Development and Synthetic Applications of Asymmetric (3,3) Sigmatropic Rearrangments

In this review we have sought to give the reader an appreciation of the many synthetic applications now known for the more popular asymmetric (3,3)sigmatropic rearrangements. The ability to predict the stereochemical outcome of the rearrangements, and the ability to prepare products containing several contiguous chiral centres makes the application of such asymmetric rearrangements an attractive proposition to the synthetic chemist.We, and others, have begun to develop the amino-Cope rearrangement as a new synthetic protocol that appears to have much untapped potential. The question of the whether the rearrangement proceeds via a stepwise or concerted mechanism, and if the mechanistic pathway can be controlled, remains to be established. Current work in our group is aimed at applying the asymmetric amino-Cope rearrangement in synthetically useful procedures, for example in the synthesis of highly functionalised oxygen and nitrogen heterocycles. Our progress in this area will be reported in due course.