1214
S.R. Shengule et al. / Tetrahedron 68 (2012) 1207e1215
from amine 34 using the method described for the synthesis of 26
IR vmax (cmꢁ1): 3310, 2954, 1653, 1447, 1320, 1140, 1058, 1018, 803.
Major isomer: Rf: 0.35 (15:85, MeOH/EtOAc); 1H NMR (CD3OD)
d 7.94 (d, 2H, J 7.8 Hz), 7.67 (t, 1H, J 7.8 Hz), 7.59 (t, 2H, J 7.6 Hz), 7.18
25
(110 mg, 39% for two steps); Rf: 0.60 (20:80, EtOAc/petrol); [a]
D
ꢁ22.24 (c 0.2, CHCl3). IR vmax (cmꢁ1): 3405, 2922, 1695, 1582, 1439,
1347, 1148, 1024, 793. 1H NMR
d
7.27e7.20 (m, 2H), 7.16e7.10 (m,
(d, 1H, J 3.4 Hz), 6.32 (d, 1H, J 3.5 Hz), 4.87 (br s, 1H), 4.05 (d, 1H, J
5.8 Hz), 3.46e3.37 (m, 1H), 3.26e3.17 (m, 1H), 2.79 (dd, 1H, J 6.2,
17.5 Hz), 2.68 (t, 2H, J 7.5 Hz), 2.14 (d, 1H, J 17.6 Hz), 1.96e1.80 (m,
3H), 6.63 (d, 1H, J 2.9 Hz), 6.11 (d, 1H, J 2.9 Hz), 4.55 (dd, 1H, J 4.8,
8.8 Hz), 3.56 (t, 2H, J 7.1 Hz), 3.00 (dd, 1H, J 8.0, 18.1 Hz), 2.65 (t, 2H, J
7.2 Hz), 2.62 (dd, 1H, J 4.8, 18.1 Hz), 1.94 (p, 2H, J 7.0 Hz). 13C NMR
2H); 13C NMR (CD3OD)
d 174.8, 162.3, 148.0, 140.5, 133.7, 129.4,
d
178.2, 174.2, 159.2, 141.1, 137.0, 129.3, 127.3, 126.4, 121.2, 108.2, 67.1,
127.4, 118.9, 107.8, 89.9, 71.2, 39.2, 38.2, 25.5, 25.1; HRMS (ESI þve)
38.6, 37.3, 26.2, 25.9. HRMS (ESI þve) calculated for C17H18NO4S
calculated for C17H20NO6S (MþHþ) 366.1006, found 366.1007.
(MþHþ) 332.0952, found 332.0953.
4.1.28. (3S)-5-Oxo-1-(3-(5-(phenylsulfonyl)furan-2-yl)propyl)pyrro-
lidine-2,3-diyl diacetate (40). The title compound was synthesised
from 39 (25 mg, 0.055 mmol) using the same method described for
the synthesis of 2b (30 mg, 98%); Rf: 0.40 (35:65, EtOAc/petrol); IR
vmax (cmꢁ1): 2952, 1714, 1447, 1373, 1328, 1216, 1141, 1042, 1013,
4.1.24. (4S)-4,5-Dihydroxy-1-(3-(5-(phenylthio)furan-2-yl)propyl)
pyrrolidin-2-one (36). The title compound was synthesised from 35
(80 mg, 0.256 mmol) using the same method described for the syn-
thesis of 2a (40 mg, 50%) and in a diastereomeric ratio of 10:8; IR vmax
(cmꢁ1): 3340, 2936, 1662, 1582, 1439, 1260, 1110, 1066, 1024, 792.
Major isomer: Rf: 0.55 (10:90, MeOH/EtOAc); 1H NMR (CD3OD)
964; 1H NMR
d 7.98 (d, 2H, J 8.5 Hz), 7.61 (t,1H, J 7.2 Hz), 7.54 (t, 2H, J
7.2 Hz), 7.11 (d, 1H, J 3.8 Hz), 6.18 (d,1H, J 3.4 Hz), 6.08 (br s,1H), 5.11
(d,1H, J 6.4 Hz), 3.59e3.48 (m,1H), 3.17e3.08 (m,1H), 2.91 (dd,1H, J
6.2, 18.0 Hz), 2.64 (t, 2H, J 7.6 Hz), 2.36 (d, 1H, J 18.0 Hz), 2.09 (s, 3H),
d
7.29e7.07 (m, 5H), 6.68 (d, 2H, J 3.0 Hz), 6.24e6.19 (m, 1H), 4.90 (s,
1H), 4.06 (d, 1H, J 6.4 Hz), 3.52e3.40 (m, 1H), 3.29e3.19 (m, 1H), 2.80
(dd, 1H, J 6.0, 17 Hz), 2.71e2.64 (m, 2H), 2.16 (dd, 1H, J 2.0, 17 Hz),
2.07 (s, 3H), 1.98e1.78 (m, 2H); 13C NMR
d 173.3, 170.2, 169.9, 161.3,
2.00e1.82 (m, 2H); 13C NMR (CD3OD)
d
174.7,160.1,140.8,137.2,128.9,
126.8, 125.9, 120.8, 107.7, 89.9, 71.2, 39.3, 38.2, 25.9, 25.4. Minor iso-
mer: Rf: 0.50 (10:90, MeOH/EtOAc); 1H NMR (CD3OD)
7.29e7.07 (m,
147.5, 140.0, 133.7, 129.4, 127.9, 118.9, 107.9, 86.6, 71.1, 40.4, 35.9,
25.8, 25.6, 21.0, 20.9; HRMS (ESI þve) calculated for C21H24NO8S
(MþHþ) 450.1232, found 450.1223.
d
5H), 6.68 (d, 2H, J 3.0 Hz), 6.24e6.19 (m, 1H), 5.03 (d, 1H, J 5.3 Hz),
4.26e4.20 (m, 1H), 3.52e3.40 (m, 1H), 3.29e3.19 (m, 1H), 2.54 (dd,
1H, J 6.8, 16.7 Hz), 2.71e2.64 (m, 2H), 2.34 (dd, 1H, J 6.0, 16.7 Hz),
4.2. X-ray crystallographic study
2.00e1.82 (m, 2H); 13CNMR (CD3OD)
d173.9,160.2,140.8,137.1,128.9,
4.2.1. Crystal data. Compound 25. C14H17NO5, M¼279.29, T¼200 K,
orthorhombic, space group P212121, Z¼4, a¼5.6983(1),
126.9, 126.0, 120.8, 107.6, 83.4, 65.6, 39.5, 37.7, 25.8, 25.6; HRMS (ESI
þve) calculated for C17H20NO4S (MþHþ) 334.1108, found 334.1114.
3
ꢀ
3
ꢀ
b¼9.3734(2), c¼25.0005(4) A, V¼1335.34(4) A , Dx¼1.389 g/cm ,
1804 unique data (
q
¼2.6e27.5ꢀ), R¼0.029 [for 1650 with I>2.0
s(I)];
4.1.25. (3S)-5-Oxo-1-(3-(5-(phenylthio)furan-2-yl)propyl)pyrroli-
dine-2,3-diyl diacetate (37). The title compound was 37 synthesised
from 36 (30 mg, 0.071 mmol) using the same method described for
the synthesis of 2b (34 mg, 91%) and in a diastereomeric ratio of
10:8; IR vmax (cmꢁ1): 2800, 1751, 1717, 1479, 1370, 1220, 1142, 1007,
964, 751. Major isomer: Rf: 0.65 (20:80, EtOAc/petrol); 1H NMR
Rw¼0.074 (all data), S¼1.01.
4.2.2. Structure determination. Images were measured on a Nonius
Kappa CCD diffractometer (Mo K , graphite monochromator,
a
18
ꢀ
l
¼0.71073 A) and data extracted using the DENZO package.
Structure solution was by direct methods (SIR92).19 The structure
was refined using the CRYSTALS program package.20 Atomic co-
ordinates, bond lengths and angles and displacement parameters
have been deposited at the Cambridge Crystallographic Data Centre
(CCDC no. 840569). These data can be obtained free-of-charge via
d
7.29e7.19 (m, 3H), 7.12 (t, 2H, J 7.3 Hz), 6.64 (d,1H, J 2.5 Hz), 6.11 (d,
1H, J 2.8 Hz), 6.0 (br s, 1H), 5.09 (d, 1H, J 6.3 Hz), 3.60e3.50 (m, 1H),
3.19e3.09 (m, 1H), 2.89 (dd, 1H, J 6.7, 17.7 Hz), 2.63 (t, 2H, J 7.8 Hz),
2.34 (d,1H, J 17.7 Hz), 2.06 (s, 3H), 2.04 (s, 3H), 2.01e1.79 (m, 2H); 13C
NMR d 173.3,170.2,169.9,159.5,140.9,137.1,129.2,127.2,121.1,108.0,
by
emailing
86.8, 71.1, 40.5, 36.0, 29.9, 26.1, 25.8, 21.0, 20.9; HRMS (ESI þve)
lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
þ44 1223 336033.
calculated for C21H23NO6SNa (MþNaþ) 440.1139, found 440.1140.
4.1.26. (S)-3-Hydroxy-1-(3-(5-(phenylsulfonyl)furan-2-yl)propyl)
pyrrolidine-2,5-dione (38). Toasolutionof35(50 mg,0.151 mmol)in
acetic acid (5 mL) was added hydrogen peroxide (30% solution in
water, 0.5 mL) and the reaction mixture was stirred at rt for 2 days. A
saturated solution of NaHCO3 (5 mL) was slowly added and the
mixture was extracted with EtOAc (3ꢂ20 mL). The extracts were
dried (MgSO4) and the solvent was removed under reduced pressure.
The crude residue was purified by FCC over silica gel using a gradient
of 50:50e80:20 EtOAc/petrol to give 38 as a thick oil (52 mg, 96%); Rf:
Acknowledgements
We thank the Australian Research Council and the University of
Wollongong for financial support.
References and notes
1. Mungkornasawakul, P.; Pyne, S. G.; Jatisatienr, A.; Supyen, D.; Lie, W.; Ung, A. T.;
Skelton, B. W.; White, A. H. J. Nat. Prod. 2003, 66, 980e982.
0.43 (60:40, EtOAc/petrol); [
a
]
25 ꢁ37.6 (c 2.0, CHCl3); IR vmax (cmꢁ1):
D
2. For reviews on N-acyliminium ion chemistry, see: (a) Speckamp, W. N.;
Hiemstra, H. Tetrahedron 1985, 41, 4367e4416; (b) Speckamp, W. N.; Moolenaar,
M. J. Tetrahedron 2000, 56, 3817e3856; (c) Maryanoff, B. E.; Zhang, H.; Cohen, J.
H.; Turchi, I. J.; Maryanoff, C. A. Chem. Rev. 2004, 104, 1431e1628; (d) Yazici, A.;
Pyne, S. G. Synthesis 2009, 339e368; (e) Yazici, A.; Pyne, S. G. Synthesis 2009,
513e541; (f) Martinez-Estibalez, U.; Gomez-SanJuan, A.; Garcia-Calvo, O.;
Aranzamendi, E.; Lete, E.; Sotomayor, N. Eur. J. Org. Chem. 2011, 20e21.
3. Martin, S. F.; Bur, S. K. Tetrahedron Lett. 1997, 38, 7641e7644; Martin, S. F.; Barr,
K. J.; Smith, D. W.; Scott, K.; Bur, S. K. J. Am. Chem. Soc. 1991, 121, 6990e6997.
4. Tannis, S. P.; Deaton, M. V.; Dixon, L. A.; McMills, M. C.; Raggon, J. W.; Collins,
M. A. J. Org. Chem. 1998, 63, 6914e6928.
3443, 2942,1696,1499,1325,1139,1082,1015, 752; 1H NMR
d
7.96 (d,
2H, 7.5 Hz), 7.60 (t, 1H, J 7.5 Hz), 7.52 (t, 2H, J 8.0 Hz), 7.09 (d, 1H, J
3.7 Hz), 6.17 (d, 1H, J 3.3 Hz), 4.61e4.54 (m, 1H), 3.53 (t, 2H, J 7.0 Hz),
3.01 (dd, 1H, J 8.4, 17.9 Hz), 2.64 (t, 2H, J 7.8 Hz), 2.65e2.58 (m, 1H),
1.92 (p, 2H, J 7.1 Hz); 13C NMR
d 178.2,174.2,161.0,148.2,140.3,133.8,
129.5, 127.9, 118.9, 108.1, 67.0, 38.3, 37.3, 25.9, 25.4; HRMS (ESI þve)
calculated for C17H18NO6S (MþHþ) 364.0850 found 364.0850.
5. Cassidy, M. P.; Oezdemir, A. D.; Padwa, A. Org. Lett. 2005, 7, 1339e1342.
6. Arutyunyan, N. S.; Akopyan, L. A.; Snkhchyan, G. M.; Papoyan, O. A.; Panosyan,
G. A.; Gevorgyan, G. A. Chem. Heterocycl. Compd. 2006, 42, 440e445.
7. Doolittle, R. E.; Heath, R. R. J. Org. Chem. 1984, 49, 5041e5050.
4.1.27. (4S)-4,5-Dihydroxy-1-(3-(5-(phenylsulfonyl)furan-2-yl)pro-
pyl)pyrrolidin-2-one (39). The title compound was synthesized
from 38 (50 mg, 0.137 mmol) using the method described for the
synthesis of 26 (27 mg, 54%) and in a diastereomeric ratio of 10:0.7;
8. Huang, P. Q.; Liu, L. X.; Wei, B. G.; Ruan, Y. P. Org. Lett. 2003, 5, 1927e1929.