The tosylate moiety is an extremely versatile, particularly stable leaving group, allowing for a wide range of synthetic uses. Methods in the literature for the synthesis of secondary tosylates are well known, but very little is known about allylic tosylates. These tosylates have proven difficult to synthesize due to the proximity to the p system leaving them susceptible to rearrangements, carbocation formation, or elimination to form dienes. The object of this research is to develop and demonstrate the generality of a method to synthesize allylic tosylates from α,β-unsatd. alcohols in good yield. In our method sodium hydride is used to generate the allylic alkoxide which is then reacted with tosyl anhydride to produce the tosylate, this alternative is utilized to avoid subsequent displacement reactions caused previously when p-toluenesulfonyl chloride was used. Product mixtures were isolated through HPLC and characterized using GC/MS and FT-NMR. In addition to the tosylate, GC/MS chromatograms show peaks that would be expected upon the loss of the tosyl group, suggesting immediate elimination when ionized. Previously, isophorol has been studied and has helped to give a better understanding of the reaction. This research focuses on tosylates from 2-ethylidenecyclohexanol and 3-phenyl-2-propenol to improve our current procedure and to generalize this synthesis to more allylic systems.

Expansion of tosylation on new allylic systems

255th National Meeting (2018)

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