JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Chiral Ionic Polymer Catalysts for Asymmetric Reaction
reaction mixture was then stirred at 0 °C for 7 h and aque-
ous solution of NaOH (0.5 N, 20.0 mL) was added to the re-
action mixture. The light yellow colored solution obtained
was concentrated in vacuo to give a solid. EtOH (6 mL)
was then added to the solid and filtered. The solid was
washed with EtOH and dried under reduced pressure to
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.0 (m,
Ar-H), 8.3~7.8 (m, Ar-H), 7.5~7.2 (m, Ar-H), 6.8~6.6 (m,
Ar-H), 5.67 (m), 5.2~4.9 (m), 4.3~3.4 (m), 2.8 (m), 2.2~1.7
(m), 1.27 (m).
Synthesis of 13aBc 90% yield. 1H NMR (d6-DMSO,
400 MHz) d ppm 9.0~8.8 (m, Ar-H), 8.6~8.5 (m, Ar-H),
8.3~7.6 (m, Ar-H), 7.5~7.1 (m, Ar-H), 6.9~6.6 (m, Ar-H),
6.2 (m), 5.7~5.6 (m), 5.3~4.9 (m), 4.5~3.9 (m), 3.7~3.4
(m). 2.9~2.6 (m), 2.1~1.9 (m), 1.7~0.7 (m).
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give 9c in 85% yield. H NMR (d6-DMSO, 300 MHz) d
8.18 (d, J = 1.5 Hz, 1H), 8.12 (d, J = 9.00 Hz), 7.61 (d, J =
9.30 Hz, 1H), 7.44 (dd, J = 1.80, 1.50 Hz, 1H), 6.87 (d, J =
8.70, 1H), 3.71 (s, 3H). Anal. Calc. for C22H16Na2O8S2: C,
50.96; H, 3.11. Found: C, 50.68; H, 3.06.
Synthesis of 13aCa 92% yield. [a]D25 = 119.25 (c
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1.0, DMSO). H NMR (d6-DMSO, 400 MHz) d ppm 9.0
General procedure for the synthesis of ionic polymer
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(m, Ar-H), 8.3 (m, Ar-H), 8.1 (m, Ar-H), 7.9~7.8 (m, Ar-
H), 7.0~7.6 (m, Ar-H), 5.7 (m), 5.2~4.9 (m), 4.5~3.8 (m),
3.5~3.4 (m), 2.9~2.7 (m). 2.54 (m), 2.1~2.0 (m), 1.5 (m),
1.3 (m).
Synthesis of 13aCb 90% yield. [a]D25 = 144.64 (c
1.0, DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.0
(m, Ar-H), 8.3~8.1 (m, Ar-H), 7.9~7.7 (m, Ar-H), 7.4~7.2
(m, Ar-H), 6.9~6.6 (m), 5.7 (m), 5.3~4.9 (m), 4.5~3.8 (m),
3.5~3.4 (m), 2.7 (m), 2.2~1.7 (m), 1.3~1.2 (m).
Synthesis of 13aCc 88% yield. [a]D25 = 157.27 (c
1.0, DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.0~
8.98 (m, Ar-H), 8.36~8.33 (m, Ar-H), 8.2~8.0 (m, Ar-H),
7.95~7.83 (m, Ar-H), 7.8~7.7 (m, Ar-H), 7.61~7.58 (m,
Ar-H), 7.45~7.42 (m, Ar-H), 6.93~6.84 (m, Ar-H), 6.6 (m),
5.7~5.6 (m). 5.3~5.2 (m), 4.95~4.92 (m), 4.32 (m), 3.99~
3.94 (m), 3.83~3.80 (m), 3.7 (m), 3.6~3.5 (m), 3.37 (m),
2.74 (m), 2.54 (m), 2.1~1.9 (m), 1.8 (m).
Synthesis of 13bAa 85% yield. [a]D25 = 2.51 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.2~9.0
(m, Ar-H), 8.7~8.5 (m, Ar-H), 8.2~8.1 (m, Ar-H), 8.0~7.8
(m, Ar-H), 7.1~7.0 (m, Ar-H), 6.8~6.5 (m), 6.35~6.30 (m),
5.96~5.92 (m), 5.8~5.6 (m), 5.49~5.46 (m), 5.03~4.96 (m),
4.6~2.58 (m), 4.26~4.22 (m), 4.0 ~3.7 (m), 3.5~3.4 (m),
2.8~2.7 (m), 2.4~2.3 (m), 2.0~1.8 (m), 1.5~1.4 (m).
Synthesis of 13bAb 80% yield. [a]D25 = 2.19 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.3~9.0
(m, Ar-H), 8.6 (m, Ar-H), 8.2~7.5 (m, Ar-H), 7.3~6.9 (m,
Ar-H), 6.6~6.02 (m), 5.9~5.5 (m), 5.0~4.0 (m), 3.7~3.4
(m), 2.1~1.0 (m).
A solution of dimeric quaternary ammonium salt 3
(0.5 mmol) and disodium disulfonate 9 (0.5 mmol) in meth-
anol (5 mL) was stirred vigorously at room temperature for
24 h. The solvent was then evaporated to give a suspension
of the ionic polymer. The precipitate was collected by fil-
tration and washed with water and hexane to give the ionic
polymer 13. The yield of the ionic polymer was in the range
of 75~90%. The intrinsic viscosity [a] of the ionic poly-
mers in DMSO at 40 °C was in the range of 0.10~0.20.
Synthesis of 13aAa 80% yield. [a]D25 = -3.11 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.1~8.6
(m, Ar-H), 8.2~7.9 (m, Ar-H), 7.3~6.7 (m, Ar-H), 6.0 (m),
5.7 (m), 5.0 (m), 4.5 (m), 3.9 (m), 3.3 (m), 3.0 (m), 2.2 (m),
1.9 (m), 1.6 (m).
Synthesis of 13aAb 82% yield. [a]D25 = 2.66 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.1~9.0
(m, Ar-H), 8.9~8.8 (m, Ar-H), 8.7~8.5 (m, Ar-H), 8.14~
8.12 (m, Ar-H), 7.9~7.8 (m, Ar-H), 7.44~7.42 (m, Ar-H),
7.4 (m), 7.3~7.2 (m, Ar-H), 7.14~7.11 (m, Ar-H), 7.0 (m,
Ar-H), 6.84~6.82 (m, Ar-H), 6.6~6.5 (m), 5.96~5.92 (m),
5.7~5.6 (m), 5.1~4.9 (m), 4.6~4.4 (m), 4.0~3.9 (m), 3.3
(m), 3.0 (m), 2.11~2.07 (m), 2.0~1.9 (m), 1.6~1.3 (m).
Synthesis of 13aAc 88% yield. [a]D25 = 1.25 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.2~ 8.6
(m, Ar-H), 8.3~7.3 (m, Ar-H), 6.9~6.8 (m, Ar-H), 6.0~5.9
(m), 5.3~4.5 (m), 3.0~2.7 (m), 2.4~1.0 (m).
Synthesis of 13aBa 85% yield. [a]D25 = 1.67 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.05~8.98
(m, Ar-H), 8.36~8.34 (m, Ar-H), 8.14~8.10 (m, Ar-H),
7.9~7.7 (m, Ar-H), 7.9~7.8 (m, Ar-H), 7.0~6.6 (m, Ar-H),
5.7~5.6 (m), 5.3~5.1 (m), 4.94~4.92 (m), 4.26 (m), 3.9~3.6
(m), 3.5~3.4 (m), 2.9~2.6 (m), 2.59~2.55 (m), 2.12~1.96
(m), 1.5 (m), 1.25 (m).
Synthesis of 13bAc 85% yield. [a]D25 = 2.25 (c 1.0,
DMSO). 1H NMR (d6-DMSO, 400 MHz) d ppm 9.2~9.0
(m, Ar-H), 8.6~8.5 (m, Ar-H), 8.2~8.0 (m, Ar-H), 7.9~7.7
(m, Ar-H), 7.6~7.5 (m, Ar-H), 7.34~7.32 (m, Ar-H), 7.0
(m, Ar-H), 6.8 (m), 6.6~6.2 (m), 6.0~5.6 (m), 5.5~5.4 (m),
5.0~4.9 (m), 4.6~4.2 (m), 3.9~3.5 (m), 3.4~3.3 (m), 2.6
(m), 2.2~1.7 (m), 1.6~1.2 (m).
Synthesis of 13aBb 88% yield. [a]D25 = 1.59 (c 1.0,
J. Chin. Chem. Soc. 2012, 59, 000-000
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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