Petko Dina, Stratton Matthew, Koh Samuel, Tam William
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada.
Curr Org Synth. 2019;16(5):787-792. doi: 10.2174/1570179416666190401204448.
The ruthenium-catalyzed Bis-Homo-Diels-Alder cycloaddition between 1,5- cyclooctadiene and alkynes was explored, and the use of commercially available cationic catalysts was investigated. It was noted that [CpRu(CH3CN)3]PF6 was effective at catalyzing this cycloaddition and yields of the desired tricyclo[4.2.2.02,5]dec-7-ene adduct ranging from 13 to 83% were achieved using this cationic catalyst. Several cycloadducts that were previously unobtainable with the use of the neutral (Cp*RuCl(COD) catalysts were also successfully made using [CpRu(CH3CN)3]PF6 albeit in low yields.
Commercially available, and previously synthesized alkynes were combined with 1,5-cyclooctadiene and treated with a ruthenium catalyst within a glovebox. The reaction mixture was stirred for 72h at temperatures ranging from 25 to 70oC. The desired cycloadduct was then isolated using flash column chromatography and analyzed and characterized using NMR, IR and MS.
Several previously unattainable adducts were synthesized using the cationic [CpRu(CH3CN)3]PF6. When this catalyst was compared to the neutral Cp*RuCl(COD) greater yields were observed.
The present study describes an improved method for the formation of the tricyclo[4.2.2.02,5]dec-7- ene framework using a commercially available cationic ruthenium catalyst. It was noted that the use of [CpRu(CH3CN)3]PF6 led to improved yields when compared to Cp*RuCl(COD).
探索了钌催化的1,5 - 环辛二烯与炔烃之间的双高狄尔斯 - 阿尔德环加成反应，并研究了市售阳离子催化剂的使用情况。注意到[CpRu(CH₃CN)₃]PF₆在催化该环加成反应方面有效，使用这种阳离子催化剂可得到所需的三环[4.2.2.0²,⁵]癸 - 7 - 烯加合物，产率在13%至83%之间。使用[CpRu(CH₃CN)₃]PF₆还成功制备了几种以前使用中性（Cp*RuCl(COD)）催化剂无法获得的环加合物，尽管产率较低。
将市售的以及先前合成的炔烃与1,5 - 环辛二烯混合，并在手套箱中用钌催化剂处理。反应混合物在25至70℃的温度下搅拌72小时。然后使用快速柱色谱法分离所需的环加合物，并使用核磁共振（NMR）、红外光谱（IR）和质谱（MS）进行分析和表征。
使用阳离子[CpRu(CH₃CN)₃]PF₆合成了几种以前无法获得的加合物。当将该催化剂与中性Cp*RuCl(COD)进行比较时，观察到了更高的产率。
本研究描述了一种使用市售阳离子钌催化剂形成三环[4.2.2.0²,⁵]癸 - 7 - 烯骨架的改进方法。注意到与Cp*RuCl(COD)相比，使用[CpRu(CH₃CN)₃]PF₆可提高产率。
