The complete series of chiral group IV sec-butoxides has been obtained by the treatment of M(NMe 2) 4 (M = Ti, Zr, Hf) with resolved ( R)-(−)- or ( S)-(+)-2-butanol. These complexes were analyzed by polarimetry, revealing a decreasing trend in molar rotation down the group, from titanium to hafnium. Catalysis screenings showed that the resolved titanium sec-butoxides, in conjunction with the resolved BINOL (BINOL = 1,1′-bi-2-naphthol) of the opposite configuration designation, catalyzed the addition of dimethyl zinc to benzaldehyde with higher enanteoselectivity than that observed for resolved BINOL with titanium(IV) isopropoxide or with the titanium(IV) sec-butoxide of the same configuration designation.