Medium-sized ring-containing organic molecules, especially seven-membered rings, are significant structural motifs. However, such frameworks are considered difficult structures to access owing to entropic effects and transannular interactions. Compared to the construction of five and six-membered rings, the synthesis of seven-membered rings can be more challenging through traditional cyclization pathways. Büchner reactions are particularly attractive and efficient synthetic strategies to construct functionalized seven-membered ring products from the benzenoid double bond with carbene. In recent years, the field of transition-metal-catalyzed Büchner ring expansion reactions of alkynes has experienced a speedy development and a diverse array of efficient synthetic procedures have been disclosed under mild experimental conditions, as the synthesis of synthetically challenging seven-membered rings is easily achieved. In this review, we will focus on the recent progress in the transition-metal-catalyzed Büchner reaction of alkynes and the mechanistic rationale is depicted where possible, with the reactions being sorted according to the type of catalyst.
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