Evolution, Development and Personal Experience in Studies of the Allyl Cyanate-to-Isocyanate Rearrangement

Evolution and development of the synthesis and rearrangement of allyl cyanate is described. Allyl cyanate-to-isocyanate rearrangement is a concerted [3.3]-sigmatropic process involving highly selective [1,3]-chirality transfer to the newly formed asymmetric center bearing nitrogen. The usefulness of this rearrangement is manifested by the synthesis of natural products containing nitrogen-substituted quaternary carbon atoms.