Silicon holds a privileged position in organic chemistry as the carbon-silicon bond can be utilised in many important transformations. As such, developing practical and efficient methods for the enantioselective and regioselective insertion of silicon into organic molecules is a worthy challenge in chemical synthesis. To this end, we have developed an affordable copper-catalysed protocol for the asymmetric silylation of lactones, lactams and amides, providing silylated products with up to >99:1 er and in good yields. Furthermore, we have demonstrated the synthetic utility of this protocol in the target synthesis of natural or biologically active molecules.We also present the first copper-catalysed silylation of allenes using a silylborane reagent. This affords useful allyl- or vinylsilane building blocks with high regioselectivity, efficiency and a large functional group tolerance. The allylcopper intermediates can be intercepted by aldehydes in a diastereoselective three-component coupling to furnish homoallylic alcohols. We extend this concept to the copper-catalysed three-component coupling of boron, allenes and imines, providing access to homoallylic amines with a vinylborane motif.
Date of Award | 31 Dec 2015 |
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Original language | English |
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Awarding Institution | - The University of Manchester
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Supervisor | David Procter (Supervisor) |
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- Allene
- Boron
- Catalysis
- Enantioselective
- Copper
- Silicon
Copper-catalysed silicon and boron functionalisation of heterocycles and allenes
Rae, J. (Author). 31 Dec 2015
Student thesis: Phd