Development and synthetic applications of asymmetric [3,3]-sigmatropic rearrangments

In this review we have sought to g,ive the reader an appreciation of the ma ny synthetic applications now known for the more popular asymmetric [3,3]-s igmatropic rearrangements. The ability to predict the stereochemical outcom e of the rearrangements, and the ability to prepare products containing sev eral contiguous chiral centres makes the application of such asymmetric rea rrangements an attractive proposition to the synthetic chemist. We, and others, have begun to develop the armine-Cope rearrangement as a ne w synthetic protocol that appears to have much untapped potential. The ques tion 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. O ur progress in this area will be reported in due course.