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. 1 Background 2 Evolution of the Allyl Cyanate-to-Isocyanate Rearrangement. A Personal History 3 The Stereochemistry and Mechanism of the Allyl Cyanateto-Isocyanate Rearrangement 4 Synthesis of Natural Products Containing Nitrogen-Substituted Quaternary Carbon Centers 5 Coda.