Synthesis of <i>o</i> -benzyl benzamides <i>via</i> NaH-mediated aryne insertion into <i>N</i> -sulfonylacetimidates

<i>o</i>-Benzylbenzoic acid derivatives are valuable synthetic intermediates, but conventional syntheses suffer from limited functional group tolerance and dependence on transition metals. Herein, we report a NaH-mediated strategy for preparing <i>o</i>-benzyl benzamides <i>via</i> regioselective aryne insertion into the C-C bond of <i>N</i>-sulfonylacetimidates. This pathway diverges from classical benzimidate-forming routes, directly affording valuable amide products in a single step. Readily available <i>o</i>-diiodoarenes generate arynes <i>in situ</i> under NaH/THF conditions. The reaction exhibits excellent functional group compatibility. This transition-metal-free protocol not only provides an efficient and practical access to <i>o</i>-benzylbenzoic acid derivatives through a proposed hydrolytic mechanism but also represents a significant advancement in aryne chemistry by enabling a previously elusive direct synthesis of amides <i>via</i> C-C bond insertion, offering a new disconnection strategy for arene functionalization.