K. Dhahagani et al. / Tetrahedron: Asymmetry 22 (2011) 857–865
865
Table 7
Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Comprehensive Asymmetric Catalysis;
Springer: Berlin, 1999; (d) Marqus-Lopez, E.; Merino, P.; Tejero, T.; Herrera, R.
P. Eur. J. Org. Chem. 2009, 2401; (e) Zhang, B.; Cai, L.; Song, H.; Wang, Z.; He, Z.
Adv. Synth. Catal. 2010, 352, 97.
Studies on the recyclability of the supported catalyst at rt
Catalyst
Run
Time (h)
Yielda (%)
ee (%)
3. Henry, L.; Hebd, C. R. Seances Acad. Sci. 1895, 120, 1265–1267.
4. Sasai, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc. 1992, 114,
4418–4420.
Cu-MCM-41
1
2
3
4
5
8
8
9
14
15
90
90
88
88
85
92
90
87
85
85
5. For reviews on the catalytic asymmetric Henry reaction, see: (a) Shibasaki, M.;
Grçger, H. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. III, pp 1075–1090; (b)
Shibasaki, M.; Grçger, H.; Kanai, M. In Comprehensive Asymmetric Catalysis;
Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 2004; pp
131–133. Supplement 1; (c) Palomo, C.; Oiarbide, M.; Mielgo, A. Angew. Chem.,
Int. Ed. 2004, 43, 5442–5444; (d) Boruwa, J.; Gogoi, J.; Saikia, P. P.; Barua, N. C.
Tetrahedron: Asymmetry 2006, 17, 3315–3326; (e) Palomo, C.; Oiarbide, M.;
Laso, A. Eur. J. Org. Chem. 2007, 2561–2574.
a
Isolated yield.
4.2.13. 1-Nitro-4-phenyl-but-3-en-2-ol (Table 6, entry 14)
1H NMR (CDCl3) d 3.01 (br, 1H), 4.50 (d, J = 7 Hz, 2H), 5.12 (m,
1H), 6.20 (dd, J = 14. 0, 7.0 Hz, 8.0 Hz, 1H), 6.85 (d, J = 14. 0 Hz,
1H), 7.21–7.42 (m, 5H) 13C NMR (CDCl3) d 135.1, 133.2, 128.2,
6. For selected examples, see: (a) Sohtome, Y.; Hashimoto, Y.; Nagasawa, K. Adv.
Synth. Catal. 2005, 347, 1643–1648; (b) Marcelli, T.; Van der Haas, R. N. S.; Van
Maarseveen, J. H.; Hiemstra, H. Angew. Chem., Int. Ed. 2006, 45, 929–931;
Reaction of
128, 732–733; Reaction of
a
-ketoesters: (c) Li, H.; Wang, B.; Deng, L. J. Am. Chem. Soc. 2006,
-ketophosphonates: (d) Mandal, T.; Samanta, S.;
127.8, 126.0, 124.3, 80.1, 69.1 ½a D24
¼ ꢀ22:2 (c 1.78, CH2Cl2) 90%
ꢁ
a
ee. HRMS (MC) calcd for C10H11NO3: 194.0817; found: 194.0821.
HPLC (DAICEL CHIRALCEL OD-H, iPrOH/hexane = 2/8, flow 0.8 mL/
min) 16.3 and 12.3 min.
Zhao, C. Org. Lett. 2007, 9, 943–945.
7. (a) Purkarthofer, T.; Gruber, K.; Gruber-Khadjawi, M.; Waich, K.; Skranc, W.;
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8. Rare-earth metals: (a) Saa, J. M.; Tur, F.; Gonzalez, J.; Vega, M. Tetrahedron:
Asymmetry 2006, 17, 99–106; (b) Tur, F.; Saa, J. M. Org. Lett. 2007, 9, 5079–
5082; Zinc: (c) Trost, B. M.; Yeh, V. S. C. Angew. Chem., Int. Ed. 2002, 41, 861–
863; (d) Palomo, C.; Oiarbide, M.; Laso, A. Angew. Chem., Int. Ed. 2005, 44, 3881–
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Juhl, K.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2002, 67, 4875–4881; (h)
Evans, D. A.; Seidel, D.; Rueping, M.; Lam, H. W.; Shaw, J. T.; Downey, C. W. J.
Am. Chem. Soc. 2003, 125, 12692–12693; (i) Ginotra, S. K.; Singh, V. K. Org.
Biomol. Chem. 2007, 5, 3932–3937; (j) Selvakumar, S.; Sivasankaran, D.; Singh,
V. K. Org. Biomol. Chem. 2009, 7, 3156; (k) Ma, K.; You, J. Chem. Eur. J. 2007, 13,
1863–1871; (l) Maheswaran, H.; Prasanth, K. L.; Krishna, G. G.; Ravikumar, K.;
Sridhar, B.; Kantam, M. L. Chem. Commun. 2006, 4066–4068; (m) Arai, T.;
Watanabe, M.; Fujiwara, A.; Yokoyama, N.; Yanagisawa, A. Angew. Chem., Int.
Ed. 2006, 45, 5978–5981; (n) Arai, T.; Watanabe, M.; Yanagisawa, A. Org. Lett.
2007, 9, 3595–3597; (o) Bandini, M.; Piccinelli, F.; Tommasi, S.; Umani-Ronchi,
A.; Ventrici, C. Chem. Commun. 2007, 616–618; Copper(I): (p) Xiong, Y.; Wang,
F.; Huang, X.; Wen, Y.; Feng, X. Chem. Eur. J. 2007, 13, 829–833; (q) Qin, B.; Xiao,
X.; Liu, X.; Huang, J.; Wen, Y.; Feng, X. J. Org. Chem. 2007, 72, 9323–9328; (r)
Blay, G.; Climent, E.; Fernández, I.; Hernández, V.; Pedro, J. Tetrahedron:
Asymmetry 2006, 17, 2046; (s) Blay, G.; Climent, E.; Fernández, I.; Hernández,
V.; Pedro, J. Tetrahedron: Asymmetry 2007, 18, 1603; (t) Blay, G.; Domingo, L. R.;
Hernández-Olmos, V.; Pedro, J. R. Chem. Eur. J. 2008, 14, 4725; (u) Noole, A.;
Lippur, K.; Metsala, A.; Lopp, M.; Kanger, T. J. Org. Chem. 2010, 75, 1313–1316;
Cobalt(II): (v) Kogami, Y.; Nakajima, T.; Ashizawa, T.; Kezuka, S.; Ikeno, T.;
Yamada, T. Chem. Lett. 2004, 33, 614–615; (w) Kogami, Y.; Nakajima, T.; Ikeno,
T.; Yamada, T. Synthesis 2004, 1947–1950; Magnesium: (x) Choudary, B. M.;
Ranganath, K. V. S.; Pal, U.; Kantam, M. L.; Sreedhar, B. J. Am. Chem. Soc. 2005,
127, 13167–13171; Chromium(III): (y) Kowalczyk, R.; Kwiatkowski, P.;
Skarz_ewski, J.; Jurczak, J. J. Org. Chem. 2009, 74, 753–756; (z) Kowalczyk, R.;
Sidorowicz, L.; Skarzewski, J. Tetrahedron: Asymmetry 2007, 18, 2581; (aa)
Zulauf, A.; Mellah, M.; Schulz, E. J. Org. Chem. 2009, 74, 2242.
4.2.14. 1-(Furan-2yl)-2-nitroethanol (Table 6, entry 15)
1H NMR (CDCl3) d 2.99 (br, 1H), 4.61–4.81 (m, 2H), 5.47 (dd,
J = 9.0, 3.0 Hz, 1H), 6.31–6.41 (m, 2H), 7.41 (d, J = 8.0 Hz, 1H). 13C
NMR (CDCl3) d 150.1, 143.0, 110.0, 108.1, 78.2, 64.8 ½a D24
¼ ꢀ26:2
ꢁ
(c 1.78, CH2Cl2) 90% ee. HRMS calcd for C6H7NO4: 157.0375; found:
157.0369; HPLC (DAICEL CHIRALCEL OB-H, iPrOH/hexane = 2/8,
flow 0.9 mL/min) 36.5 and 36.9 min.
4.2.15. 1-Cyclohexyl-2-nitroethanol (Table 6, entry 17)
1H NMR (CDCl3, 200 MHz): d = 0.22 (s, 9H), 1.88 (s, 3H), 6.35–
6.40 (m, 1H), 6.47–6.50(m, 1H), 7.41–7.43 (m, 1H). 13C NMR
(CDCl3): d = 0.49, 28.37, 65.89, 108.14, 110.68, 120.23, 143.09,
151.63. HRMS: calcd for C8H15NO3: 173.1052, found 173.1060;
HPLC (DAICEL CHIRALCEL OB-H, iPrOH/hexane = 2/8, flow
0.98 mL/min) 31.0 and 31.8 min.
4.2.16. 3,3-Dimethyl-1-nitrobutan-2-ol (Table 6, entry 18)
1H NMR (CDCl3, 200 MHz): d = 1.01 (9H, s); 2.41 (1H, d,
J = 4.5 Hz); 4.10–4.15 (1H, m); 4.31–4.55 (2H, m). ½a D24
¼ ꢀ28:1 (c
ꢁ
1.78, CH2Cl2) 69% ee. HRMS: calcd for C6H13NO3: 147.0895, found
147.0887; HPLC (DAICEL CHIRALCEL OB-H, iPrOH/hexane = 2/8,
flow 0.9 mL/min) 25.5 and 26.3 min.
4.2.17. 1-Nitro-2-heptanol (Table 6, entry 19)
1H NMR (CDCl3, 200 MHz): d = 0.85 (t, J = 7.0 Hz, 3H), 1.30–1.43
(m, 5H), 1.39–1.51 (m, 3H), 2.80 (d, J = 5.0 Hz, 1H), 4.24–4.28 (m,
1H), 4.39 (dd, J = 13.0, 8.0 Hz, 1H), 4.32 (dd, J = 13.0, 3.0 Hz, 1H),
13C NMR (CDCl3) d = 14.6, 23.1, 24.9, 31.1, 35.3, 68.1, 80.5.
9. Cheng, L.; Dong, J.; You, J.; Gao, G.; Lan, J. Chem. Eur. J. 2010, 16, 6761–6765.
10. Sanjeevakumar, N.; Periasamy, M. Tetrahedron: Asymmetry 2009, 20, 1842–
1847.
11. (a) Jin, W.; Li, X.; Huang, Y.; Wu, F.; Wan, B. Chem. Eur. J. 2010, 16, 8259–8261;
(b) Steurer, M.; Bolm, C. J. Org. Chem. 2010, 75, 3301–3310.
12. Mastrorilli, P.; Nobile, C. F. Coord. Chem. Rev. 2004, 248, 377–395.
13. (a) Corma, A. Chem. Rev. 1997, 97, 2373; (b) On, D. T.; Desplantier-Giscard, D.;
Danumah, C.; Kaliaguine, S. Appl. Catal. A 2003, 253, 545; (c) Taguchi, A.;
Schusth, F. Microporous Mesoporous Mater. 2005, 77, 1.
½
a 2D4
ꢁ
¼ ꢀ28:2 (c 1.78, CH2Cl2) 70% ee. HRMS: calcd for C7H15NO3:
161.1052; found 161.1040. HPLC (DAICEL CHIRALCEL OB-H,
iPrOH/hexane = 2/8, flow 0.9 mL/min) 33.7 and 28.2 min.
14. Bhatt, A. P.; Pathak, K.; Jasra, R. V.; Kureshy, R. I.; Khan, N. H.; Abdi, S. H. R. J.
Mol. Catal. A: Chem. 2006, 244, 110–117.
Acknowledgment
15. (a) Mayani, V. J.; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Agrawal, S.; Jasra, R. V.
J. Chromatogr., A 2008, 223, 1191; (b) Mayani, V. J.; Abdi, S. H. R.; Kureshy, R. I.;
Khan, N. H.; Agrawal, S.; Jasra, R. V. J. Chromatogr., A 2006, 186, 1135; (c)
Mayani, V. J.; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Agrawal, S.; Jasra, R. V.
Chirality 2008, 21, 255.
Financial support from the University Grants Commission, New
Delhi [Grant No: F. No. 38-70/2009(SR)] is gratefully acknowledged.
16. Mayani, V. J.; Abdi, S. H. R.; Kureshy, R. I.; Khan, N. H.; Das, A.; Bajaj, H. C. J. Org.
Chem. 2010, 75, 6191–6195.
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