The reduction of ketones with pinacolborane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) is catalyzed by 5 mol % NaOt-Bu at ambient temperature. The reaction is high yielding and general, providing complete conversion of aryl and dialkyl ketones. Although spectroscopic studies of the active hydride source in benzene-d(6) were complicated due to poor solubility, the data are consistent with the active hydride source being the trialkoxyborohydride, which is believed to be present in low concentration under the reaction conditions. Performing analogous studies in tetrahydrofuran resulted in a complex equilibrium between several different boron-containing species in which the trialkoxyborohydride compound was the major species.

The iridium-catalyzed arene C-H borylation reaction of benzylic amines has been developed, which inverts the typical steric-controlled product distribution to provide ortho-substituted boronate esters. Picolylamine was found to be an ideal ligand to replace 4,4'-di-tert-butylbipyridine to induce the directing effect. Preliminary experiments are consistent with a mechanism involving dissociation of one amine of the hemilabile diamine ligand.

Treatment of benzylic amines as well as phenethylamines and imidazolidine derivatives of type (XII) with the boronate (II) results in selective formation of ortho‐borylated products.