1098
A. V. Si6akumar et al. / Tetrahedron: Asymmetry 12 (2001) 1095–1099
4.3.4. Compound 3c. White solid, mp 158–160°C; [h]2D0=
reaction mixture was extracted with ether (5×20 mL).
The aqueous portion was evaporated to dryness in
vacuo. The hydrochloride of b-amino-b-phenylpropi-
onic acid was obtained contaminated with other inor-
ganic impurities. The hydrochloride was dissolved in
water and filtered through a column of strong acidic
ion-exchange resin (5 g, amberlite IR-120, H+ form)
using first water (100 mL) and then 1N ammonia (200
mL) as eluents. Evaporation of the ammonia gave free
amino acid 7a (100 mg, 77%); mp 215–217°C [Lit.16 for
(S)-7a, mp 216°C], [h]2D0=−6.9 (c=1.00, H2O). [Lit.15
1
+96.50 (c 1.00, acetone); H NMR (CDCl3, 300 MHz):
l 1.30 (s, 9H), 2.31 (s, 3H), 2.44 (s, 3H), 3.56 (d,
J=5.49 Hz, 1H), 3.6 (s, 3H), 3.8 (s, 3H), 4.7 (m, 1H),
6.35–6.48 (m, 3H), 6.59 (d, J=8.24 Hz, 1H), 7.04 (d,
J=8.05 Hz, 2H), 7.36 (d, J=8.05 Hz, 2H), 7.44 (d,
J=8.24 Hz, 2H), 7.60 (d, J=8.24 Hz, 2H). IR (KBr):
3247, 2927, 1729, 1611, 1341, 1268, 1156 cm−1. Anal.
calcd for C29H35NO7S2: C, 60.71; H, 6.14; N, 2.44.
Found: C, 60.68; H, 6.12; N, 2.40%.
1
4.3.5. Compound 3d. White solid, mp 120–122°C;
for (S)-7a, [h]2D5=7.5 1]; H NMR (D2O, 300 MHz): l
1
[h]2D0=+121.0 (c 1.00, acetone); H NMR (CDCl3, 300
2.88 (dd, J 16, 7 Hz, 1H, 1/2CH2), 2.98 (dd, J 16, 8 Hz,
1H, 1/2CH2), 4.69–4.85 (m, 1H), 7.48–7.61 (m, 5H). IR
(KBr): 2612, 2205, 1625, 1580 cm−1.
MHz): l 1.28 (s, 9H), 2.35 (s, 3H), 2.44 (s, 3H), 3.51 (d,
J=5.12 Hz, 1H), 4.65 (m, 1H), 6.60 (d, J=8.42 Hz,
1H), 6.85 (d, J=8.42 Hz, 2H), 7.03–7.05 (m, 4H), 7.36
(d, J=8.06 Hz, 2H), 7.46 (d, J=8.06 Hz, 2H), 7.58 (d,
J=8.42 Hz, 2H). IR (KBr): 3357, 3259, 2922, 1722,
1596, 1341, 1164 cm−1. Anal. calcd for C27H30NO5S2Cl:
C, 59.16; H, 5.51; N, 2.55. Found: C, 58.94; H, 5.48; N,
2.34%.
Acknowledgements
We thank DST for the financial support and RSIC, IIT
Mumbai and TIFR for spectral data.
4.4. Preparation of tert-butyl 3-(4-toluenesulfonamido)-
3-phenylpropanoate 5a
To a mixture of adduct 3a (500 mg, 0.974 mmol) and
anhydrous disodium hydrogen phosphate (550 mg, 3.89
mmol) in dry methanol (30 mL) at 0°C was added
pulverized sodium amalgam (2 g). The solution was
stirred for 20 min at 0°C and the mixture was allowed
to warm to room temperature. Stirring was continued
for another 0.5 h and the reaction mixture was poured
into water and extracted with ethyl acetate. The organic
extract was dried over Na2SO4. The solvent was evapo-
rated in vacuo and the residue was purified by chro-
matography over silica gel (100–200 mesh), elution with
ethyl acetate/petroleum ether (1:9), yielded tert-butyl
3-(4-tolenesulfonamido)-3-phenylpropanoate 5a as a
white crystalline solid (348 mg, 95%), mp 104–106°C;
References
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1
[h]2D0=−14.0 (c 1.00, acetone); H NMR (CDCl3, 300
MHz): l 1.30 (s, 9H), 2.36 (s, 3H), 2.62 (dd, J=15.8,
6.6 Hz, 1H, 1/2CH2), 2.74 (dd, J=15.7, 6.2 Hz, 1H,
1/2CH2), 4.68 (dd, J=6.2, 7.3 Hz, 1H), 5.84 (d, J=7.3
Hz, 1H), 7.06–7.19 (m, 7H), 7.58 (d, J=8.42 Hz, 2H).
IR (KBr): 3256, 2920, 1729, 1670, 1295, 1156 cm−1.
Anal. calcd for C20H25NO4S: C, 64.0; H, 6.7; N, 3.7.
Found: C, 63.9; H, 6.8; N, 3.6%.
4.5. Preparation of (S)-b-amino-b-phenylpropionic acid
7a
7. Patel, R. N.; Banerjee, A.; Howell, J. M.; McNamee, C.
G.; Brozozowski, D.; Mirfakhrae, D.; Nanduri, V.; Thot-
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A solution of 5a (300 mg, 0.802 mmol) and potassium
hydroxide (450 mg, 8.02 mmol) in ethanol/water (1:1,
15 mL) was heated at 60°C for 1 h. The ethanol was
evaporated in vacuo and the pH of the residue was
adjusted to 3 with concentrated hydrochloric acid and
extracted with chloroform (2×50 mL). The organic
layer was evaporated in vacuo to give acid 6a (250 mg,
0.789 mmol). Compound 6a was treated with sodium
(200 mg, 8.7 mmol) in liquid ammonia (20 mL) at
reflux for 3 h. The mixture was then evaporated to
dryness and the residue was diluted with water (2 mL)
and acidified to pH 6 with aqueous HCl (10%). The