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Diastereomeric splitting of the doublet signal due to the CH3-protons of the isopropyl group was seen at 0.47 and 0.53 ppm.
Solution of (R)-(+)-[(+)-menthyloxy]methyl(1-naphthyl)phenylsilane (4.1 g, 10.1 mmol, 99% d.e.)6 in CHCl3 (80 mL) was reacted with CHCl3 solution of bromine (0.5 mol dm−3, 20 mL, 10.0 mmol) at −64°C for 60 min. The d.e. of the product was determined from the integral ratio of the signals at 0.62 and 0.79 ppm due to the CH3-protons of the isopropyl group to be 78.9%. 1H NMR (CDCl3, ppm): 0.62, 0.79 (two d, 3H, J=6.8 Hz, Hi), 0.84 (s, 3H, SiCH3), 0.85–0.93 (m, 9H, Ha, Hc, Hi), 1.07 (m, 1H, Hg), 1.27 (m, 1H, He), 1.37 (m, 1H, Hb), 1.64 (m, 1H, Hd), 1.99 (m, 3H, Hg, SiCH2), 2.18 (m, 1H, Hh), 3.79 (m, 1H, Hf), 7.05–8.25 (m, 5H, phenyl protons).
To a cooled (at −78°C) ether (40 mL) solution containing excess allylmagnesium bromide, the solution of the products of above reaction was transferred using Teflon tube at −64°C, and reacted for 3.5 h. After eluting formed bromonaphthalene with hexane, the product was isolated by silica gel column chromatography with hexane:ethyl acetate=20:1 (Rf=0.2). 59.3% yield. Diastereomer excess determined from the integral ratio of the signals at 0.60 and 0.63 ppm due to the CH3 protons of the isopropyl group was 76.5%. 1H NMR (CDCl3, ppm): 0.407, 0413 (two s, 3H, SiCH3), 0.60, 0.63 (two d, 3H, J=6.8 Hz, Hi), 0.78–0.90 (m, 9H, Ha, Hc, Hi), 0.98–1.07 (m, 1H, Hg), 1.15–1.21 (m, 1H, He), 1.24–1.34 (m, 1H, Hb), 1.54–1.62 (m, 1H, Hd), 1.79–1.94 (m, 3H, Hg, SiCH2), 2.17–2.25 (m, 1H, Hh), 3.43 (m, 1H, Hf), 4.86 (d with fine coupling, J=9.0 Hz, 1H, cis-CH2CH=CH2), 4.90 (d with fine coupling, J=16.5 Hz, 1H, trans-CH2CH=CH2), 5.74–5.83 (m, 1H, CH2CH=CH2), 7.34–7.41,7.57–7.60 (m, 5H, phenyl protons). IR (neat, cm−1): 3070 (ν aromatic and vinylic C-H), 2956 (νas CH3), 2921 (νas CH2), ∼2870 (νs CH3 and CH2), 1630 (ν C=C).
(S)-Allyl[(+)-menthyloxy]methylphenylsilane (2.67 g, 8.5 mmol) was reduced by lithium aluminum hydride (0.40 g, 10.6 mmol) in diethyl ether (10 mL) and dibutyl ether (12 mL) mixed solvent at 80–90°C for 10 h. The product was isolated by silica gel column chromatography (eluent:hexane) and further purified by distillation. 54–56°C (1.1 mmHg). 54.4% yield. [α]D26=+24.0 (c 1.00, pentane). 1H NMR (CDCl3, ppm): 0.36 (d, J=3.5 Hz, 3H, SiCH3), 1.79–1.90 (m, 2H, SiCH2), 4.36 (tq, J1=J2=3.5 Hz, 1H, SiH), 4.89 (d with fine coupling, J=10.0 Hz, 1H, cis-CH2CH=CH2), 4.92 (d with fine coupling, J=17.0 Hz, 1H, trans-CH2CH=CH2), 5.77–5.86 (m, 1H, CH2CH=CH2), 7.34–7.41, 7.53–7.56 (m, 5H, phenyl protons). IR (neat, cm−1): 3100–3000 (ν aromatic and vinylic C-H), 2964 (νas CH3), 2918 (νas CH2), 2889 (νs CH3), 2123 (ν Si-H), 1631 (ν C=C).
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Polymerizations were carried out similarly as reported by ref 5. 1H NMR and IR spectra of the polymers showed reasonable data.
K. Kobayashi, T. Kato, M. Unno, and S. Masuda, Bull. Chem. Soc. Jpn., 70, 1393 (1997).
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Kawakami, Y., Takahashi, T., Yada, Y. et al. Elucidation of the Stereochemical Pathway to Isotactic Poly[(methylphenylsilylene)trimethylene] from Allylmethylphenylsilane. Polym J 30, 1001–1003 (1998). https://doi.org/10.1295/polymj.30.1001
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