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P. Radha Krishna et al. / Tetrahedron Letters 45 (2004) 1183–1185
1185
combined organic layers were washed with brine, dried
(Na2SO4) and concentrated under reduced pressure. The
residues thus obtained were purified by column chroma-
tography to afford adducts 1a–1e, 2a–2c, 3a, 4a, 5a–c, 6a–
b, 7a–c, 8a and 8b in 66–96% yield. Compounds 2a–c, 4a,
5b–c and 7b–c are already reported in literature as cited in
Ref. 5.
Acknowledgements
One of the authors, V. K., acknowledges CSIR,
New Delhi for financial support in the form of a
fellowship.
1
17. Spectral data for selected compounds: 1b: Yellow oil; H
NMR (300 MHz, CDCl3, TMS): d 8.20 (d, 2H, J ¼ 8:7 Hz,
Ar–H), 7.54 (d, 2H, J ¼ 8:3 Hz, Ar–H), 6.66 (s, 1H,
olefinic), 6.23 (s, 1H, olefinic), 5.98 (s, 1H, benzylic), 3.12
(d, 1H, J ¼ 5:66 Hz, –OH), 2.32 (s, 3H, –CH3); 13C NMR
(50 MHz, CDCl3): d 26.32, 29.65, 72.14, 123.55, 123.75,
127.23, 127.74, 147.29, 148.95, 200.07; IR (neat): m 3418,
1713, 1619 1519 cmꢀ1; EIMS: m=z: 204 (M- 17)þ; Anal.
calcd for C11H11NO4; C, 59.73; H, 5.01; found: C, 59.57;
H, 5.06. 1c: Yellow oil; 1H NMR (200 MHz, CDCl3,
TMS): d 8.24 (d, 2H, J ¼ 8:7 Hz, Ar–H), 7.63 (d, 2H,
J ¼ 8:4 Hz, Ar–H), 6.39 (s, 1H, olefinic), 6.20 (s, 1H,
olefinic), 6.02 (s, 1H, allylic), 5.38 (br s, 1H, –OH); 13C
NMR (50 MHz, CDCl3): d 72.07, 123.22, 126.07, 127.20,
References and notes
1. Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653.
2. Basavaiah, D.; Rao, P. D.; Hyma, R. S. Tetrahedron 1996,
52, 8001.
3. Ciganek, E. The Morita–Baylis–Hillman reaction. In
Organic Reactions; Paquette, L. A., Ed.; John Wiley &
Sons: New York, 1997; Vol. 51, p 201.
4. Langer, P. Angew. Chem., Int. Ed. 2000, 39, 3049.
5. Basavaiah, D.; Rao, A. J.; Satyanarayana, T. Chem. Rev.
2003, 103, 811.
6. (a) Yu, C.; Liu, B.; Hu, L. J. Org. Chem. 2001, 66, 5413;
(b) Yu, C.; Hu, L. J. Org. Chem. 2002, 67, 219; (c)
Aggarwal, V. K.; Dean, D. K.; Mereu, A.; Williams, R.
J. Org. Chem. 2002, 67, 510; (d) Cai, J.; Zhou, Z.; Zhao,
G.; Tang, C. Org. Lett. 2002, 4, 4723.
7. Kumar, A.; Pawar, S. S. Tetrahedron 2003, 59, 5019.
8. (a) Aggarwal, V. K.; Mereu, A. Chem. Commun. 1999,
2311; (b) Aggarwal, V. K.; Emme, I.; Fulford, S. Y.
J. Org. Chem. 2003, 68, 692.
9. Kundu, M. K.; Mukherjee, S. B.; Balu, N.; Padmakumar,
R.; Bhat, S. V. Synlett 1994, 444.
130.59, 147.09, 147.88; IR (neat): m 3440, 2228, 1607 cmꢀ1
.
3a: Colourless oil; 1H NMR (200 MHz, CDCl3, TMS):
d 7.55 (d, 1H, J ¼ 7:0 Hz, Ar–H), 7.39–7.21 (m, 3H, Ar–
H), 6.28 (s, 1H, olefinic), 5.92 (d, 1H, J ¼ 3:7 Hz,
benzylic), 5.52 (s, 1H, olefinic), 4.22 (q, 2H, J ¼ 7:4 Hz,
–CH2), 3.25 (d, 1H, J ¼ 3:7 Hz, –OH), 1.28 (t, 3H,
J ¼ 7:4 Hz, –CH3); IR (neat): m 3396, 1720, 1614 cmꢀ1
;
EIMS: m=z: 241 (Mþ+1); Anal. calcd for C12H13ClO3; C,
59.88; H, 5.44; found: C, 59.71; H, 5.40. 5a: 1H NMR
(300 MHz, CDCl3, TMS): d 8.43–8.39 (m, 2H, ArH), 7.71
(d, 1H, J ¼ 7:8 Hz, ArH), 7.24–7.20 (m, 1H, ArH), 6.34 (s,
1H, olefinic), 5.92 (s, 1H, olefinic), 5.55 (s, 1H, benzylic),
4.18 (q, 2H, J ¼ 6:9 Hz, –CH2), 1.23 (t, 3H, J ¼ 6:9 Hz,
–CH3); 13C NMR (75 MHz, CDCl3): d 23.11, 51.62, 74.52,
117.68, 126.63, 126.68, 129.00, 130.58, 140.06; IR (neat): m
3387, 1722, 1638 cmꢀ1; EIMS m=z 207 (Mþ); Anal. calcd
for C11H13NO3; C, 63.76; H, 6.32; found: C, 63.65; H,
6.29. 7a: 1H NMR (300 MHz, CDCl3, TMS) d 6.22 (s, 1H,
olefinic), 5.79 (s, 1H, olefinic), 4.40 (t, 1H, J ¼ 6:4 Hz,
allylic), 4.24 (q, 2H, J ¼ 7:2 Hz, –CH2), 2.73 (br s, 1H,
–OH), 1.70–1.62 (m, 2H, –CH2), 1.39–1.25 (m, 9H), 0.93–
0.84 (m, 3H, –CH3); 13C NMR (75 MHz, CDCl3, TMS):
d 12.06, 19.84, 23.33, 29.56, 33.44, 58.72, 69.21, 122.87,
141.14, 164.07; IR (neat): m 3385, 1717, 1628 cmꢀ1. EIMS
m=z 201 (Mþ+1); Anal. calcd for C11H20O3; C, 65.97; H,
10. Rosa, J. N.; Afonso, C. A. M.; Santos, A. G. Tetrahedron
2001, 57, 4189.
11. (a) Drewes, S. E.; Freese, S.; Emslie, N. D.; Roos, G. H. P.
Synth. Commun. 1988, 18, 1565; (b) Basavaiah, D.; Sarma,
P. K. S. Synth. Commun. 1990, 20, 1611; (c) Bailey, M.;
Marko, I. E.; Ollis, W. D.; Rasmussen, P. R. Tetrahedron
Lett. 1990, 31, 4509.
12. (a) Hill, J. S.; Isaacs, N. S. Tetrahedron Lett. 1986, 27,
5007; (b) Schuurman, R. J. W.; van der Linden, A.;
Grimbergen, R. P. F.; Nolte, R. J. M.; Scheeren, H. W.
Tetrahedron 1996, 52, 8307.
13. (a) Radha Krishna, P.; Kannan, V.; Ilangovan, A.;
Sharma, G. V. M. Tetrahedron: Asymmetry 2001, 12,
829; (b) Radha Krishna, P.; Kannan, V.; Sharma, G. V.
M.; Ramana Rao, M. H. V. Synlett 2003, 888; (c) Radha
Krishna, P.; Raja Sekhar, E.; Kannan, V. Tetrahedron
Lett. 2003, 44, 4973.
1
10.07; found: C, 65.83; H, 10.02. 8b: H NMR (300 MHz,
CDCl3) d 6.29 (s, 0.2H, olefinic), 6.26 (s, 0.8H, olefinic),
6.18 (s, 0.2H, olefinic), 6.11 (s, 0.8H, olefinic), 5.86 (s, 1H,
J ¼ 3:8 Hz, H-1), 4.60–4.48 (m, 2H, H-5, H-2), 4.25–4.17
(m, 1H, H-4), 3.82 (d, 1H, J ¼ 3:7 Hz, H-3), 3.51 (s, 3H,
–OMe), 2.41 (s, 3H, –CH3), 1.46 (s, 3H, –CH3), 1.33 (s,
3H, –CH3); 13C NMR (50 MHz, CDCl3): 26.75, 57.95,
69.54, 80.18, 81.49, 84.23, 86.47, 105.01, 111.70, 128.01,
14. Isaacs, N. S.; Hill, J. S. Eur. Patent Appl. EP 196708,
1986; Chem. Abstr. 1987, 106, 19155h.
15. Yu, C.; Hu, L. J. Org. Chem. 2002, 67, 219.
16. General experimental procedure: To a stirred solution of
aldehyde (1 mmol) in sulpholane (1 mL) were added
DABCO (0.5 mmol) and the alkene (3 mmol) and the
reaction mixture stirred for 0.5 to 10 h at room temper-
ature. Then the reaction mixture was diluted with water
(20 mL) and extracted with diethyl ether (3 · 10 mL). The
147.11, 200.90; IR (neat): m 3428, 1715, 1626 cmꢀ1
;
FABMS: m=z: 273 (Mþ+1); Anal. calcd for C13H20O6; C,
57.34; H, 7.40; found: C, 57.27; H, 7.36.