Pushing the Ir-catalyzed C-H polyborylation of aromatic compounds to maximum capacity by exploiting reversibility

J Am Chem Soc. 2012 Sep 19;134(37):15169-72. doi: 10.1021/ja307547j. Epub 2012 Sep 5.


Small amounts of base (e.g., 10% potassium t-butoxide or sodium methoxide) have been found to promote equilibration of the kinetically favored products from Ir-catalyzed C-H polyborylations of aromatic compounds. In the presence of excess borylating agent, bis(pinacolato)diborane (B(2)pin(2)), repetitive deborylation/reborylations reposition the Bpin substituents until a pattern that accommodates the maximum number of Bpin substituents is achieved. A high-yield, one-step synthesis of 1,3,5,7,9-pentakis(Bpin)corannulene is reported that illustrates this useful extension of the Ir-catalyzed borylation reaction.