Gold-Catalyzed Dehydrogenative Cycloaddition of Tethered 1,<i>n</i>-Dihydrodisilanes to Alkynes
作者:Vasiliki Kotzabasaki、Ioannis N. Lykakis、Charis Gryparis、Androniki Psyllaki、Eleni Vasilikogiannaki、Manolis Stratakis
DOI:10.1021/om3011678
日期:2013.1.28
5-hexamethyltrisiloxane (4), and 1,2-bis(dimethylsilyl)benzene (5), to alkynes, forming cycloadducts and releasing H2. Under the same conditions, polymeric methylhydrosiloxane is completely unreactive. For the majority of terminal alkynes and 1,n-dihydrodisilanes the yields are excellent (up to 99%). In general, terminal alkynes are more reactive as compared to internal. The reaction tolerates several
负载在TiO 2(0.1–2%mol)上的金纳米颗粒在温和条件下催化脱链添加1,n-二氢二硅烷,例如1,1,3,3-四甲基二硅氧烷(1),1,1,3,3 -四苯基二硅氧烷(2),1,1,1,3,5,7,7,7-八甲基四硅氧烷(3),1,1,3,3,5,5-六甲基三硅氧烷(4)和1,2-双(二甲基甲硅烷基)苯(5),形成炔烃,形成环加合物并释放H 2。在相同条件下,聚合的甲基氢硅氧烷是完全不反应的。对于大多数末端炔烃和1,n-二氢乙硅烷的收率非常好(高达99%)。通常,末端炔烃与内部炔烃相比更具反应性。该反应容许几个官能团,并且可以在多种溶剂中进行。在1,1,3,3-四甲基二硅氧烷的情况下,建议金纳米颗粒通过脱氢途径形成中间体环-金-四甲基二硅氧烷,该途径经历炔烃的正式[3 + 2]环加成。