The synthesis of organoboron compounds by metal-catalyzed carbon-hydrogen borylation of alkanes and arenes

Alkanes, although one of the most abundant chemical feedstocks, are relatively unreactive. A process that could directly convert alkanes into terminally functionalized compounds would be of great synthetic value. Two chapters of this dissertation describe the progress made towards the development of catalysts for alkane borylation systems. A series of ruthenium complexes has been found that catalyzes the selectively borylation of alkanes at the terminal position, yielding alpha-alkylboronic esters in excellent yields. It has been shown that these complexes will also catalyze the borylation of the least sterically hindered terminal methyl group both in branched alkanes and in substrates that contain heteroatoms, including ethers, fluoroalkanes, and amines. Hydrotris(pyrazolyl)borate iridium complexes have been shown to catalyze the reaction of alkanes with bis(pinacolato)diboron (B2pin 2), and it was observed that the addition of ionic additives significantly affects the yield of this borylation reaction. Also, we investigated the reaction of octane with B2pin2 catalyzed by the combination of Ru or Rh complexes and ionic additives, and these borylation reactions provide moderate to high yields of octylBpin at lower reaction temperatures.;Arene functionalization through C-H activation is more developed compared to alkane borylation chemistry. The development of a mild, efficient, and regioselective iridium catalyzed arene borylation system has allowed access to 3,5-disubstituted arylboronic esters in excellent yields starting from the corresponding arene. The Ir-catalyzed borylation of arenes has led to alternative syntheses of 3,5-disubstituted arylboronic acids, potassium aryltrifluoroborates, aryl bromides, and aryl chlorides. The development and the scope of these transformations are described in this dissertation.