Stereochemistry of Asymmetric Silicon. The Silicon-Sulfur Bond

Orthogonal reactivity of thiols toward chlorovinylsilanes: selective thiol-ene chemistry

“…Previous reports in the literature have shown that thiol-terminated compounds, which are inherently nucleophilic, react with chlorosilanes by displacing the chloride atom; 16,17 however, in the wide breadth of the current study, this was not the case. Additionally, the selective thiol-ene reaction of chlorovinylsilanes results in new thioether-substituted chlorosilanes, which may be very useful in organic synthesis as well as organometallic and materials chemistry.…”

“…This is likely due to the low rate of substitution in the absence of an acid acceptor, which is normally required for the formation of silyl thioethers from chlorosilanes and thiols. 16,17 Conclusion…”

Organosilicon Derivatives of Sulfur

“…8ilanethiols are readily oxidized by iodine and react with lead, copper, nickel, and mercury carbonates and acetates; this may be used for their quantitative and qualitative determination [725]. The reduction of silanethiols with LiAlH( forms hydrosilanes [664]. N-Phenyla-chlorobenzalimine cleaves the 8i -8 bond in triphenylsilanethiol on heating in xylene.…”

“…K) (2.32) Lithium does not react with triphenylsilanethiol under analogous conditions. However lithIum triphenylsilanethiolate may be obtained by the reaction of triphenylsilanethiol with phenyllithium at room temperature (81% yield) [196]: (2.33) The diethylamine salt of a-naphthyl(phenyl)methylsilanethiol, which was formed by the hydrolysis of the corresponding disilthiane with an aqueous solution of diethylamine, has also been characterized [664].…”

“…The reduction of optically active O'-naphthylphenylmethyl-(methylthio)silane with lithium aluminum hydride in boiling ether to O'-naphthylphenylmetliylsilane proceeds stereospecifically and, in contrast to the corresponding oxygen analog, with inversion of the configuration [664,964]. 65,104,211,377,403,489,552,703,704].…”