Sulfur chemistry on the solid phase

This thesis is concerned with the chemistry of thioesters immobilised on solid supports, and radical cyclisations of solid-supported 1,6-dienes using sulfur-centred radicals. A new method for linking substrates to a solid support using a thioester linkage is described, in which a thioamide is reacted with either Merrifield resin or a brominated Wang linker on a polystyrene bead, in the presence of aqueous DMF and sodium iodide. New methods for cleaving substrates linked to a solid support through a thioester linker are discussed, leading to tertiary alcohols, ketones and lactones, all in good yield. The cyclisation of a range of 1,6-dienes using phenylthiyl radicals is described, both for resin-bound substrates and those in solution. The 1,6-dienes are immobilised on solid-support using a malonate linker. The diastereoselectivity of the cyclisation reaction is also reported. Radical cyclisations of the aforementioned 1,6-dienes using p-tolyl benzeneselenosulfonate are also described, for both resin-bound substrates and those in solution. The diastereoselectivity of the cyclisation reaction is also reported.