In the research presented herein, low-valent-tungsten-catalyzed hydroboration of esters and nitriles was investigated. Aromatic and aliphatic substrates were smoothly reduced to corresponding alcohol derivatives and N , N -diborylamines in the presence of W(CO) 4 (NCMe) 2 . Valuable derivatives were conveniently accessed by introducing a further functionalization process to crude hydroboration mixtures in one pot.