Organosilicon reagents in carbon-carbon bond forming reactions: towards the total synthesis of incednine

Thesis

This thesis investigates a total synthesis of the incednine aglycon by utilising alkenylsilane reagents to assemble the pentaenyl and tetraenyl systems through cross-coupling reactions. The early chapters develop methodology to access both cyclic alkenylsiloxanes and functionalised (E)-alkenylsilanes by the controlled hydrogenation of alkynylsiloxanes and silylolefination of aldehydes, respectively, and culminate in the synthesis of a C6-C13 bis(alkenylsilane)incednine fragment (Scheme 1).

The C1-C5 and C14-C23 coupling partners are synthesised in three and ten steps from propargyl alcohol and L-alanine methyl ester through phosphorous-based olefination strategies. In the final chapter we describe our first generation approach to incednine which entails orthogonal cross-couplings to construct the C5-C6 and C13-C14 bonds (Scheme 2).

Authors: Lim, D

• Publication date: 2013
• DOI: 10.5287/ora-9ezrvxrbv
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: Oxford University, UK
• Language: English
• Keywords: Organosilicon; Incednine; Cross-coupling
• Subjects: Organic chemistry; Organic synthesis; Natural products