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 O2 atmosphere. For example, a 10/1 (v/v) MeOH · H2O‐insoluble polymer with a number‐average molecular weight of 3.8 × 103, 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. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4528–4534, 2004

ABSTRACT:The asymmetric oxidative coupling polymerization of 6,6 0 -dihydroxy-2,2 0 -binaphthalene derivatives or methyl 3,7-dihydroxy-2-naphthoate, having an unsymmetric 2-naphthol structure, with copper catalysts under an O 2 atmosphere was carried out. The polymerization using the CuCl-(S)-2,2 0 -isopropylidenebis(4-phenyl-2-oxazoline) catalyst afforded a polymer with a high cross-coupling selectivity of up to 99%, which showed a number average molecular weight of 5:0{9:1 Â 10 3 . To estimate the stereoselectivity during the polymerization, a model reaction was examined which resulted in good to high cross-coupling selectivities, while the enantioselectivities were low. The polymer composed of a homo-coupling unit showed a photoluminescence spectral pattern similar to that of the model compound. In contrast, a very different emission, which may be due to the excimer, from that of the model was observed for the polymer consisted of the cross-coupling unit.