In 1975, Kono and Ito reported that Wilkinsons catalyst (Rh(PPh)Cl) can undergo oxidative addition with catecholborane (HBcat) or 4,4,6-trimethyl-1,3,2-dioxaborinane. These two borane compounds are otherwise slow to participate in hydroboration. In 1985, Männig and Nöth demonstrated for the first time that Wilkinsons catalyst indeed catalyzes hydroboration of alkenes with HBcat.
Whereas uncatalyzed hydroboration using HBcat leads to reduction of the carbonyl group, the catalyzed version is selective for the alkene.
As indicated by subsequent research, transition metal-catalyzed hydroboration proceeds with attractive functional group-, regio-, stereo-, and chemo- selectivity.