Arynes in glycochemistry: Emerging tools for carbohydrate functionalization

By exploiting the unique reactivity of benzynes toward carbohydrate frameworks, particularly their inherent propensity to undergo effective functionalization on vicinal positions of an arene ring, significant advances have been achieved in carbohydrate chemistry. These transformations have enabled the development of diverse and efficient strategies for modifying carbohydrate skeletons using benzyne intermediates. As a result, new pathways have emerged for the construction of structurally complex molecules and glycoconjugates that are otherwise challenging to access. In this review, we highlight recent progress in aryne-mediated transformations of carbohydrate substrates, with a particular emphasis on their application in the synthesis of novel glycoconjugates. Over the past decade, this rapidly evolving field has expanded considerably, offering innovative opportunities for molecular design and broadening the scope of synthetic glycoscience.