This proposal describes methods for enantioselective organocatalytic radical cascade polycyclisation reactions based on using the newly discovered techonology of SOMO catalysis. The past 8 years has seen tremendous progress in the field of organocatalysis. In particular the advent of both LUMO lowering imnium ion catalysis and HOMO raising enamine catalysis has seen the development of more than 60 new asymmetric methodologies. Very recently, the MacMillan group disclosed a new strategy which provides alternative reactivity compared with enamine or iminium catalysis. It was realised that the intimate equilibrium between enamine and iminium intermediates can be interrupted chemically by a single electron oxidation to form a 3pi-electron species containing a singly occupied molecular orbital (SOMO). This radical cation species was found to be capable of the typical reactivity pathways associated within the realm of radical chemistry and allowed access to a previously unknown set of organocatalytic transformations. This methodology is proposed to be applicable to the formation of multiple carbocyclic rings where the catalyst triggers an initial cyclisation resulting in a cascade reaction to form a complex steroid like framework. A biologically active steroid also has been identified as a target for this methodology. This possesses a interesting biological profile and potency against certain cancer cell lines. The methodology will also be flexible enough for analogue synthesis with the aim of discovering more potent compounds with potential for the treatment of cancer. In the return phase the applicant will study in the field of C-H activation which will compliment his training on the forefront of synthetic chemistry.
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