , Bohang An , Xiaozhou Huang , Xiao Zhang . Unveiling inverse vulcanized polymers as metal-free, visible-light-driven photocatalysts for cross-coupling reactions. Chinese Chemical Letters, 2024, 35(4): 108832-. doi: 10.1016/j.cclet.2023.108832
10. [10]
  Yuhan Liu , Jingyang Zhang , Gongming Yang , Jian Wang . Highly enantioselective carbene-catalyzed δ-lactonization via radical relay cross-coupling. Chinese Chemical Letters, 2025, 36(1): 109790-. doi: 10.1016/j.cclet.2024.109790
11. [11]
  Junxin Li , Chao Chen , Yuzhen Dong , Jian Lv , Jun-Mei Peng , Yuan-Ye Jiang , Daoshan Yang . Ligand-promoted reductive coupling between aryl iodides and cyclic sulfonium salts by nickel catalysis. Chinese Chemical Letters, 2024, 35(11): 109732-. doi: 10.1016/j.cclet.2024.109732
12. [12]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
13. [13]
  Ze-Yuan Ma , Mei Xiao , Cheng-Kun Li , Adedamola Shoberu , Jian-Ping Zou . S-(1,3-Dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate (SDDP): A practical electrophilic reagent for the phosphorothiolation of electron-rich compounds. Chinese Chemical Letters, 2024, 35(5): 109076-. doi: 10.1016/j.cclet.2023.109076
14. [14]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
15. [15]
  Caihong Mao , Yanfeng He , Xiaohan Wang , Yan Cai , Xiaobo Hu . Synthesis and molecular recognition characteristics of a tetrapodal benzene cage. Chinese Chemical Letters, 2024, 35(8): 109362-. doi: 10.1016/j.cclet.2023.109362
16. [16]
  Ruilong Geng , Lingzi Peng , Chang Guo . Dynamic kinetic stereodivergent transformations of propargylic ammonium salts via dual nickel and copper catalysis. Chinese Chemical Letters, 2024, 35(8): 109433-. doi: 10.1016/j.cclet.2023.109433
17. [17]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
18. [18]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
19. [19]
  Qiang Wu , Baofeng Wang . Exploring synthetic strategy for stabilizing nickel-rich layered oxide cathodes through structural design. Chinese Chemical Letters, 2024, 35(12): 110089-. doi: 10.1016/j.cclet.2024.110089
20. [20]
  Jumei Zhang , Ziheng Zhang , Gang Li , Hongjin Qiao , Hua Xie , Ling Jiang . Ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes. Chinese Chemical Letters, 2025, 36(2): 110278-. doi: 10.1016/j.cclet.2024.110278

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(792)
HTML views(26)

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