The oxidative coupling polymerizations of racemic-, (R)-, and (S)-2,2'-dimethoxymethoxy-1,1'-binaphthalene-3,3'-diols were carried out with a copper catalyst with various ligands, such as N,N,N',N'-tetramethylethylenediamine (TMEDA), (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine, (-)-sparteine, and (S)-(-)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline) [(-)-Phbox], under an O-2 atmosphere. For example, a 10/1 (v/v) MeOH (.) H2O-insoluble polymer with a number-average molecular weight of 3.8 x 10(3), from a polymerization with CuCl-TMEDA followed by acetylation of the hydroxyl groups, was obtained in a 71% yield. Polymerization with (-)-Phbox proceeded in an S-selective manner to give a polymer with the highest negative specific rotation from the (S)monomer. The obtained polymer was successfully converted into a polymer with the optically pure 1,1'-bi-2-naphthol unit based on the original monomer structure, which could be used as a polymeric chiral auxiliary and showed catalytic activity for the asymmetric diethylzinc addition reaction to aldehydes. (C) 2004 Wiley Periodicals, Inc.