Stereoselective Synthesis of Optically Active Disilanes and Selective Functionalization by the Cleavage of Silicon−Naphthyl Bonds with Bromine
作者:Keigo Suzuki、Yusuke Kawakami、Devadasan Velmurugan、Takashi Yamane
DOI:10.1021/jo049398y
日期:2004.8.1
cholorosilanes and retention for the silyl anions. Optically active disilanes with two chiral centers, (1R,2R)-1,2-dimethyl-1,2-di(naphth-1-yl)-1,2-diphenyldisilane and (1S,2S)-1,2-di(4-methoxynaphth-1-yl)-1,2-dimethyl-1,2-diphenyldisilane, were obtained in high optical purity by the reactions of corresponding optically active halogenosilanes (Cl or F) with optically active silyllithiums. The silicon−silicon bond
具有一个手性硅中心的光学活性乙硅烷,(R)-1,2-二甲基-1-(萘-1-基)-1,2,2-三苯基乙硅烷和(R)-1,2,2-三甲基-2通过(S)-甲基(萘-1-基)苯基氯硅烷(> 99%ee)反应获得-(4-甲氧基萘-1-基)-1-(萘-1-基)-1-苯基乙硅烷与甲基二苯基甲硅烷基锂或由甲基二苯基氯硅烷与旋光性(S)-甲基(萘-1-基)苯基甲硅烷基锂反应并由(S)-甲基(萘-1-基)苯基氯硅烷(> 99%ee)与二甲基(4-甲氧基萘-1-基)甲硅烷基锂。在优化的条件下,反应进行时,氯硅烷几乎完全转化,而甲硅烷基阴离子却保留了下来。具有两个手性中心的光学活性乙硅烷(1 R, 2 R)-1,2-二甲基-1,2-二(萘-1-基)-1,2-二苯基乙硅烷和(1 S, 2 S)-1通过相应的旋光性卤代硅烷(Cl或F)与旋光性甲硅烷基锂的反应,以高旋光性获得了1,2-二(4-甲氧基萘-1-基)-1,2-二甲基-1