Catalyzed hydroboration of nitrostyrenes and 4-vinylaniline: a mild and selective route to aniline derivatives containing boronate esters

Transition metal catalyzed reactions of catecholborane (HBcat; cat = 1,2-O2C6H4) with β-nitrostyrene and 3-nitrostyrene lead to products derived from competing hydrogenation and hydroboration of the alkene unit along with reduction of the nitro group. Hydroboration of 4-vinylaniline gave regioselective formation of either the branched or the linear organoboronate ester depending upon the catalyst precursors (i.e., RhCl(PPh3)3 or Rh(acac)(dppe) vs [Cp∗IrCl2]2) used to facilitate this reaction. Hydroboration products were converted to air-stable primary amines by addition of pinacol.