Rearrangements of allyl sulfonium ylides are useful sp3-sp3 carbon-carbon bond forming processes that can be married with an in-situ ylide formation to develop powerful synthetic transformations. This talk will discuss several strategies we have developed to access the synthetic potential of sulfonium ylide rearrangements from organogold species. These approaches allow the formation of ylides directly from C-C triple bonds to achieve efficient reactions. The mode of formation of the intermediate carbenoid is shown to have a direct influence on the outcome of the rearrangement (Figures 1 and 2).[1,2]An ynamide based route has been developed featuring a fully intermolecular oxidation and ylide formation sequence allowing reactions of sulfur ylides to be accessed in a predictable fashion (Figure 2).[2]This approach allows the pre-installation and handling of potentially hazardous and high-energy diazo groups to be avoided. The reaction development and substrate scope will be discussed alongside the selectivity issues associated with the observed reactivity.[1] P. W. Davies and S. J. C. Albrecht, Synlett, 2012  , 23, 70-73; P. W. Davies and S. J. C. Albrecht, Chem. Commun., 2008  , 238.[2] M. Dos Santos and P. W. Davies,* Submitted manuscript

Gold-catalysed diazo-free approaches to access sulfur ylide based reactivity

248th National Meeting (2014)

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