Citation: Wang Lingxiao, Li Ningbo, Wang Haojiang, Liu Wen, Diao Haipeng, Xu Xinhua. Efficient Synthesis of Unsymmetrical Selenides Promoted by Titanocene Perfluorobutanesulfonate/Zinc Catalytic System[J]. Chinese Journal of Organic Chemistry, ;2019, 39(6): 1802-1807. doi: 10.6023/cjoc201812033 shu

Efficient Synthesis of Unsymmetrical Selenides Promoted by Titanocene Perfluorobutanesulfonate/Zinc Catalytic System

Wang Lingxiao ^a ,
Li Ningbo ^a,, ,
Wang Haojiang ^a ,
Liu Wen ^a ,
Diao Haipeng ^a,, ,
Xu Xinhua ^b

a.
Basic Medical College, Shanxi Medical University, Taiyuan 030001
b.
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082

Corresponding author: Li Ningbo, ningboli@sxmu.edu.cn Diao Haipeng, diaohp@sxmu.edu.cn
Received Date: 19 December 2018
Revised Date: 3 February 2019
Available Online: 22 June 2019
Fund Project: the National Natural Science Foundation of China 21802093the Shanxi Province Science Foundation for Youths 201701D221035the PhD Start-up Foundation of Shanxi Medical University 03201501Project supported by the the National Natural Science Foundation of China (No. 21802093), the Shanxi Province Science Foundation for Youths (No. 201701D221035), and the PhD Start-up Foundation of Shanxi Medical University (No. 03201501)

Figures(3)

In the presence of 10 mol% titanocene perfluorobutanesulfonate (1·H₂O·THF), reductive cleavage Se-Se bond by zinc dust (1.2 equiv.) at room temperature led to nucleophilic selenium anion species, which reacted with bromoalkanes to afford unsymmetrical selenides in good to excellent yield using commercial tetrahydrofuran (THF) as solvent under N₂ atmosphere. The possible reaction mechanism is that zinc dust reduces Cp₂Ti^Ⅳ(OPf)₂ (Pf=SO₂C₄F₉) to produce Cp₂Ti^ⅢOPf, which reacts with diaryl diselenides to form the intermediate Cp₂Ti^ⅣSeAr(OPf). Then it further reacts with bromoalkanes to produce unsymmetrical selenides. In this paper, the synthesis of asymmetrical selenides catalyzed by 1·H₂O·THF/Zn system is first reported. This method has the advantages of mild reaction conditions, simple operation and high yield.
- titanocene perfluorobutanesulfonate,
- zinc dust,
- diaryl diselenides,
- bromoalkanes,
- unsymmetrical selenides
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