Phosphine-Catalyzed Reductions of Alkyl Silyl Peroxides by Titanium Hydride Reducing Agents: Development of the Method and Mechanistic Investigations
作者:Jason R. Harris、M. Taylor Haynes、Andrew M. Thomas、K. A. Woerpel
DOI:10.1021/jo1008367
日期:2010.8.6
A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields
提出了一种通过使用催化量的膦来还原保护的氢过氧化物的方法。钛(IV)醇盐和硅氧烷的组合允许在烷基甲硅烷基过氧化物的存在下化学选择性还原氧化膦。随后通过膦还原过氧化物部分,以有用的产率提供了相应的甲硅烷基化的醇。包括交叉实验在内的机械实验支持其中过氧化物基团被还原并且甲硅烷基基团在一致的步骤中被转移的机理。用17种O标记的过氧化物进行的标记研究表明,与硅原子相邻的氧原子已从甲硅烷基过氧化物中除去。