2212
Y. J. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 2209–2212
25
D
1
2b: ½a ¼ þ56:5 (c 0.49, MeOH); H NMR (300 MHz,
tory Program from MOST, a Center for Molecular
Design and Synthesis at KAIST and a KIST. We would
also like to thank Professor K. M. Kim for X-ray
analysis and Leadgene Co. Ltd who generously supplied
the cyclic b-enamino acid derivatives.
CDCl3) rotamer (major): d 1.18 (t, J ¼ 7:2 Hz, 3H,
CH3), 1.75 (m, 1H, 1/2CH2), 1.83–2.03 (m, 3H, 3/2CH2),
1.98 (s, 3H, CH3), 2.26 (dd, J ¼ 9:5, 15.4 Hz, 1H, 1/
2CH2), 2.90 (dd, J ¼ 3:9, 15.4 Hz, 1H, 1/2CH2), 3.39 (m,
2H, CH2), 4.05 (m, 2H, OCH2), 4.33 (m, 1H, CH);
rotamer (minor): d 1.21 (t, J ¼ 7:2 Hz, 3H, CH3), 1.75
(m, 1H, 1/2CH2), 1.83–2.03 (m, 3H, 3/2CH2), 2.06 (s,
3H, CH3), 2.38 (dd, J ¼ 10:1, 15.4 Hz, 1H, 1/2CH2),
2.50 (dd, J ¼ 3:7, 15.4 Hz, 1H, 1/2CH2), 3.39 (m, 2H,
CH2), 4.05 (m, 2H, OCH2), 4.19 (m, 1H, CH); 13C NMR
(75.5 MHz, CDCl3): d 14.06, 21.65, 21.90, 22.78, 23.69,
29.96, 31.12, 37.43, 39.44, 45.33, 47.73, 53.63, 55.11,
60.19, 60.69, 168.93, 169.15, 170.49, 171.32.
References and notes
1. (a) Harrison, J. R.; O’Brien, P.; Porter, D. W.; Smith, N.
M. J. Chem. Soc., Perkin Trans. 1 1999, 3623; (b) Sielecki,
T. M.; Wityak, J.; Liu, J.; Mousa, S. A.; Thoolen, M.;
Wexler, R. R.; Olson, R. E. Bioorg. Med. Chem. Lett. 2000,
€
10, 449; (c) Muller, G.; Albers, M.; Fischer, R.; Heßler, G.;
Lehmann, T. E.; Okigami, H.; Tajimi, M.; Bacon, K.;
25
D
1
2c: ½a ¼ þ39:0 (c 0.42, MeOH); H NMR (300 MHz,
€
Rolle, T. Bioorg. Med. Chem. Lett. 2001, 11, 3019; (d)
CDCl3): d 1.45 (s, 9H, CH3), 1.78–1.88 (m, 3H, 3/2CH2),
2.04 (m, 1H, 1/2CH2), 2.29 (dd, J ¼ 9:8, 15.0 Hz, 1H, 1/
2CH2), 2.86 (dd, J ¼ 14:1, 36.8 Hz, 1H, 1/2CH2), 3.33
Mahboobi, S.; Popp, A.; Burgemeister, T.; Schollmeyer, D.
Tetrahedron: Asymmetry 1998, 9, 2369; (e) DeVita, R.;
Goulet, M. T.; Wyvratt, M. J.; Fisher, M. H.; Lo, J.-L.;
Yang, Y. T.; Cheng, K.; Smith, R. G. Bioorg. Med. Chem.
Lett. 1999, 9, 2621.
(m, 2H, CH2), 3.66 (s, 3H, CH3), 4.11 (m, 1H, CH); 13
C
NMR (75.5 MHz, CDCl3): d 22.70, 23.44, 28.42, 30.50,
31.21, 38.42, 39.01, 46.12, 46.45, 51.50, 53.95, 79.20,
79.50, 154.20, 171.95.
2. (a) O’Neil, I. A.; Murray, C. L.; Potter, J.; Kalindjin, S. B.
Tetrahedron Lett. 1997, 38, 3609; (b) Davies, S. B.;
McKervey, M. A. Tetrahedron Lett. 1999, 40, 1229.
3. (a) Enders, D.; Weidemann, J. Liebigs Ann./Receuil 1997,
699; (b) Obrien, P.; Porter, D. W.; Smith, N. M. Synlett
2000, 9, 1336; (c) Chippindale, A. M.; Davies, S. G.;
Iwamoto, K.; Parkin, R. M.; Smethrust, C. A. P.; Smith, A.
D.; Rodriguez-Solla, H. Tetrahedron 2003, 59, 3253; (d)
25
D
1
2d: ½a ¼ þ37:0 (c 0.28, MeOH); H NMR (300 MHz,
CDCl3): d 1.26 (t, J ¼ 7:1 Hz, 3H, CH3), 1.76–1.96 (m,
3H, 3/2CH2), 2.08 (m, 1H, 1/2CH2), 2.33 (dd, J ¼ 9:6,
15.3 Hz, 1H, 1/2CH2), 2.90 (dd, J ¼ 15:5, 46.9 Hz, 1H,
1/2CH2), 3.39 (m, 2H, CH2), 3.68 (s, 3H, CH3), 4.12–
4.16 (m, 3H, CH, and OCH2); 13C NMR (75.5 MHz,
CDCl3): d 14.73, 22.74, 23.52, 30.58, 31.34, 38.20, 38.98,
46.30, 46.54, 51.53, 53.79, 54.34, 60.84, 61.00, 154.94,
171.86.
ꢁ ꢁ
Ledoux, S.; Celerier, J.-P.; Lhommet, G. Tetrahedron Lett.
1999, 40, 9019; (e) Calvet, S.; David, O.; Vanucci-Bacque,
ꢁ
C.; Frageau-Bellassoued, M.-C.; Lhommet, G. Tetrahedron
2003, 59, 6333; (f) Hussaini, S. R.; Moloney, M. G. Org.
Biomol. Chem. 2003, 1, 1838.
4. (a) Zhu, G.; Chen, Z.; Zhang, X. J. Org. Chem. 1999, 64,
6907; (b) Heller, D.; Holz, J.; Drexler, H.-J.; Lang, J.;
€
Drauz, K.; Krimmer, H.-P.; Borner, A. J. Org. Chem. 2001,
3.5. Determination of enantiomeric excesses
66, 6816; (c) Yasutake, M.; Gridnev, I. D.; Higashi, N.;
Imamoto, T. Org. Lett. 2001, 3, 1701; (d) Zhou, Y.-G.;
Tang, W.; Wang, E.-B.; Li, W.; Zhang, X. J. Am. Chem.
Chiral Capillary GC column: CP-Chiralsil-Dex-CB
column (dimensions 30 m · 0.32 mm (i.d.)). Carrier gas:
N2 (2 mL/min). The racemic products were obtained by
hydrogenation of the substrates 1a–d with Pd/C. The
following are the retention times for the racemic prod-
ucts.
~
Soc. 2002, 124, 4952; (e) Pena, D.; Minnaard, A. J.; de
Vries, J. G.; Feringa, B. L. J. Am. Chem. Soc. 2002, 124,
14552; (f) Tang, W.; Zhang, X. Org. Lett. 2002, 4, 4159; (g)
Heller, D.; Drexler, H.-J.; You, J.; Baumann, W.; Drauz,
€
K.; Krimmer, H.-P.; Borner, A. Chem. Eur. J. 2002, 8,
5196; (h) Heller, D.; Holz, J.; Drexler, H. J.; You, J.; Drauz,
€
K.; Borner, A. Tetrahedron: Asymmetry 2002, 13, 2735; (i)
Holz, J.; Monsees, A.; Jiao, H.; You, J.; Komarov, I. V.;
2a: (130 ꢁC, isothermal) retention time: (R)-isomer ¼
12.40 min, (S)-isomer ¼ 13.68 min.
€
Fischer, C.; Drauz, K.; Borner, A. J. Org. Chem. 2003, 68,
1701; (j) Wu, J.; Chen, X.; Guo, R.; Yeung, C.-H.; Chan, A.
S. C. J. Org. Chem. 2003, 68, 2490; (k) You, J.; Drexler, H.
J.; Zhang, S.; Fischer, C.; Heller, D. Angew. Chem., Int. Ed.
2003, 42, 913; (l) Tang, W.; Wang, W.; Chi, Y.; Zhang, X.
Angew. Chem., Int. Ed. 2003, 42, 3509.
2b: (130 ꢁC, isothermal) retention time: (R)-isomer ¼
16.10 min, (S)-isomer ¼ 17.52 min.
2c: (115 ꢁC, isothermal) retention time: (R)-isomer ¼
22.73 min, (S)-isomer ¼ 23.75 min.
5. Tang, W.; Wu, S.; Zhang, X. J. Am. Chem. Soc. 2003, 125,
9570.
ꢁ ꢁ
6. (a) Celerier, J.-P.; Richaud, M. G.; Lhommet, G. Synthesis
2d: (120 ꢁC, isothermal) retention time: (R)-isomer ¼
15.11 min, (S)-isomer ¼ 16.26 min.
ꢁ ꢁ
1983, 195; (b) Celerier, J.-P.; Deloisy, E.; Lhommet, G.;
Maitte, P. J. Org. Chem. 1979, 44, 3089.
ꢁ ꢁ
7. Brunerie, P.; Celerier, J.-P.; Petit, H.; Lhommet, G. J.
Heterocycl. Chem. 1986, 23, 1183.
Acknowledgements
8. (a) Lee, S.-g.; Zhang, Y. J.; Song, C. E.; Lee, J. K.; Choi, J.
H. Angew. Chem., Int. Ed. 2002, 41, 847; (b) Lee, S.-g.;
Zhang, Y. J. Tetrahedron: Asymmetry 2002, 13, 1039; (c)
Lee, S.-g.; Zhang, Y. J. Org. Lett. 2002, 4, 2429.
This work was supported by a Korea National Center
for Cleaner Production, a National Research Labora-