Functionalization of Dodecaborates by Mild and Efficient Pd-Catalyzed Formation of B-C Bonds with Boronic Acids

Hybrid organic-inorganic molecules have recently received great interest due to their unique properties, which give access to their implementation in biological and material sciences. Herein, a new synthetic approach for the direct-linkage of the purely inorganic dodecaborate cluster to organic building blocks through B-C bond is established, using boronic acids as functional groups on the organic moiety, reacting under Suzuki-Miyaura coupling conditions with iodo-undecahydridododecaborate. The choices of ligand (DavePhos) and solvent (N-methylpyrrolidone for electron-poor, CD3CN for electron-rich groups) are essential for the successful coupling. Ultimately, the newly described methodology is found to be functional-group tolerant covering a wide spectrum of substrates including electron-poor arenes. Suzuki cross-coupling between iodo-dodecaborate and organic boronic acids succeeds. DavePhos is optimal as ligand. For electron-rich aromatics and aliphatics, CD3CN is best solvent, and N-methylpyrrolidone for electron-poor aromatics.**image