Among the available methods to increase the molecular complexity, sigmatropic rearrangements occupy a distinct position in organic synthesis. Despite being known for over a century sigmatropic rearrangement reactions of ylides via carbene transfer reaction have only recently come of age. Most of the ylide mediated rearrangement processes involve rupture of a σ‐bond and formation of a new bond between π‐bond and negatively charged atom followed by simultaneous redistribution of π‐electrons. This minireview describes the advances in this research area made in recent years, which now opens up metal‐catalyzed enantioselective sigmatropic rearrangement reactions, metal‐free photochemical rearrangement reactions and novel reaction pathways that can be accessed via ylide intermediates.

Depending on the solvent used, benzyl sulfides undergo in the presence of a rhodium( ii ) catalyst either [1,2]- or [2,3]-sigmatropic rearrangement.