Ireland-Claisen Rearrangement as a Stereocontrolled Bond-Construction Strategy in Natural Product Total Synthesis.

Among stereoselective C-C bond-forming transformations in organic synthesis, the Ireland-Claisen rearrangement plays a distinct role as a reliable method for the construction of stereogenic centers and geometrically defined double bonds. Its synthetic value arises from the efficient transfer of stereochemical information through a highly ordered six-membered transition state, enabling rapid increases in molecular complexity under mild reaction conditions. This review highlights recent applications of the Ireland-Claisen rearrangement in natural product total synthesis, covering literature published during 2015-2025. The examples discussed demonstrate the broad utility of this transformation across structurally diverse natural product classes and illustrate how substrate structure, enolization conditions, and reaction design determine the stereochemical outcome in complex synthetic settings.