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NMR (270 MHz; CDCl3): d = 0.84 (d, J = 8.3 Hz, 2 H), 7.52 (d,
J = 8.3 Hz, 2 H), 6.75 (dd, J = 10.7, 17.6 Hz, 1 H), 5.89 (d,
J = 17.6 Hz, 1 H) , 5.43 (d, J = 10.7 Hz, 1 H), 5.26 (d, J = 6.4 Hz,
1 H), 3.82±3.70 (m, 2 H), 1.96 (d, J = 3.9 Hz, 1 H), 1.78±1.05 (m,
5 H), 0.85 (s, 3 H), 0.83 (s, 3 H), 0.80 (s, 3 H); [a]2D3 32.9 (c 3.0,
CH2Cl2); anal. calcd for C18H25NO3S (335.46): C 64.45, H 7.51,
N 4.18%; found: C 64.40, H 7.52, N 4.17%.
Experimental Section
General Methods
All reactions were carried out under an atmosphere of dry
nitrogen. Tetrahydrofuran (THF) and diethyl ether were
freshly distilled from sodium benzophenone ketyl under ni-
trogen immediately before use. Divinylbenzene (96% divi-
nylbenzene, 4% ethylbenzene) was a gift from Nippon Steel
Chemical Co., Ltd. N-(Trimethylsilyl)imines were obtained
by reaction of the corresponding aldehydes with lithium
hexamethyldisilazide according to the literature proce-
dure.[13] Reactions were monitored by thin layer chromato-
graphy (TLC) using Merck precoated silica gel plates
(Merck 5554, 60F254). Flash column chromatography was
performed over Wako silica gel (Wakogel C-200, 100±
200 mesh). Microanalyses were obtained using a YANACO
MT-3 CHN CORDER. 1H NMR spectra were measured on a
JEOL JNM-GX270 spectrometer using Me4Si as an internal
standard. Infrared spectra (IR) were recorded with a JEOL
JIR-7000 FT-IR spectrometer and are reported in reciprocal
centimeter (cm±1). Optical purity was determined with a
JASCO HPLC system composed of 3-line degasser DG-980-
50, HPLC pump PV-980, and column oven CO-965, equipped
with a chiral column (Chiralcel OD-H, Daicel) using hex-
ane : 2-propanol : diethylamine (90 : 10 : 0.1). A UV detector
(JASCO UV-975) was used for the peak detection. Optical ro-
tations were taken on a JASCO DIP-140 digital polarimeter
using a 10 cm thermostated microcell. Loadings of the poly-
mers are expressed in millimoles of functional groups per
gram of dry resin (mmol/g) or as degree of functionalization
(DF). For example, DF = 0.10 if 10% of the styrene units are
functionalized.
Chiral monomer 3: ((1R,2S)-2-(4-vinylbenzenesulfonyl)-
amino-1-phenylpropan-1-ol):
Yield: 96%; mp 93±95 °C; 1H NMR (270 MHz; CDCl3): d = 7.84
(d, J = 8.3 Hz, 2 H), 7.51, (d, J = 8.3 Hz, 2 H), 7.34±7.22 (m,
5 H), 6.74 (dd, J = 10.7, 17.6 Hz, 1 H), 5.87 (d, J = 17.6 Hz,
1 H), 5.43 (d, J = 10.7 Hz, 1 H), 5.16 (d, J = 8.8 Hz, 1 H), 4.80
(d, J = 2.9 Hz, 1 H), 3.62±3.55 (m, 1 H), 2.75 (br, s, 1 H), 0.85
(d, J = 6.8 Hz, 3 H); [a]2D3 ±12.07 (c 2.78, CHCl3); anal. calcd
for C17H19NO3S (317.40): C 64.33, H 6.03, N 4.41%; found: C
64.40, H 6.00, N 4.42%.
Chiral monomer 4: ((1S,2R)-2-(4-vinylbenzenesulfo-
nyl)amino-1-phenylpropan-1-ol):
Yield: 96%; mp 93±95 °C; 1H NMR (270 MHz; CDCl3): d = 7.84
(d, J = 8.3 Hz, 2 H), 7.51, (d, J = 8.3 Hz, 2 H), 7.34±7.22 (m,
5 H), 6.74 (dd, J = 10.7, 17.6 Hz, 1 H), 5.87 (d, J = 17.6 Hz,
1 H), 5.43 (d, J = 10.7 Hz, 1 H), 5.16 (d, J = 8.8 Hz, 1 H), 4.80
(d, J = 2.9 Hz, 1 H), 3.62±3.55 (m, 1 H), 2.75 (br, s, 1 H), 0.85
(d, J = 6.8 Hz, 3 H); [a]2D3 12.07 (c 2.78, CHCl3); anal. calcd for
C17H19NO3S (317.40): C 64.33, H 6.03, N 4.41%; found:
C 64.27, H 5.97, N 4.40%.
Preparation of Polymer-Supported Chiral N-Sulfonyla-
mino Alcohols
Chiral polymer 5
A solution of 1 (3.35 g, 10 mmol), styrene (8.32 g, 80 mmol),
divinylbenzene (1.36 g, 10 mmol), and 2,2'-azobis(2,4-di-
methylvaleronitrile) (0.25 g, 1 mmol) in a mixed solvent of
benzene-THF (4 : 1) was added to a well stirred solution of
poly(vinyl alcohol) (0.4 g, degree of polymerization: 2000,
78±82% hydrolyzed) in 200 mL of water at 0 °C. After 1 h of
stirring at 0 °C to homogenize the particle size, the tempera-
ture was raised to 80 °C and the reaction mixture was stirred
vigorously for 24 h at the same temperature. The resulting
polymer beads were filtered and washed with water, meth-
anol, THF-methanol, THF, and methanol, respectively. After
drying in vacuo at 40 °C, 11.5 g of polymer 5 were obtained.
Elemental analysis indicated a loading of N-sulfonylamino
alcohol corresponding to 0.77 mmol/g (DF = 0.10). IR:
Synthesis of Chiral Monomers
Chiral monomer 1: ((1R,2S,3R,4S)-3-(4-vinylbenzenesul-
fonyl)amino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol)
(±)-exo-2-Hydroxy-exo-3-aminobornane was prepared from
(1R)-(+)-camphor according to the literature method.[14]
A
THF solution of 4-vinylbenzenesulfonyl chloride[15]
(10 mmol) prepared from sodium 4-vinylbenzene sulfonate
was added to a solution of the exo-amino alcohol (1.69 g,
10 mmol) and triethylamine (1.4 mL, 10 mmol) in 50 mL of
dry THF. After being stirred for 3 h at room temperature,
the reaction mixture was poured into 1 M aqueous HCl at
0 °C, and the THF was evaporated under vacuum. The re-
sulting aqueous solution was extracted with ether
(3 ´ 25 ml). The combined extracts were dried over MgSO4
and evaporated at reduced pressure to give the crude pro-
duct. Recrystallization from ethanol-water gave 1 in 86%
yield; mp 149 °C; 1H NMR (270 MHz; CDCl3): d = 7.84 (d,
J = 8.3 Hz, 2 H), 7.52 (d, J = 8.3 Hz, 2 H), 6.76 (dd, J = 10.7,
17.6 Hz, 1 H), 5.88 (d, J = 17.6 Hz, 1 H), 5.44 (d, J = 10.7 Hz,
1 H), 5.33 (d, J = 6.8 Hz, 1 H), 3.60±3.55 (m, 1 H), 3.28-3.22
(m, 1 H), 2.19 (d, J = 4.4 Hz, 1 H), 1.70±1.17 (m, 5 H), 1.05 (s,
3 H), 0.89 (s, 3 H), 0.76 (s, 3 H); [a]2D3 ±25.9 (c 1.50, ethanol);
anal. calcd for C18H25NO3S (335.46): C 64.45, H 7.51, N
4.18%; found: C 64.38, H 7.45, N 4.18%.
m = 3500, 3300, 1320, 1150, 1090 cm±1
(C8H8)0.8(C10H10 0.1(C19H25NO3S)0.1: C 85.21, H 7.61, N 1.07,
; anal. calcd for
)
S 2.44%; found C 85.11, H 7.60, N 1.07, S 2.45%.
Chiral polymer 6
Suspension polymerization of 2 (3.35 g, 10 mmol), styrene
(8.32 g, 80 mmol), divinylbenzene (1.36 g, 10 mmol) gave
11.6 g of polymer 6. Both sulfur and nitrogen analyses indi-
cated a loading of chiral amino alcohol corresponding to
0.77 mmol/g (DF = 0.10).
Chiral polymer 7b
Chiral monomer 2: ((1R,2R,3S,4S)-3-(4-vinylbenzenesul-
fonyl)amino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol):
(±)-endo-2-Hydroxy-endo-3-aminobornane was prepared
from (1R)-(+)-camphor according to the literature meth-
od.[16] Compound 2 was obtained in 73% yield; mp 147 °C; 1H
Suspension polymerization of 3 (3.17 g, 10 mmol), styrene
(8.32 g, 80 mmol), divinylbenzene (1.36 g, 10 mmol) gave
11.7 g of polymer 7 b. Both sulfur and nitrogen analyses indi-
cated a loading of chiral amino alcohol corresponding to
0.78 mmol/g (DF = 0.10).
Adv. Synth. Catal. 2001, 343, 89±94
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