The formation of a single product from terminal functionalization of linear alkanes from a transition metal-catalyzed reaction is reported. The rhodium complex Cp*Rh(eta(4)-C6Me6) (Cp*, C5Me5; Me, methyl) catalyzes the high-yield formation of linear alkylboranes from commercially available borane reagents under thermal conditions. These reactions now allow catalytic, regiospecific functionalization of alkanes under thermal conditions. The organoborane products are among the most versatile synthetic intermediates in chemistry and serve as convenient precursors to alcohols, amines, and other common classes of functionalized molecules.