Iridium-Catalyzed sp³ C–H Borylation in Hydrocarbon Solvent Enabled by 2,2′-Dipyridylarylmethane Ligands

Abstract

Iridium-catalyzed alkane C-H borylation has long suffered from poor atom economy, resulting from both the inclusion of only 1 equiv of boron from the diboron reagent and a requirement for neat substrate. An appropriately substituted dipyridylarylmethane ligand was found to give highly active alkane borylation catalysts that facilitate C-H borylation with improved efficiency. This system provides for complete consumption of the diboron reagent, producing 2 molar equivalents of product at low catalyst loadings. The superior efficacy of this system also enables borylation of unactivated alkanes in hydrocarbon solvent with a reduced excess of substrate and improved functional group compatibility. The effectiveness of this ligand is displayed across a selection of functional groups, both under traditional borylation conditions in neat substrate and under atypical conditions in cyclohexane solvent. The utility of this catalytic system is exemplified by the borylation of substrates containing polar functionality, which are unreactive toward C-H borylation under neat conditions.