Woodward-Hoffmann forbidden [1,3]-sigmatropic rearrangement) through a dissociative intramolecular fragmentation-recombination event with high enantiospecificity (Fig. ). Substitution reactions that proceed with retention of configuration are rare, although recognised for alcohols via an SNi mechanism that proceed via contact ion-paired intermediates . Traditionally the stereospecificity of nucleophilic substitution processes leads to inversion of configuration in SN2 reaction processes at secondary centres and partial or complete racemisation in SN1 processes at tertiary centres. However recent advances have showcased stereospecific substitution at tertiary and even quaternary centres in which stereochemical information is conferred despite ionization of a substrate . In this context, the high enantiospecificity of the observed chirality transfer protocol that leads to [1,2]-products with retention of configuration, while proceeding through an ionic fragmentation and recombination process, is significant and holds promise for the elucidation of alternative reaction pathways for generating chiral products with high enantioselectivity.