Optically active (1,2-disubstituted arene)chromium tricarbonyl complexes with a diamine and a phosphorus group in the two ortho benzylic positions were stereoselectively synthesized from a commercially available (+)-(4,6-O-benzylidene)methyl-α-D-glucopyranoside. These chromium complexes have been used as chiral ligands in the preparation of rhodium catalysts for the hydroboration of styrene derivatives. Moderate enantioselectivities were observed in the hydroboration of vinylarenes.