Carbene-induced ring-opening reactions of five-/six-membered cyclic ethers: expanding the frontiers of functional group introduction and molecular architecture construction

The multi-component ring-opening reactions of cyclic ethers offer an efficient strategy for the rapid introduction of multiple functional groups and the construction of complex molecular architectures. Despite the minimal ring strain in five- and six-membered rings presenting a significant challenge for ring-opening, advancements have been made. Traditional acid-catalyzed pathways have been complemented by a novel approach involving carbene-induced oxonium intermediate formation, which has emerged in recent years and expanded the selectivity of ring-opening reactions. This review outlines the evolution of carbene-induced ring-opening reactions of cyclic ethers over the past two decades, focusing on the development of carbene precursors and the pathways of carbene formation. The insights provided are anticipated to inform and inspire the creation of new carbene sources and the advancement of oxonium intermediates, thereby contributing to the field's progress.