2444
S. M. Silvestre, J. A. R. Salvador / Tetrahedron 63 (2007) 2439–2445
1
3025 cmꢂ1; H NMR (CDCl3, 300 MHz): d 0.68 (s, 3H,
18-CH3), 0.86 (d, J¼6.6 Hz, 6H, 26-CH3, 27-CH3), 0.92
(d, J¼6.5 Hz, 3H, 21-CH3), 1.20 (s, 3H, 19-CH3), 2.03 (s,
3H, CH3CO), 4.69 (m, 1H, 3a-CH), 5.70 (m, 1H, 6-CH);
13C NMR (CDCl3, 75 MHz): d 72.17 (C-3), 126.64 (C-6),
163.82 (C-5), 170.22 (CH3CO), 201.87 (C-7).
(d, J¼7.6 Hz, 1H, 5-CH), 7.39 (t, J¼7.5 Hz, 1H, 7-CH),
7.54 (m, 1H, 6-CH), 8.08 (d, J¼7.7 Hz, 1H, 8-CH); 13C
NMR (CDCl3, 75 MHz): d 27.64 (C-4), 67.19 (C-3),
125.11, 127.14, 127.52, 130.18, 133.55, 139.44 (arom.),
165.02 (C-1).
Acknowledgements
4.3.2. Compound 8. Mp 150–153 ꢀC (MeOH); lit.53 152–
153 ꢀC; IR (ATR): 1244, 1630, 1669, 1704, 1727, 2941,
J.A.R.S. thanks Universidade de Coimbra for financial
1
3037 cmꢂ1; H NMR (CDCl3, 300 MHz): d 0.66 (s, 3H,
~
^
support. S.M.S. thanks Fundac¸ao para a Ciencia e Tecnolo-
gia for a grant (SFRH/BD/11087/2002). We kindly acknowl-
edge the Center of NMR Spectroscopy and Center for
Neurosciences and Cell Biology, University of Coimbra,
Portugal (Professor C. Geraldes) and Professor J. Laranjinha
(Center for Neurosciences and Cell Biology, University of
Coimbra, Portugal) for the ESR experiments.
18-CH3), 1.21 (s, 3H, 19-CH3), 2.06 (s, 3H, CH3CO), 2.14
(s, 3H, 21-CH3), 4.72 (m, 1H, 3a-CH), 5.73 (m, 1H, 6-
CH); 13C NMR (CDCl3, 75 MHz): d 72.00 (C-3), 126.41
(C-6), 164.13 (C-5), 170.23 (CH3CO), 201.11 (C-7),
209.64 (C-20).
4.3.3. Compound 9. Mp 229–232 ꢀC (MeOH); lit.53 232.5–
233 ꢀC; IR (ATR): 1298, 1630, 1649, 1719, 2941, 3025,
1
3480 cmꢂ1; H NMR (CDCl3, 300 MHz): d 0.90 (s, 3H,
References and notes
18-CH3), 1.23 (s, 3H, 19-CH3), 3.68 (m, 1H, 3a-CH), 5.75
(m, 1H, 6-CH); 13C NMR (CDCl3, 75 MHz): d 70.2 (C-3),
125.7 (C-6), 166.2 (C-5), 200.7 (C-7), 219.8 (C-17).
1. (a) Muzart, J. Bull. Soc. Chim. Fr. 1986, 65; (b) Bulman Page,
P. C.; McCarthy, T. J. Comprehensive Organic Synthesis; Trost,
B. M., Flemming, I., Eds.; Pergamon: Oxford, New York, NY,
Seoul, Tokyo, 1991; Vol. 7, pp 83–117; (c) Sheldon, R. A.;
Kochi, J. K. Metal-Catalyzed Oxidations of Organic Com-
pounds; Academic: New York, NY, London, Toronto, Sydney,
San Francisco, CA, 1981.
2. Arsenou, E. S.; Fousteris, M. A.; Koutsourea, A. I.;
Nikolaropoulos, S. S. Mini Rev. Med. Chem. 2003, 3, 557.
3. Sousa, M. E.; Pinto, M. M. M. Curr. Med. Chem. 2005, 12,
2447.
4.3.4. Compound 10. Mp 31–34 ꢀC; lit.54 33–35 ꢀC; IR
(ATR): 1617, 1663, 2933, 3029, 3079 cmꢂ1 1H NMR
;
(CDCl3, 300 MHz): d 0.94 (d, J¼6.8 Hz, 3H, 15-CH3),
1.09 (s, 3H, 14-CH3), 1.71 (s, 3H, 13-CH3), 4.70 (m, 2H,
12-CH2), 5.74 (s, 1H, 1-CH); 13C NMR (CDCl3, 75 MHz):
d 109.12 (C-12), 124.44 (C-1), 148.87 (C-11), 170.82
(C-10), 199.79 (C-2).
4.3.5. Compound 15. Mp 169–171 ꢀC (PhH); lit.55 172–
4. (a) Dauben, W. G.; Lorber, M.; Fullerton, D. S. J. Org. Chem.
1969, 34, 3587; (b) Fullerton, D. S.; Chen, C.-M. Synth.
Commun. 1976, 6, 217.
173 ꢀC; IR (ATR): 757, 1145, 1345, 1456, 1479, 1605,
1655, 2937, 3079 cmꢂ1 1H NMR (CDCl3, 300 MHz):
;
d 7.38 (t, J¼7.9 Hz, 2H, 2-CH, 7-CH), 7.49 (d, J¼8.4 Hz,
2H, 4-CH, 5-CH), 7.73 (m, 2H, 3-CH, 6-CH), 8.34 (dd,
J¼7.9, 1.7 Hz, 2H, 1-CH, 8-CH); 13C NMR (CDCl3,
75 MHz): d 117.95 (C-4, C-5), 121.81 (C-8a, C-9a),
123.87 (C-2, C-7), 126.70 (C-1, C-8), 134.78 (C-3, C-6),
156.14 (C-4a, C-10a), 177.19 (C-9).
5. Salmond, W. G.; Barta, M. A.; Havens, J. L. J. Org. Chem.
1978, 43, 2057.
6. Parish, E. J.; Chitrakorn, S.; Wei, T.-Y. Synth. Commun. 1986,
16, 1371.
7. Parish, E. J.; Wei, T.-Y. Synth. Commun. 1987, 17, 1227.
8. Chidambaram, N.; Chandrasekaran, S. J. Org. Chem. 1987, 52,
5048.
9. Marshall, C. W.; Ray, R. E.; Laos, I.; Riegel, B. J. Am. Chem.
Soc. 1957, 79, 6308.
4.3.6. Compound 16. Mp 79–82 ꢀC (MeOH); lit.55 81–
1
82 ꢀC; IR (ATR): 1297, 1449, 1598, 1712, 3060 cmꢂ1; H
NMR (CDCl3, 300 MHz): d 7.28 (m, 2H, 2-CH, 7-CH),
7.48 (m, 4H, 3-CH, 4-CH, 5-CH, 6-CH), 7.65 (d,
J¼7.4 Hz, 2H, 1-CH, 8-CH); 13C NMR (CDCl3, 75 MHz):
d 120.27 (C-4, C-5), 124.27 (C-1, C-8), 129.03 (C-2, C-7),
134.09 (C-8a, C-9a), 134.65 (C-3, C-6), 144.38 (C-4a,
C-4b), 193.89 (C-9).
10. Amann, A.; Ourisson, G.; Luu, B. Synthesis 1987, 1002.
11. Parish, E. J.; Sun, H.; Kizito, S. A. J. Chem. Res., Synop. 1996,
544.
12. Bora, U.; Chaudhuri, M. K.; Dey, D.; Kalita, D.;
Kharmawphlang, W.; Mandal, G. C. Tetrahedron 2001, 57,
2445.
13. Marwah, P.; Lardy, H. A. U.S. Patent 6,384,251 B1, 2002.
14. Hudlickꢀy, M. Oxidations in Organic Chemistry; ACS
Monograph 186; American Chemical Society: Washington,
DC, 1990 and references cited therein.
4.3.7. Compound 17. Mp 46–47.5 ꢀC (MeOH); lit.56 47–
49 ꢀC; IR (ATR): 810, 1276, 1447, 1594, 1650,
1
3057 cmꢂ1; H NMR (CDCl3, 300 MHz): d 7.46 (m, 4H,
4-CH, 6-CH, 10-CH, 12-CH), 7.57 (m, 2H, 5-CH, 11-CH),
7.80, (m, 4H, 3-CH, 7-CH, 9-CH, 13-CH); 13C NMR
(CDCl3, 75 MHz): d 128.19 (C-4, C-6, C-10, C-12),
129.96 (C-3, C-7, C-9, C-13), 132.34 (C-5, C-11), 137.48
(C-2, C-8), 196.66 (C-1).
15. (a) Bennur, T. H.; Sabne, S.; Deshpande, S. S.; Srinivas, D.;
Sivasanker, S. J. Mol. Catal. A: Chem. 2002, 185, 71; (b)
Klopstra, M.; Hage, R.; Kellogg, R. M.; Feringa, B. L. Tetra-
hedron Lett. 2003, 44, 4581; (c) Maksimchuk, N. V.; Melgu-
ꢀ
nov, M. S.; Mrowiec-Bia1on, J.; Jarzxbski, A. B.; Kholdeeva,
O. A. J. Catal. 2005, 235, 175.
4.3.8. Compound 18. Colourless oil;57 IR (film): 695, 747,
1092, 1121, 1244, 1295, 1394, 1459, 1607, 1721, 2951,
16. Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Chem. Rev. 2005,
105, 2329 and references cited therein.
17. Salvador, J. A. R.; Silvestre, S. M.; Moreira, V. M. Curr. Org.
Chem. 2006, 10, 2227.
3070 cmꢂ1
;
1H NMR (CDCl3, 300 MHz): d 3.05 (t,
J¼6 Hz, 2H, 4-CH2), 4.53 (t, J¼6 Hz, 2H, 3-CH2), 7.27