Stereochemistry in anionic polymerization of styrene derivatives bearing optically active amino groups at ortho-position

Three ortho-substituted styrenes, 2-[(S)-2-(1-pyrrolidinylmethyl)-1-pyrrolidinylmethyl] styrene (1), 2- [(S)-2-(methoxymethyl)-1-pyrrolidinylmethyl] styrene (2), and 2-[(S)-2-(N,N-diethylaminomethyl)-1-pyrrolidinylmethy 1] styrene (3), were synthesized, and the effects of the ortho-substituents on polymerizability and the stereoregularity and chiroptical property of the polymers obtained by anionic method were examined. The anionic polymerization of 1-3 with n-BuLi in toluene at 0degreesC gave optically active polymers in good yields. Although the polymer obtained from 2 with n-BuLi at 0degreesC showed a low stereoregularity, the anionic polymerization of 1 and 3 gave the polymers with a high stereoregularity, which was supported by C-13 NMR analysis. The poly(l) and poly(3) are likely to have regular conformation. Enantioselective oxidative coupling of a naphthol derivative was carried out using poly(1)s as a chiral ligand to obtain a corresponding 2,2'-binaphthol derivative.