Detailed project information

This project generally aims at the development of novel methodology for the synthesis of oxygen heterocycles based on transition metal-mediated reactions of alkoxyallenes (alkyl 1,2-propadienyl ethers) that were recently developed in our group. The project can be divided inbto two parts:

- investigation of novel synthetic possibilities of differently substituted alkoxyallenes (or equivalents thereof) in the synthesis of heterocyclic building blocks and the exploration of follow-up chemistry. Given the occurrence of a wide variety of oxygen heterocycles, bicycles and more complicated structures in different classes of natural products with potent biological activity, extension of this methodology will be general interest.

- An important aspect of most parts of this proposal is functionalization of the obtained acetals via oxycarbenium ion-mediated CC-bond formation. Since the existing methods to do so are rather limited (an excess of Lewis acid is required, enantioselective versions do not exist), studies towards improvement of the current methodology will be undertaken. Therefore, the second part of this proposal comprises the determination of the scope and limitations of new classes of lanthanide-based Lewis acids for optimisation of oxycarbenium ion mediated CC-bond formation and the search for chiral Lewis acids that could catalyse this reaction in an enantioselective manner.

Financial support is requested for the appointment of a Ph.D.-student for a period of four years, an annual contribution for consumables of 15 kf and an amount of 30 kf to purchase chiral columns and an auto sampler for one of the GC-machines.