Abstract
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-pyrrolidinylmethyl]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 0°C gave optically active polymers in good yields. Although the polymer obtained from 2 with n-BuLi at 0°C showed a low stereoregularity, the anionic polymerization of 1 and 3 gave the polymers with a high stereoregularity, which was supported by 13C NMR analysis. The poly(1) 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.
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6: 1H NMR (400 MHz, CDCl3, δ, ppm): 1.58–1.73 (m, 3H, CH2), 1.94 (m, 1H, CH2), 2.19 (m, 1H, NCH2), 2.37 (s, 3H, CH3Ph), 2.72 (m, 1H, NCH2), 2.88 (m, 1H, NCH), 3.33 (s, 3H, OCH3), 3.29–3.44 (m, 3H, PhCH2N, and CH2O), 4.11 (d, 1H, J=13.2 Hz, CH2O), 7.10–7.29 (m, 4H, aromatic). IR (neat, cm-1) 2962, 2872, 2807, 1699, 1604, 1460, 1196, 1111, 743. MS (FAB) m/z 220 ([M+H]+).
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Ajiro, H., Habaue, S. & Okamoto, Y. Stereochemistry in Anionic Polymerization of Styrene Derivatives Bearing Optically Active Amino Groups at ortho-Position. Polym J 34, 57–62 (2002). https://doi.org/10.1295/polymj.34.57
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DOI: https://doi.org/10.1295/polymj.34.57