This thesis describes the development of a novel Cu(I)-NHC catalysed silylation of allenes using a commercial available silylborane reagent and the synthesis of a range of vinylsilanes. During the development of the approach, a series of NHC ligands were synthesised and applied in reactions for optimizing the regioselectivity. Excellent regiocontrol was achieved with the use of a 7-membered cyclic NHC ligand. Moreover, a library of aryl allene derivatives synthesised in this work could be used in the Cu(I)-NHC catalysed silylation of allenes to afford a variety of vinylsilanes with high efficiency. Allylcoppper intermediates generated catalytically can be trapped by aldehydes to furnish homoallylic alcohols with high diastereoselectivity in a three-component coupling reaction. A range of vinylsilanes having significant potential in Hiyama cross-coupling and Fleming-Tamao oxidation reactions were successfully synthesised by the protocol of Cu(I)-NHC catalysed silylation of allenes and extension to the three-component coupling.
|Date of Award
|31 Dec 2014
- The University of Manchester
|David Procter (Supervisor) & Michael Ingleson (Supervisor)
- allenes · copper · homogeneous catalysis · Nheterocyclic carbenes · silylation