Third Year Organic Chemistry

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The Sharpless Asymmetric Epoxidation

Tutorial link: Oxidation
The Sharpless Asymmetric Epoxidation is arguably one of the most important reaction discovered in the last 30 years. This has been recongnised by the award of the 2001 Nobel Prize to Professor Barry Sharpless.

Sharpless's asymmetric epoxidation converts the double bond of allyl alcohols into epoxides using a transition metal catalyst (Ti(O-iPr)4), titanium tetra-isopropoxide) and a chiral additive (diethyl tartrate, DET). The source of the oxidant is cheap tertiary-butyl peroxide. The mechanism of the Sharpless epoxidation is quite complicated. Copy Info Folder Save Print

Co-ordination of the chiral ligand DET and the oxidant source t-BuOOH to the metal centre forms the catalytically active species. It is generally believed that this species is dimeric, i.e. two metal centres are bridged via two oxygen ligands giving the overall shape of two edge-fused octahedra. For greater clarity the DET ligand is only represented as blue lines in the figure above. Co-ordination of the substrate can only occur in one orientation without causing severe sterical interactions. Note, how the co-ordination in the complex on the left brings the double-bond over the peroxide oxygen of the t-BuOOH ligand. Oxidation can only occur from the bottom face leading overall to a highly enantioselective process.

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4/14/2008 10:55 PM