S. Itsuno, K. Komura / Tetrahedron 58 (2002) 8237–8246
8245
1
1
Compound 16a. H NMR (DMSO-d6) 8.06 (br, 4H), 7.43
Compound 20b. H NMR (CDCl3) 8.18–7.05 (br, 22H),
6.40 (s, 2H), 5.93 (s, 2H), 3.68 (br, 2H), 3.41 (br, 2H), 2.13
(s, 6H), 0.61 (t, 4H), 0.27s, 12H).
(br, 8H), 5.41 (br, 2H), 5.13 (br, 2H), 3.55–3.27 (m,
4H), 0.49 (s, 6H). IR (KBr) 3471, 1681, 1208, 814.
[a]D¼þ101, [F]405¼þ1670 (c 1.00, DMSO). Anal. calcd
for (C26H26O4Si)n: C, 68.09; H, 5.71. Found: C, 67.89; H,
5.69.
1
Compound 21a. H NMR (CDCl3) 7.88–7.03 (br, 26H),
6.38 (t, 2H), 5.93 (s, 2H), 3.63 (br, 2H), 3.32 (br, 2H), 2.13
(s, 6H), 0.59 (s, 6H), 0.44 (s, 6H).
1
Compound 16b. H NMR (CDCl3) 8.03 (br, 4H), 7.45 (br,
8H), 5.32 (br, 2H), 3.37 (br, 6H), 0.63 (s, 4H), 0.24 (s, 12H).
1
Compound 21b. H NMR (CDCl3) 7.96–7.03 (br, 26H),
6.38 (t, 2H), 5.94 (s, 2H), 3.64 (br, 2H), 3.32 (br, 2H), 2.13
(s, 6H), 0.59 (s, 6H), 0.18 (t, 4H), 0.07 (s, 12H).
IR (KBr) 3476, 2953, 1681, 1207. [a]D¼þ76, [F]435
¼
þ1021 (c 1.00, THF). Anal. calcd for (C30H36O4Si2)n: C,
69.73; H, 7.02. Found: C, 69.54; H, 6.98%.
4.5.2. Asymmetric polymerization of 5 and 7. According
to the general method chiral polymer 17 was isolated as
white powder.
Acknowledgements
This work was partially supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education,
Science, Sports and Culture of Japan. Financial support
by the Amano Institute of Technology is also gratefully
acknowledged.
1
Compound 17a. H NMR (CDCl3) 7.90–7.39 (br, 16H),
5.33 (br, 2H), 3.50 (br, 2H), 3.33 (s, 4H), 0.59 (s, 6H), 0.54
(s, 6H). IR (KBr) 3466, 2956, 1677, 1212. [a]D¼þ78,
[F]435¼þ1143 (c 1.00, THF). Anal. calcd for
(C34H36O4Si2)n: C, 72.30; H, 6.42. Found: C, 72.41; H,
6.48.
References
1
Compound 17b. H NMR (CDCl3) 7.91–7.53 (br, 16H),
5.31 (br, 2H), 3.51 (br, 2H), 3.34 (s, 4H), 0.64 (s, 4H), 0.59
(s, 6H). IR (KBr) 3467, 2953, 1677, 1250. [a]D¼þ61,
[F]435¼þ1058 (c 1.00, THF). Anal. calcd for
(C38H46O4Si3)n: C, 70.11; H, 7.12. Found: C, 70.01; H,
7.13%.
1. Okamoto, Y.; Nakano, T. Chem. Rev. 1994, 94, 349.
2. Coates, G. W. Comprehensive Asymmetric Catalysis,
Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer:
Berlin, 1999; Vol. III, p 1329.
3. Nozaki, K. Kobunshi Ronbunshu 2001, 58, 375.
4. Comprehensive Asymmetric Catalysis, Jacobsen, E. N., Pfaltz,
A., Yamamoto, H., Eds.;, 1999; Vols. I–III.
4.6. Preparation of O-acetylmandelate of aldol adduct 3c
5. Catalytic Asymmetric Synthesis. 2nd ed. Ojima, I., Ed.;
Wiley–VCH: New York, 2000.
O-acetylmandelate 19 was prepared according to the
procedure described in the literature.21
6. Kamahori, K.; Tada, S.; Ito, K.; Itsuno, S. Macromolecules
1999, 32, 541.
Compound 19. 1H NMR (CDCl3) 7.93–7.06 (m, 15H), 6.40
(t, J¼6.7 Hz, 1H), 5.96 (s, 1H), 3.64 (dd, J¼7.4, 17 Hz, 1H),
3.35 (dd, J¼5.8, 17 Hz, 1H), 2.15 (s, 3H). 13C NMR
(CDCl3) 195.79, 170.39, 167.74, 139.28, 136.81, 133.80,
133.62, 129.41, 128.92, 128.89, 128.61, 128.39, 128.16,
126.45, 74.54, 73.76, 45.21, 20.94. Anal. calcd for
C25H22O5: C, 74.61; H, 5.51. Found: C, 74.55; H, 5.47%.
7. (a) Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976,
1295–1298. (b) Hosomi, A. Acc. Chem. Res. 1988, 21, 200.
8. Kumagai, T.; Itsuno, S. Macromolecules 2001, 34, 7624.
9. Kumagai, T.; Itsuno, S. Macromolecules 2000, 33, 4995.
10. (a) Komura, K.; Itsuno, S. Chem. Lett. 2001, 730. (b) Komura,
K.; Itsuno, S. J. Macromol. Chem. Phys. 2002, 203, 931.
11. (a) Kiyooka, S.; Kaneko, Y.; Komura, M.; Matsuo, H.;
Nakano, M. J. Org. Chem. 1991, 56, 2267. (b) Kiyooka, S.
J. Synth. Org. Chem. Jpn 1997, 55, 313.
4.7. Preparation of O-acetylmandelate of chiral polymer
12. (a) Ishihara, K.; Kondo, S.; Yamamoto, Y. Synlett 1999, 1283.
(b) Ishihara, K.; Kondo, S.; Yamamoto, Y. J. Org. Chem.
2000, 65, 9125.
To a solution of chiral polymer (113 mg) (R)-O-acetylman-
delic acid (100 mg, 0.5 mmol) and dimethylaminopyridine
(10 mg) in CH2Cl2 (2 mL) was added a solution of
1,3-dicyclohexylcarbodiimide (100 mg, 0.48 mmol) at
2108C. After being stirred at room temperature for 12 h
precipitated urea was filtered and the solvent was evapo-
rated. The residue was dissolved in CH2Cl2 and the
remained urea was filtered again and the solvent was
evaporated. The solid obtained was dissolved in THF and
poured into MeOH/H2O (1:1) to precipitate the polymer.
After filtration the polymer was dried in vacuo at 408C for
4 h. The optical purity of the chiral polymer was determined
by the ratio of the diastereomeric methylene protons.
13. Kumagai, T.; Itsuno, S. Tetrahedron: Asymmetry 2001, 12,
2509.
14. Komura, K.; Nishitani, N.; Itsuno, S. Polym. J. 1999, 31, 1045.
15. Peishoff, C. E.; Jorgensen, W. L. J. Org. Chem. 1983, 48,
1970.
16. (a) Nozaki, K.; Nakano, K.; Hiyama, T. J. Am. Chem. Soc.
1999, 121, 11008. (b) Chen, M.; Darling, N. A.; Lobkovsky,
E. B.; Coates, G. W. Chem. Commun. 2007, 2000. (c) Ito, Y.;
Miyake, T.; Hatano, S.; Shima, R.; Ohara, T.; Suginome, M.
J. Am. Chem. Soc. 1998, 120, 11880. (d) Okamoto, Y.;
Yashima, E.; Nakano, T.; Hatada, K. Chem. Lett. 1987, 759.
17. Seco, J. M.; Quinora, E.; Riguera, R. Tetrahedron: Asymmetry
2000, 12, 2915.
Compound 20a. 1H NMR (DMSO-d6) 8.27–7.13 (br, 18H),
6.30 (s, 2H), 5.56 (s, 2H), 3.40 (br, 2H), 3.17 (br, 2H), 2.20
(s, 6H), 2.07 (s, 6H).
18. Sen reported that the degree of asymmetric induction in the
formation of propylene–carbon monoxide copolymer was