Recent Advances in Cycloaddition Reactions of Donor‐Acceptor Oxiranes via Carbon–Carbon Bond Cleavage

Oxiranes exhibit two distinct ring‐opening modes: cleavage of the C–O bond or cleavage of the C–C bond. Among these, reactions involving C–O bond cleavage have been extensively reviewed. This article provides an overview of the research progress over the past several decades on the cycloaddition reactions of donor‐acceptor (D‐A) oxiranes via C–C bond cleavage. Under suitable catalytic conditions, D‐A oxiranes undergo ring‐opening through C–C bond cleavage to form carbonyl ylides, which can participate in [3+n] cycloaddition reactions with aldehydes, imines, alkenes, alkynes, indoles, purines, etc.