Chiral nucleophilic podand catalysts for asymmetric phosphoryl transfer

ORGN 752

Alan Rolfe, chp02ar@sheffield.ac.uk and Simon Jones, simon.jones@sheffield.ac.uk. Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, United Kingdom
In recent years there has been a great deal of interest in the development of nucleophilic catalysts that can achieve high levels of stereoselectivity in a range of synthetic transformations. Nucelophilic catalysts 1 & 2 have been proposed as catalysts for the resolution of secondary alcohols by phosphoryl group transfer. The simplicity of the catalyst structure allows for large substrate diversity while maintaining high catalytic rate. The reduction in rate due to the steric bulk of the polyether side-chain is overcome by the addition of metal salts to give a co-operative rate enhancement. This co-operative effect controls the conformation of the catalyst system such to allows key sterogenic elements to be placed along the trajectory of approach of an incoming nucleophile. The use of these catalysts in the asymmetric phosphorylation of racemic alcohol substrates is discussed.