Chemical synthesis relies on the presence of functional groups to control the formation of new bonds. The area of catalytic C–H bond functionalisation offers a pioneering opportunity to develop highly efficient, ‘green’ and new chemical transformation that will be pivotal in the future development of chemical synthesis. While we are not suggesting that this approach will replace the conventional tactics of molecule assembly it does offer the synthetic chemist the chance to explore completely unknown strategies. More specifically, it allows us to put the standard rulebook of disconnections to one side and invent a new set of reactions that allow us to break down a molecule without needing to locate a functional group in the synthons. Breaking a C–C, C–N or C–O bond back to a number of C–H bonds represents the pinnacle of modern synthetic chemistry. To achieve this would allow metal catalysed C–H bond functionalisation strategies to offer a conceptually new approach to synthesis that will compliment conventional synthesis and enable us to move a step closer to being able to assemble any desired molecule. As part of this proposal we aim to develop a metal catalyzed C–H bond functionalization strategy that will enable the rapid and flexible synthesis of the intriguing tubulin destabilizing agent, rhazinilam. Furthermore, we will also investigate a totally unprecedented natural product re-arrangement strategy that enables the facile conversion of the rhazinilam framework into the aspidospermidine framework. This rearrangement blueprint, that the Host group name ‘retro-biosynthesis’ as it goes against the proposed classical biosynthetetic pathway, provides immediate access to a family of compounds (the vinca alkaloids) that have potent biological activities in cancer medicine.