Reactions of Allylsilanes with Iodine

Allylsilanes

“…Preparation of the requisite allylsilane by anion silylation required favourable alkoxide coordination of the allyl-lithium for success, with failure being experienced with homologous, longer chain, primary alcohols. Based on an earlier report 63 on the reaction of allyltrimethylsilane with iodine, in which only allyl iodide was isolated, Jung has re-investigated this reaction as a source of iodotrimethylsilane (Scheme 9.32). Based on an earlier report 63 on the reaction of allyltrimethylsilane with iodine, in which only allyl iodide was isolated, Jung has re-investigated this reaction as a source of iodotrimethylsilane (Scheme 9.32).…”

Total Syntheses of Amphidinolides T1, T3, and T4

“…[21,22] Base-mediated Peterson elimination of the intermediate tertiary alcohol delivered an allylic silane, which was then converted into the bromide 24 by treatment with pyrrolidone hydrotribromide (PHT). [23] Deprotonation of N-propionyloxazolidinone (25) with NaHMDS and enolate alkylation with bromide 24 followed by reductive cleavage of the oxazolidinone auxiliary provided alcohol 26. [24] Oxidation of the alcohol 26 and conversion of the resulting aldehyde into the corresponding…”

Synthesis of the functionalised core of neoliacinic acid

“…6,7 The allylic silane 4 was then converted to the allylic bromide 5 by treatment with pyrrolidone hydrotribromide. 8,9 This reagent was used to deliver the precise amount of bromine required, circumventing the problem of over-bromination that was encountered when molecular bromine was employed for the transformation.…”