The reduction of diaryldiselenides by Cp2TiCl2/BuiMgBr/THF led to arylselenium complex of titanocene [Cp2TiSeAr]. This species reacted smoothly with electrophilic substrates such as acylhalides, α-bromocarbonyl compo...The reduction of diaryldiselenides by Cp2TiCl2/BuiMgBr/THF led to arylselenium complex of titanocene [Cp2TiSeAr]. This species reacted smoothly with electrophilic substrates such as acylhalides, α-bromocarbonyl compounds, diaryliodonium salts, α,β-unsaturated carbonyl compounds to afford the corresponding organic selenides in high yields.展开更多
Under N\-2 atmosphere and at room temperature, the reaction of diaryl diselenid（1\^0 mmol） with terminal alkynes（2\^2 mmol） catalyzed by cesium hydroxy gave exclusively （Z）-1,2-bis（arylseleno）-1-alkenes, but u...Under N\-2 atmosphere and at room temperature, the reaction of diaryl diselenid（1\^0 mmol） with terminal alkynes（2\^2 mmol） catalyzed by cesium hydroxy gave exclusively （Z）-1,2-bis（arylseleno）-1-alkenes, but under air and at -100 ℃, the reaction gave alkyne selenides in 83%95% yields based on the selenium atoms. The method for the preparation of alkyne selenides has advantages of available starting materials and simple procedures. The reaction mechanism was proposed.展开更多
以对叔丁基苯酚为原料,经一步法制得对叔丁基杯[6]芳烃。通过逆傅克反应、亲核取代反应制得二烷基化杯[6]芳烃。最后通过磺化、亲核取代等反应,合成了下缘含喹啉基长链的新型夹状醚杯[6]芳烃化合物( 2a~ 2c ),其结构经 1 H NMR, 13 C NM...以对叔丁基苯酚为原料,经一步法制得对叔丁基杯[6]芳烃。通过逆傅克反应、亲核取代反应制得二烷基化杯[6]芳烃。最后通过磺化、亲核取代等反应,合成了下缘含喹啉基长链的新型夹状醚杯[6]芳烃化合物( 2a~ 2c ),其结构经 1 H NMR, 13 C NMR和HR-MS(ESI-QTOF)表征。以10.0 mol%杯[6]芳烃化合物( 2b )为相转移催化剂,20.0 mol%KOH为催化剂,THF为溶剂,较高产率和高选择性地合成了一系列( Z )-1,2-二芳硒基烯化合物,其结构经 1 H NMR和NOESY确证。 2b 重复使用6次,催化活性无明显降低。展开更多
在铁粉存在下,以商用N,N-二甲基甲酰胺(DMF)作溶剂,90℃、氮气保护下,二芳基二硒醚与α-溴代羰基化合物反应,得到一系列α-芳硒基羰基化合物.考察了温度、时间、溶剂及铁粉用量对反应的影响,其中,温度对反应的影响最为明显.α-溴代羰基...在铁粉存在下,以商用N,N-二甲基甲酰胺(DMF)作溶剂,90℃、氮气保护下,二芳基二硒醚与α-溴代羰基化合物反应,得到一系列α-芳硒基羰基化合物.考察了温度、时间、溶剂及铁粉用量对反应的影响,其中,温度对反应的影响最为明显.α-溴代羰基化合物中羰基上取代基对反应有很大影响,取代基为苯基时,转化率较甲基或烷氧基时低.反应机理可能是铁插入Se—Se键中形成亲核性Se Fe Se,随后与亲电底物α-溴代羰基化合物发生亲核取代.本方法使用铁粉促进断裂Se—Se键具有原料安全无毒、廉价易得、实验操作简便等优点.展开更多
文摘The reduction of diaryldiselenides by Cp2TiCl2/BuiMgBr/THF led to arylselenium complex of titanocene [Cp2TiSeAr]. This species reacted smoothly with electrophilic substrates such as acylhalides, α-bromocarbonyl compounds, diaryliodonium salts, α,β-unsaturated carbonyl compounds to afford the corresponding organic selenides in high yields.
文摘Under N\-2 atmosphere and at room temperature, the reaction of diaryl diselenid（1\^0 mmol） with terminal alkynes（2\^2 mmol） catalyzed by cesium hydroxy gave exclusively （Z）-1,2-bis（arylseleno）-1-alkenes, but under air and at -100 ℃, the reaction gave alkyne selenides in 83%95% yields based on the selenium atoms. The method for the preparation of alkyne selenides has advantages of available starting materials and simple procedures. The reaction mechanism was proposed.
文摘在铁粉存在下,以商用N,N-二甲基甲酰胺(DMF)作溶剂,90℃、氮气保护下,二芳基二硒醚与α-溴代羰基化合物反应,得到一系列α-芳硒基羰基化合物.考察了温度、时间、溶剂及铁粉用量对反应的影响,其中,温度对反应的影响最为明显.α-溴代羰基化合物中羰基上取代基对反应有很大影响,取代基为苯基时,转化率较甲基或烷氧基时低.反应机理可能是铁插入Se—Se键中形成亲核性Se Fe Se,随后与亲电底物α-溴代羰基化合物发生亲核取代.本方法使用铁粉促进断裂Se—Se键具有原料安全无毒、廉价易得、实验操作简便等优点.
