摘要/Abstract

在室温条件，氮气氛围下，以商用四氢呋喃（THF）为溶剂，10 mol%的茂钛全氟丁基磺酸盐（1·H₂O·THF）/锌粉（1.2 equiv.）体系催化二芳基二硒醚与溴代烷反应，高产率地合成了一系列不对称的单硒醚化合物.其可能机理为，锌粉还原Cp₂Ti^IV（OPf）₂（Pf=SO₂C₄F₉）生成三价钛配合物Cp₂Ti^ⅢOPf，然后Cp₂Ti^ⅢOPf与ArSeSeAr反应形成中间体Cp₂Ti^IVSeAr（OPf），随后与溴代烷反应生成不对称单硒醚化合物.首次报道1·H₂O·THF/Zn体系催化合成不对称单硒醚，该方法具有反应条件温和，操作简单，反应收率高等优点.
关键词: 茂钛全氟丁基磺酸盐, 锌粉, 二芳基二硒醚, 溴代烷, 不对称单硒醚
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.
Key words: titanocene perfluorobutanesulfonate, zinc dust, diaryl diselenides, bromoalkanes, unsymmetrical selenides


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