Palladium‐Catalyzed Aryloxycarbonylayion of Aryl Bromides with Phenols Using Inositol Hexaformate as an Efficient CO Source

Carbonylation represents a straightforward and powerful strategy for installing carbonyl groups into organic molecules. However, the widespread adoption of carbon monoxide gas in laboratories is hampered by its toxicity, flammability, and smell‐less properties. To address these challenges, we developed a new carbon monoxide surrogate, inositol hexaformate (HFI), and demonstrated its utility in the palladium‐catalyzed aryloxycarbonylation of aryl bromides with phenols. Notably, HFI efficiently releases six equivalents of carbon monoxide, showing a significant improvement in efficiency over commonly used formate surrogates. This work provides a practical and robust method for conducting carbonylation reactions, which is expected to broaden the accessibility of this important transformation in synthetic chemistry.