Synthesis of aryltrifluoroborates
A nickel-catalyzed Miyaura borylation of aryl and heteroaryl halides and pseudohalides using tetrahydroxydiboron (BBA) proved to be widely functional group tolerant and applicable to the synthesis of a broad range of aryltrifluoroborates at room temperature.
A. Molander, L. N. Cavalcanti, C. García-García, J. Org. Chem., 2013, 78, 6427-6439.
A simple transition-metal-free borylation reaction of aryl bromides with bis-boronic acid (BBA) provides arylboronic acids at mild temperatures directly without any deprotection steps and purified by conversion to trifluoroborate salts. The functional group tolerance was considerably high.
T. Lim, J. Y. Ryoo, M. S. Han, J. Org. Chem., 2020, 85, 10966-10972.
A simple and efficient palladium-catalyzed reaction of aryl chlorides with tetrahydroxydiboron gives arylboronic acids. To ensure preservation of the carbon-boron bond, the boronic acids were efficiently converted in situ to trifluoroborate derivatives or boronates in very good yields. Finally, a two-step, one-pot method for the synthesis of biaryls from two aryl chlorides was developed.
G. A. Molander, S. L. J. Trice, S. D. Dreher, J. Am. Chem. Soc., 2010, 132, 17701-17703.
Arylboronic acids and aryl trifluoroborates are synthesized in a one-pot sequence by Ir-catalyzed borylation of arenes. To prepare the arylboronic acids, the Ir-catalyzed borylation is followed by oxidative cleavage of the pinacol boronates with NaIO4. To prepare the aryltrifluoroborate, the Ir-catalyzed borylation is followed by displacement of pinacol by KHF2.
J. M. Murphy, C. C. Tzschucke, J. F. Hartwig, Org. Lett., 2007, 9, 757-760.