152896-13-4Relevant academic research and scientific papers
Regio- and stereochemistry and kinetics in the addition reactions of alcohols to phenyl-substituted disilenes
Sekiguchi, Akira,Maruki, Ikutaro,Sakurai, Hideki
, p. 11460 - 11466 (2007/10/02)
A phenyl-substituted disilene, PhMeSi=SiMe2, and stereoisomeric disilenes (E)- and (Z)-PhMeSi=SiMePh were generated photochemically from newly designed precursors. These phenyl-substituted disilenes were detected spectroscopically in an argon matrix at 10 K. Introduction of the phenyl group(s) caused a large red shift in the Si=Si absorption. The reactions of these disilenes with alcohols such as i-PrOH, t-BuOH, and EtOH were examined. PhMeSi=SiMe2 gave the addition products PhMeHSi - SiMe2OR, regioselectively. (E)- and (Z)-PhMeSi=SiMePh gave the corresponding alkoxyhydrodisilanes in high diastereoselectivity arising from syn addition of alcohols to the intermediate disilenes. A mechanism involving a four-membered intermediate is proposed for the addition reaction of alcohols to disilenes. The transient absorptions of these disilenes were also observed by laser flash photolysis, and kinetic studies revealed that disilenes were quenched by alcohols very rapidly (k2 = 107-108 M-1 s-1).
