The asymmetric desymmetrisation of meso compounds.

This thesis is concerned with the asymmetric desymmetrisation of meso compounds. It commences with an introduction to the areas of two-directional synthesis and asymmetric desymmetrisation. This is followed by a review of asymmetric desymmetrisation of achiral and meso compounds, illustrating the power of this technique and the diversity of substrates and reagents that can be employed. Chapter one details the asymmetric desymmetrisation of centrosymmetric meso 2-pyridone [4 + 4]-photodimer derivatives, as a strategy towards the synthesis of functionalised amino acids. The reductive enantioselective desymmetrisation of jY-Boc tetrahydro photodimer 227 using Corey’s oxazaborolidine catalyst 236 was achieved in good yield (76%) and excellent ee (>97%), representing the first ever asymmetric desymmetrisation of a centrosymmetric compound. Chapter two details the synthesis and asymmetric desymmetrisation of meso decalin diallylc alcohols as part of a strategy towards the synthesis of core structures of bioactive Celastracecie sesquiterpenes. The two-directional synthesis of diallylic alcohol 298 (a classical meso compound containing a plane of symmetry) was completed and its subsequent desymmetrisation using a novel Zr modified Sharpless asymmetric epoxidation proceeded in reasonable yield (54%) and excellent ee (>95%)