CHCl3). IR mmax/cm−1 (film) 3026, 2934, 2855, 1654, 1495, 1451,
1348, 1228, 1127, 980; H NMR (CDCl3, 400 MHz) d 1.45 (bs,
2 For reviews on the nitroaldol reaction, see: (a) D. Seebach, A. K. Beck,
T. Mukhopadhyay and E. Thomas, Helv. Chim. Acta, 1982, 65, 1101;
(b) G. Rosini, in Comprehensive Organic Synthesis, ed. B. M. Trost,
I. Fleming and C. H. Heathcock, , Pergamon, New York, 1996, vol. 2,
p. 321; (c) N. Ono, The Nitro Group in Organic Synthesis, Wiley-VCH,
New York, 2001, ch. 3, p. 30; (d) F. A. Luzio, Tetrahedron, 2001, 57,
915.
3 (a) M. Yamaguchi, T. Shiraishi and M. Hirama, J. Org. Chem., 1996,
61, 3520; (b) M. Yamaguchi, Y. Igarashi, R. S. Reddy, T. Shiraishi and
M. Hirama, Tetrahedron, 1997, 53, 11223.
1
4H), 1.62 (bs, 2H), 1.92–2.07 (m, 4H), 2.64 (dd, J = 13.6, 8.5 Hz,
2H), 3.11 (dd, J = 13.7, 4.6 Hz, 2H), 3.99 (dd, J = 8.5, 7.1 Hz,
2H), 4.14 (t, J = 8.6 Hz, 2H), 4.38–4.46 (m, 2H), 7.19–7.30 (m,
10H); 13C NMR (CDCl3, 100 MHz) d 22.5, 25.4, 32.4, 41.4, 43.1,
67.2, 71.5, 126.4, 128.4, 129.4, 137.8, 168.2; HRMS (ES+): Exact
mass calcd for C26H30N2O2 [M + H]+, 403.2385, Found 403.2383.
4 (a) R. Breslow, Science, 1982, 218, 532; (b) A. J. Kirby, Angew. Chem.,
Int. Ed. Engl., 1996, 35, 707.
(4S,4ꢀS)-2,2ꢀ -(2,3-Dihydro-1H -indene-2,2-diyl)-bis(4-benzyl-
4,5-dihydrooxazole) (6e). The compound was purified by silica
gel column chromatography using EtOAc–pet ether. It was
obtained in a maximum of 51% yield as a colorless oil. [a]2D5 +2.8
(c 1.75, CHCl3). IR mmax/cm−1 (film) 3026, 2923, 1658, 1492, 1454,
1352, 1233, 1155, 1029, 965; 1H NMR (CDCl3, 400 MHz) d 2.64
(dd, J = 13.7, 8.0 Hz, 2H), 2.98 (dd, J = 13.7, 4.9 Hz, 2H), 3.47
(d, J = 16.1 Hz, 2H), 3.70 (d, J = 16.4 Hz, 2H), 4.02 (dd, J =
8.6, 6.8 Hz, 2H), 4.20 (t, J = 8.8 Hz, 2H), 4.36–4.43 (m, 2H)
7.08–7.26 (m, 14H);13C NMR (CDCl3, 100 MHz) d 41.1, 41.5,
48.8, 66.9, 72.2, 124.2, 126.3, 126.6, 128.3, 129.4, 137.4, 140.4,
168.0; HRMS (ES+): Exact mass calcd for C29H28N2O2 [M + H]+,
437.2229, Found 437.2227.
5 B. M. Trost, V. S. C. Yeh, H. Ito and N. Bremeyer, Org. Lett., 2002, 4,
2621.
6 (a) H. Sasai, T. Suzuki, N. Itoh, S. Arai and M. Shibasaki, Tetrahedron
Lett., 1983, 34, 2657; (b) H. Sasai, N. Itoh, T. Suzuki and M. Shibasaki,
Tetrahedron Lett., 1983, 34, 855; (c) H. Sasai, Y. M. A. Yamada, T.
Suzuki and M. Shibasaki, Tetrahedron, 1994, 50, 12313.
7 (a) D. A. Lednicer and L. A. Mitscher, The Organic Chemistry of Drug
Synthesis, John Wiley and Sons, New York, 1975; (b) P. M. Koskinen
and M. P. Koskinen, Synthesis, 1998, 1075.
8 For recent reviews on the catalytic asymmetric nitroaldol reaction, see:
(a) C. Palomo, M. Oiarbide and A. Mielgo, Angew. Chem., Int. Ed.,
2004, 43, 5442; (b) C. Palomo, M. Oiarbide and A. Laso, Eur. J. Org.
Chem., 2007, 2561.
9 (a) H. Sasai, T. Suzuki, S. Arai, T. Arai and M. Shibasaki, J. Am. Chem.
Soc., 1992, 114, 4418; (b) T. Arai, Y. M. A. Yamada, N. Yamamoto, H.
Sasai and M. Shibasaki, Chem. Eur. J., 1996, 2, 1368; (c) M. Shibasaki
and N. Yoshikawa, Chem. Rev., 2002, 102, 2187.
(4S,4ꢀS)-2,2ꢀ -(1,3-Diphenylpropane-2,2-diyl)-bis(4-benzyl-4,5-
dihydrooxazole) (6f). The compound was purified by silica gel
column chromatography using EtOAc–pet ether. It was obtained
in a maximum of 75% yield as a colorless oil. [a]2D5 −18.4 (c 1.35,
CHCl3). IR mmax/cm−1 (film) 3027, 2927, 1656, 1452, 1176, 1082,
10 B. M. Trost and V. S. C. Yeh, Angew. Chem., Int. Ed., 2002, 41,
861.
11 (a) Y. Kogami, T. Nakajima, T. Ikeno and T. Yamada, Synthesis, 2004,
12, 1947; (b) Y. Kogami, T. Nakajima, T. Ashizawa, S. Kezuka, T. Ikeno
and T. Yamada, Chem. Lett., 2004, 33, 614.
12 D. A. Evans, D. Seidel, M. Rueping, H. W. Lam, J. T. Shaw and C. W.
Downey, J. Am. Chem. Soc., 2003, 125, 12692.
13 (a) C. Christensen, K. Juhl and K. A. Jørgensen, Chem. Commun., 2001,
2222; (b) C. Christensen, K. Juhl, R. G. Hazell and K. A. Jørgensen,
J. Org. Chem., 2002, 67, 4875.
14 (a) S. F. Lu, D. M. Du, S. W. Zhang and J. X. Xu, Tetrahedron:
Asymmetry, 2004, 15, 3433; (b) D. M. Du, S. F. Lu, T. Fang and J. X.
Xu, J. Org. Chem., 2005, 70, 3712.
15 (a) C. Palomo, M. Oiarbide and A. Laso, Angew. Chem., Int. Ed., 2005,
44, 3881; (b) C. Palomo, M. Oiarbide, A. Halder, A. Laso and R. Loper,
Angew. Chem., Int. Ed., 2006, 45, 117.
1
1031, 961; H NMR (CDCl3, 400 MHz) d 2.32 (dd, J = 13.6,
9.3 Hz, 2H), 2.99 (d, J = 13.6, 5.4 Hz, 2H), 3.37 (s, 4H), 3.89 (t,
J = 8.6 Hz, 2H), 4.13 (t, J = 9.3 Hz, 2H), 4.28–4.36 (m, 2H) 7.11–
7.32 (m, 20H); 13C NMR (CDCl3, 100 MHz) d 39.3, 41.5, 48.2,
67.3, 71.9, 126.4, 126.8, 128.0, 128.5, 129.1, 130.5, 136.8, 138.0,
166.7; HRMS (ES+): Exact mass calcd for C35H34N2O2 [M + H]+,
515.2698, Found 515.2697.
16 (a) B. M. Choudary, K. V. S. Ranganath, U. Pal, M. L. Kantam and B.
Sreedhar, J. Am. Chem. Soc., 2005, 127, 13167; (b) T. Purkarthofer,
K. Gruber, M. G. Khadjawi, K. Waich, W. Skranc, D. Mink and
H. Grirngl, Angew. Chem., Int. Ed., 2006, 45, 3454; (c) T. Arai, M.
Watanabe, A. Fujiwara, N. Yokoyama and A. Yanagisawa, Angew.
Chem., Int. Ed., 2006, 45, 5978; (d) H. Maheswaran, K. L. Prasanth,
G. G. Krishna, K. Ravikumar, B. Sridhar and M. L. Kantam, Chem.
Commun., 2006, 4066; (e) M. Bandini, M. Benaglia, R. Sinisi, S.
Tommasi and A. Umani-Ronchi, Org. Lett., 2007, 9, 2151; (f) K. Ma
and J. You, Chem. Eur. J., 2007, 13, 1863; (g) M. Bandini, F. Piccinelli, S.
Tommasi, A. Umani-Ronchi and C. Ventrici, Chem. Commun., 2007,
616; (h) Y. Xiong, F. Wang, X. Huang, Y. Wen and X. Feng, Chem.
Eur. J., 2007, 13, 829; (i) T. Arai, M. Watanabe and A. Yanagisawa,
Org. Lett., 2007, 9, 3595.
17 (a) Y. Sohtome, Y. Hashimoto and K. Nagasawa, Adv. Synth. Catal.,
2005, 347, 1643; (b) Y. Sohtome, Y. Hashimoto and K. Nagasawa,
Eur. J. Org. Chem., 2006, 2894.
18 (a) T. Marcelli, R. N. S. van der Haas, J. H. van Maarseveen and H.
Hiemstra, Angew. Chem., Int. Ed., 2006, 45, 929; (b) H. Li, B. Wang
and L. Deng, J. Am. Chem. Soc., 2006, 128, 732.
General procedure for the enantioselective Henry reaction
To a oven-dried 5 mL round-bottomed flask a solution of
appropriate ligand (0.06 mmol) and Cu(OAc)2·H2O (10.0 mg,
0.05 mmol) in the appropriate solvent (2 mL) was stirred for
2 h at room temperature. To the resulting clear blue solution
nitromethane (10 mmol) and the aldehyde (1 mmol) were added.
The reaction mixture was left at room temperature until the
reaction was complete (disappearance of aldehyde by TLC),
during which time the color of the solution changed to green.
After evaporation of the solvent, the residue was purified by
column chromatography on silica gel (EtOAc–pet ether) to afford
the nitroaldol product.
Acknowledgements
19 (a) A. DattaGupta and V. K. Singh, Tetrahedron Lett., 1996, 37, 2633;
(b) G. Sekar, A. DattaGupta and V. K. Singh, J. Org. Chem., 1998,
63, 2961; (c) S. K. Ginotra and V. K. Singh, Tetrahedron, 2006, 62,
3573; (d) S. K. Ginotra and V. K. Singh, Org. Biomol. Chem., 2006, 3,
4370.
V.K.S. thanks DST, India, for a Ramanna fellowship. S.K.G.
thanks CSIR for a senior research fellowship.
20 A. DattaGupta, D. Bhuniya and V. K. Singh, Tetrahedron, 1994, 50,
13725.
References
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3936 | Org. Biomol. Chem., 2007, 5, 3932–3937
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