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M.-C. Wang et al. / Tetrahedron: Asymmetry 15 (2004) 3853–3859
compound 5e were in complete agreement with the re-
ported data.8
(d, J = 12.8Hz, each 1H, FcCHH0N), 4.11–4.22 (m,
9H, FcH). 13C NMR (100MHz, CDCl3): d 22.54,
22.63,22.75, 28.54, 28.62, 29.72, 32.24, 32.30, 34.85,
37.78, 44.34, 58.88, 68.01, 68.38, 68.48, 68.98, 69.10,
70.04, 84.14. IR (KBr pellet): 3440, 3259, 3096, 2954,
2866, 1635, 1463, 1409, 1374, 1328, 1327, 1157, 1099,
1031, 1002, 817. MS: m/z (ESI) 412 (M++1), 434
(M++Na). HRMS (MALDI): calcd for C24H37FeNO
M+ 411.2219, found: 411.2242.
4.7.4. (2S)-1-Ferrocenylmethylaziridin-2-yl(di-n-
butyl)methanol 5f. Following the general procedure
gave compound 5f as an orange red oil (200mg, 71%).
20
D
½a ¼ ꢀ27:1 (c 1, CHCl3). 1H NMR (400MHz,
CDCl3): d 0.88 (m, 6H, 2 · CH3), 1.22–1.41 (m, 13H,
H–C(3), 2 · CH2CH2CH2CH3), 1.53 (dd, J1 = 6.0Hz,
J2 = 3.6Hz, 1H, H–C(2)), 1.82 (d, J = 3.2Hz, 1H, H–
C(3)), 2.40(br, 1H, OH), 3.27, 3.33 (d, J = 12.8Hz, each
1H, FcCHH0N), 4.11–4.22 (m, 9H, FcH). 13C NMR
(100MHz, CDCl3): d 14.08, 23.28, 23.41, 25.53, 25.70,
29.66, 37.04, 39.97, 44.25, 58.89, 67.96, 68.30, 68.48,
68.97, 69.05, 70.00, 84.11. IR (KBr pellet): 3446, 3093,
2932, 2864, 1634, 1461, 1409, 1376, 1329, 1153, 1032,
1001, 818. MS: m/z (ESI) 384 (M++1), 406 (M++Na).
HRMS (MALDI): calcd for C22H33FeNO M+
383.1906, found: 383.1929.
4.7.8.
(2S)-1-Ferrocenylmethylaziridin-2-yl(diphenyl)-
methanol 5j. Following the general procedure to give
compound 5j as an orange red crystal. All the physical
and spectroscopic data for compound 5e were in com-
plete agreement with the reported data.8
4.8. General procedure for the enantioselective addition of
Et2Zn to arylaldehydes
A solution of diethylzinc (1M in n-hexane, 1.1mL) was
added to a solution of a chiral catalyst (0.015mmol,
6.3mg, 3mol%) in dry toluene under a nitrogen atmos-
phere. The mixture was cooled to 0ꢁC, and stirred for
30min. Freshly distilled benzaldehyde (0.05mL,
0.5mmol) was added to the mixture. The resulting mix-
ture was stirred for 10h in 0–5 ꢁC and was allowed to
warm to room temperature, and kept stirring for an-
other 38h at the same temperature. The reaction was
quenched by the addition of saturated aqueous NH4Cl
(4mL). The mixture was extracted with Et2O
(3 · 8mL). The combined organic layers were washed
with brine, dried over anhydrous Na2SO4 and evapo-
rated under reduced pressure. Purification of the residue
by the preparative silica gel TLC plate (hexane/
EtOAc = 4/1) afforded the (S)-1-phenyl-1-propanol in
97% yield. The ee was determined by HPLC analyses
using a chiral column.
4.7.5. (2S)-1-Ferrocenylmethylaziridin-2-yl(di-i-butyl)-
methanol 5g. Following the general procedure gave
compound 5g as an orange red oil (163mg, 61%).
20
D
½a ¼ ꢀ30:7 (c 1.274, CHCl3). 1H NMR (400MHz,
CDCl3): d 0.92 (m, 12 H, 4 · CH3), 1.34 (m, 4H,
2 · CH2CH3), 1.39 (d, J = 6.0Hz, 1H, H–C(3)), 1.52
(dd, J1 = 6.4Hz, J2 = 3.6Hz, 1H, H–C(2)), 1.75–1.85
(m, 3H, H–C(3), 2 · CH), 2.41 (br, 1H, OH), 3.14,
3.49 (d, J = 12.8Hz, each 1H, FcCHH0N), 4.10–4.20
(m, 9H, FcH). 13C NMR (100MHz, CDCl3): d 23.77,
23.86, 24.76, 24.81, 24.88, 29.79, 45.29, 46.62, 49.51,
58.69, 67.97, 68.18, 68.47, 68.80, 68.99, 71.24, 84.14.
IR (KBr pellet): 3373, 3098, 2949, 2866, 1638, 1465,
1410, 1365, 1325, 1236, 1106, 1039, 1013, 817. m/z
(ESI) 384 (M++1), 406 (M++Na). HRMS (MALDI):
calcd for C22H33FeNO M+ 383.1906, found: 383.1928.
4.7.6. (2S)-1-Ferrocenylmethylaziridin-2-yl(di-n-pentyl)-
methanol 5h. Following the general procedure gave
compound 5h as an orange red oil (233mg, 80%).
Acknowledgements
20
½a ¼ ꢀ24:2 (c 1.0, CHCl3). 1H NMR (400MHz,
D
CDCl3): d 0.88 (m, 6H, 2 · CH3), 1.16–1.38 (m, 17H,
We are grateful to the National Natural Sciences Foun-
dation of China (NNSFC:20172047), Henan Outstand-
ing Youth Program 2001, and the Education
Department of Henan Province for the financial
supports.
H–C(3),
2 · CH2CH2CH2CH2CH3),
1.53
(dd,
J1 = 6.4Hz, J2 = 4.0Hz, 1H, H–C(2)), 1.81 (d,
J = 4.4Hz, 1H, H–C(3)), 2.42 (br, 1H, OH), 3.26, 3.31
(d, J = 12.8Hz, each 1H, FcCHH0N), 4.10–4.22 (m,
9H, FcH). 13C NMR (100MHz, CDCl3): d 14.11,
22.65, 23.01, 23.21, 29.62, 32.42, 32.57, 37.24, 40.15,
44.21, 58.90, 67.99, 68.32, 68.47, 68.97, 69.06, 70.04,
84.19. IR (KBr pellet): 3447, 3094, 2931, 2862, 1635,
1461, 1409, 1375, 1330, 1237, 1150, 1102, 1028, 1105,
818. MS: m/z (ESI) 412 (M++1), 434 (M++Na). HRMS
(MALDI): calcd for C24H37FeNO M+ 411.2219, found:
411.2244.
References
1. Noyori, R. Asymmetric Catalysis in Organic Synthesis;
Wiley: New York, 1994, Chapter 5.
2. (a) Reviews on enantioselective diorganozinc additions to
aldehydes: Noyori, R.; Kitamura, M. Angew.Chem,. Int.
Ed.Engl. 1991, 30, 49; (b) Soai, K.; Niwa, S. Chem.Rev.
1992, 92, 833; (c) Pu, L.; Yu, H.-B. Chem.Rev. 2001, 101,
757.
3. (a) Patti, A.; Nicolosi, G.; Howell, J. A. S.; Humphries, K.
Tetrahedron: Asymmetry 1998, 9, 4381–4394; (b) Deng,
W.-P.; Hou, X.-L.; Dai, L.-X. Tetrahedron: Asymmetry
1999, 10, 4689–4693; (c) Bastin, S.; Delebecque, N.;
4.7.7. (2S)-1-Ferrocenylmethylaziridin-2-yl(di-i-pentyl)-
methanol 5i. Following the general procedure gave
compound 5i as an orange red oil (204mg, 70%).
[a]D = ꢀ23.6 (c 0.958, CHCl3). 1H NMR (400MHz,
CDCl3): d 0.86 (m, 12H, 4 · CH3), 1.13–1.21 (m, 5H,
H–C(3), 2 · CH2), 1.32–1.46 (m, 6H,2 · CH2CH), 1.53
(dd, J1 = 6.4Hz, J2 = 3.6Hz, 1H, H–C(2)), 1.83 (d,
J = 3.2Hz, 1H, H–C(3)), 2.41 (br, 1H, OH), 3.24, 3.36
´
Agbossou, F.; Brocard, J.; Pelinski, L. Tetrahedron:
Asymmetry 1999, 10, 1647–1651; (d) Bastin, S.; Brocard,
´
J.; Pelinski, L. Tetrahedron Lett. 2000, 41, 7303–7307; (e)