| Abstract: | The synthesis and applications of carboxy‐MIDA‐boronate, a novel C1 building block, are described. This molecule is accessible via a ruthenium tetraoxide‐mediated cleavage of commercially available ethynyl‐MIDA‐boronate. In the course of this study, carboxy‐MIDA‐boronate was found to possess ambident reactivity towards nucleophiles. Carboxylic acid derivatization produces a broad range of previously unknown carbamoyl‐, oxycarbo‐ and thiocarboboronates. Carboxy‐MIDA‐boronate and its derivatives undergo condensations to access borylated heterocycles with boron at positions that are difficult to access using alternate methods. The resulting heterocycles participate in the Suzuki–Miyaura cross‐coupling reaction, enabling entry into diverse bis(heteroaryl) motifs. The carbon monoxide‐releasing capacity of carboxy‐MIDA‐boronate was also examined and applied in palladium‐catalyzed carbonylation. |
