The synthesis of Cr(CO) 3 -complexed aromatic nitrones 2 is reported. These new planar-chiral complexes were fully characterized in solution by 1 H and 13 C NMR, IR and cyclic voltammetry. Moreover, structural data were obtained from X-ray structures of nitrones 2b, 2d, 2e and 2f. These analyses converge to give evidence of a favoured anti conformation of ortho-substituted nitrones, with an unusual N-O···H aryl intramolecular interaction forming a six-membered ring. The reactivity of these chiral nitrones in SmI 2 -induced pinacol-type reactions was investigated. The reductive cross-coupling of nitrones 2a-d with carbonyl compounds proved to be highly chemo- and diastereoselective and afforded precursors of enantioenriched β-amino alcohols in excellent yields.