H. Huang et al. / Tetrahedron: Asymmetry 14 (2003) 1285–1289
1289
80.00, 81.20, 82.01, 103.38, 104.85, 109.56, 112.59,
121.62, 137.22, 156.95, 157.67; HRMS (ESI) calcd for
C19H27NO6 (M++1): 366.1911, found: 366.1897.
gel column chromatography, the enantiomeric excess was
determined by GC or HPLC.
Acknowledgements
4.2.4. Synthesis of N,O ligand 4. The above procedure was
followed using 2,6-lutidine and chiral ketone 8. After
work-up, it gave 3.5 g (78%) of 4: mp 103–104°C; [h]1D2=+
29.4 (c 0.64, CHCl3); 1H NMR (CDCl3): l 1.31–1.82 (m,
20H), 2.52 (s, 3H), 2.82 (d, 1H, J=14.8 Hz), 3.29 (d, 1H,
J=14.8 Hz), 3.94–4.02 (m, 2H), 4.09 (t, 1H, J=7.6 Hz),
4.10–4.20 (m, 2H), 5.75 (d, 1H, J=3.6 Hz), 5.79 (br, 1H),
7.03–7.06 (m, 2H), 7.53 (t, 1H, J=7.8 Hz); 13C NMR
(CDCl3): l 23.38, 23.77, 23.90, 24.79, 25.03, 34.79, 35.91,
36.07, 36.21, 38.04, 67.36, 73.05, 79.73, 81.41, 81.52,
103.04, 109.95, 113.09, 121.64, 137.29, 156.68, 157.21;
HRMS (ESI) calcd for C25H35NO6 (M++1): 446.2537,
found: 446.2511. Anal. calcd for C25H35NO6: C, 67.39; H,
7.92; N, 3.14. found: C, 67.37; H, 7.56; N, 3.21%.
Financial support from the National Science Foundation
of China (29933050) is gratefully acknowledged. The
authors thank Dr. Yonggui Zhou and Dr. Xinquan Hu
for helpful discussions.
References
1. For reviews, see: (a) Noyori, R.; Kitamura, M. Angew.
Chem., Int. Ed. Engl. 1991, 30, 49; (b) Soai, K.; Niwa, S.
Chem. Rev. 1992, 92, 833; (c) Blaser, H. U. Chem. Rev. 1992,
29, 359; (d) Pu, L.; Yu, H. B. Chem. Rev. 2001, 101, 757.
2. Oguni, N.; Omi, T. Tetrahedron Lett. 1984, 25, 2823.
3. Corey, E. J.; Yuen, P. W.; Hammon, F. J. D.; Wierda, A. J.
Org. Chem. 1990, 55, 784.
4.2.5. Synthesis of N,O ligand 5. The above procedure was
followed using 2-methylquinoline and chiral ketone 7.
After work-up, it gave 2.3 g (57%) 5: mp 151–152°C;
4. (a) Bolm, C.; Zehnder, M.; Bur, D. Angew. Chem., Int. Ed.
Engl. 1990, 29, 205; (b) Bolm, C.; Ewald, M.; Felder, M.;
Schlingloff, G. Chem. Ber. 1992, 125, 1169; (c) Bolm, C.;
Schlingloff, G.; Harms, K. Chem. Ber. 1992, 125, 1191; (d)
Chelucci, G.; Soccolini, F. Tetrahedron: Asymmetry 1992, 3,
1235; (e) Collomb, P.; Von Zelewsky, A. Tetrahedron:
Asymmetry 1998, 9, 3911; (f) Kwong, H. L.; Lee, W. S. Tet-
rahedron: Asymmetry 1999, 10, 3791; (g) Ishizaki, M.; Fujita,
K.; Shimamoto, M.; Hoshino, O. Tetrahedron: Asymmetry
1994, 5, 411; (h) Ishizaki, M.; Hoshino, O. Chem. Lett 1994,
337; (i) Williams, D.; Fromhold, M. G. Synlett 1997, 523; (j)
Macedo, E.; Moberg, C. Tetrahedron: Asymmetry 1995, 6,
549; (k) Kang, J.; Kim, H.-Y.; Kim, J.-H. Tetrahedron:
Asymmetry 1999, 10, 2523; (l) Kotsuki, H.; Nakagawa, Y.;
Moriya, N.; Tateishi, H.; Ochi, M.; Suzuki, T.; Isobe, K.
Tetrahedron: Asymmetry 1995, 6, 1165; (m) Kotsuki, H.;
Hayakawa, H.; Tateishi, H.; Wakao, M.; Shiro, M. Tetra-
hedron: Asymmetry 1998, 9, 3203; (n) Wu, Y.; Yun, H.; Wu,
Y.; Ding, K.; Zhou, Y. Tetrahedron: Asymmetry 2000, 11,
3543; (o) Yun, H.; Wu, Y.; Wu, Y.; Ding, K.; Zhou, Y. Tet-
rahedron Lett. 2000, 41, 10263; (p) Zhang, H.; Xue, F.; Mak,
T. C. W.; Chan, K. S. J. Org. Chem. 1996, 61, 8002; (q)
Zhang, H.; Chan, K. S. J. Chem. Soc., Perkin. Trans. 1 1999,
381; (r) Soai, K.; Shibata, T.; Sato, I. Acc. Chem. Res. 2000,
33, 382; (s) Goanvic, D. L.; Holler, M.; Pale, P. Tetrahedron:
Asymmetry 2002, 13, 119; (t) Zhong, Y. W.; Lei, X. S.; Lin,
G. Q. Tetrahedron: Asymmetry 2002, 13, 2251.
1
[h]1D2=+53.3 (c 0.41, CHCl3); H NMR (CDCl3): l 1.24
(s, 3H), 1.31 (s, 3H), 1.49 (s, 3H), 1.59 (s, 3H), 3.17 (d, 1H,
J=14.8 Hz), 3.57 (d, 1H, J=14.8 Hz), 4.00–4.05 (m, 2H),
4.15 (t, 1H, J=7.6 Hz), 4.24–4.30 (m, 2H), 5.88 (d, 1H,
J=3.6 Hz), 7.52 (d, 1H, J=8.4 Hz), 7.60 (t, 1H, J=8.0
Hz), 7.75 (t, 1H, J=8.0 Hz), 7.86 (d, 1H, J=8.0 Hz), 8.14
(d, 1H, J=8.4 Hz), 8.20 (d, 1H, J=8.4 Hz); 13C NMR
(CDCl3): l 25.29, 26.38, 26.66, 26.76, 38.47, 67.88, 73.46,
80.14, 81.67, 81.77, 103.67, 109.70, 112.61, 123.43,
126.94, 127.59, 130.49, 137.86, 158.17; HRMS (ESI)
calcd for C22H27NO6 (M++1): 402.1911, found: 402.1900.
4.2.6. Synthesis of N,O ligand 6. The above procedure was
followed using 2-methylquinoline and chiral ketone 8.
After work-up, it gave 3.1 g (64%) 6: mp 153–154°C;
[h]1D2=+61.6 (c 0.57, CHCl3); 1H NMR (CDCl3): l 1.30–
1.82 (m, 20H), 3.02 (d, 1H, J=14.8 Hz), 3.54 (d, 1H, J=
14.8 Hz), 3.97–4.00 (m, 2H), 4.08 (t, 1H, J=7.6 Hz),
4.22–4.27 (m, 1H), 4.33 (d, 1H,, J=3.6 Hz), 5.25 (br, 1H),
5.82 (d, 1H, J=3.6 Hz), 7.46 (d, 1H, J=8.4 Hz), 7.53 (t,
1H, J=8.0 Hz), 7.71 (t, 1H, J=8.0 Hz), 7.81 (d, 1H, J=
8.0 Hz), 8.03 (d, 1H, J=8.8 Hz), 8.12 (d, 1H, J=8.4 Hz);
13C NMR (CDCl3): l 23.40, 23.72, 23.85, 23.98, 24.80,
25.06, 34.78, 35.93, 36.21, 38.80, 67.68, 73.16, 80.00,
81.14, 82.07, 103.31, 110.18, 113.23, 123.68, 126.83,
126.96, 127.57, 130.37, 137.59, 158.23; HRMS (ESI)
calcd for C28H35NO6 (M++1): 482.2537, found: 482.2555.
5. Zhou, Y. G.; Dai, L. X.; Hou, X. L. Chin. J. Chem. 2000, 18,
121.
6. Huang, H.; Chen, H.; Hu, X.; Bai, C.; Zheng, Z. Tetra-
hedron: Asymmetry 2003, 14, 297.
4.3. General procedures for the asymmetric addition of
diethylzinc to aldehydes
7. (a) Hockett, R. C.; Miller, R. E.; Scattergood, A. J. Am.
Chem. Soc. 1949, 71, 3072; (b) James, K.; Tatchell, A. R.;
Ray, P. K. J. Chem. Soc. (C) 1967, 2681; (c) Singh, P. P.;
Gharia, M. M.; Dasgupta, F.; Srivastava, H. C. Tetrahedron
Lett. 1977, 439.
8. (a) Asami, M.; Watanabe, H.; Honda, K.; Inoue, S. Tetra-
hedron: Asymmetry 1998, 9, 4165; (b) Kang, J.; Lee, J. W.;
Kim, J. I. J. Chem. Soc., Chem. Commun. 1994, 2009; (c)
Watanabe, M.; Araki, S.; Butsugan, Y.; Uemura, M. J. Org.
Chem. 1991, 56, 2218; (d) Kitamura, M.; Suga, S.; Kawai,
K.; Noyori, R. J. Am. Chem. Soc. 1986, 108, 6071; (e) Kang,
S. K.; Jenon, J. H.; Yamaguchi, T.; Kim, J. S.; Ko, B. S. Tet-
rahedron: Asymmetry 1995, 6, 2139.
Chiral ligand (0.05 mmol, 5 mol%) in dry toluene (3 mL)
was cooled to 0°C and 1 M diethylzinc in hexane (2.2
mmol, 2.2 mL) was added slowly. After stirring for 30
min at 0°C, freshly distilled aldehyde (1 mmol) was added
and the reaction was monitored by TLC. When the reac-
tion was completed, 1N HCl (5 mL) was added. The lay-
ers were separated and the aqueous layer was extracted
with diethylether (3×15 mL). The combined organic
phases were washed with brine, dried by Na2SO4 and
concentrated in vacuo. The residue was purified by silica