K. R. Prasad, S. L. Gholap / Tetrahedron Letters 48 (2007) 4679–4682
4681
J.-P.; Vatele, J.-M. Tetrahedron 1999, 55, 13011–13028; For
syntheses of 6-epi-goniodiol and leiocarpin A: (o) Chen, J.;
Lin, J. Q.; Liu, H. Q. Tetrahedron Lett. 2004, 45, 8111–8113.
6. (a) Prasad, K. R.; Gholap, S. L. Synlett 2005, 2260–2262;
(b) Prasad, K. R.; Gholap, S. L. J. Org. Chem. 2006, 71,
3643–3645; (c) Prasad, K. R.; Anbarasan, P. Tetrahedron:
Asymmetry 2005, 16, 3951–3953; (d) Prasad, K. R.;
Anbarasan, P. Tetrahedron Lett. 2006, 47, 1433–1435; (e)
Prasad, K. R.; Anbarasan, P. Synlett 2006, 2087–2088; (f)
Prasad, K. R.; Anbarasan, P. Tetrahedron: Asymmetry
2006, 17, 1146–1151; (g) Prasad, K. R.; Anbarasan, P.
Tetrahedron 2006, 62, 8303–8308; (h) Prasad, K. R.;
Chandrakumar, A.; Anbarasan, P. Tetrahedron: Asymme-
try 2006, 17, 1979–1984; (i) Prasad, K. R.; Anbarasan, P.
Tetrahedron 2007, 63, 1089–1092.
corresponding methoxymethyl (MOM) ethers 19 and 20
using standard conditions. Selenation and deselenation
of lactones 19 and 20 resulted in a,b-unsaturated lac-
tones 21 and 22. Deprotection of the MOM ethers in
22 and 21 with FeCl3Æ6H2O afforded goniodiol 1 and
8-epi-goniodiol 2, respectively, in 78% and 80% yields,
the spectral and physical data of which were consistent
with that reported in the literature.9 Treatment of 2 with
DBU furnished 9-deoxygoniopypyrone in 78% yield5j
(Scheme 3).
In summary, a facile synthesis of the cytotoxic styryl-
lactones goniodiol and 9-deoxygoniopypyrone was
accomplished starting from D-(À)-tartaric acid. The
synthetic sequence en route to the title compound is
highly diastereoselective with good overall yields (20%
for 8-epi-goniodiol and 17% for goniodiol from the
dimethylamide 12) and is amenable for the synthesis of
similar natural products and their analogues.
7. The diastereomeric ratio of the alcohols was estimated by
1H NMR.
8. Balogh, V.; Fetizon, M.; Golfier, M. J. Org. Chem. 1971,
36, 1339–1341.
9. Selected spectral data: Compound 9: [a]D +40.6 (c 1.1,
CHCl3); 1H NMR (300 MHz, CDCl3) d 7.41–7.22 (m, 5H),
5.65 (ddt, J = 16.8, 10.2, 6.6 Hz, 1H), 4.96–4.84 (m, 2H),
4.58 (d, J = 5.7 Hz, 1H), 3.93–3.68 (m, 2H), 2.83 (br s, 1H),
1.94–1.81 (m, 2H), 1.45 (s, 3H), 1.42 (s, 3H) 1.40–1.12 (m,
2H), 1.04–0.85 (m, 2H); 13C NMR (75 MHz, CDCl3) d
139.8, 138.3, 128.6, 128.4, 126.9, 114.6, 109.0, 84.3, 77.8,
75.4, 33.3, 32.5, 27.5, 27.2, 24.9; HRMS for C17H24O3+Na
calcd 299.1625; found 299.1623. Compound 17: [a]D À82.4
(c 0.9, CHCl3); 1H NMR (300 MHz, CDCl3) d 7.52–7.21
(m, 5H), 4.91 (d, J = 7.5 Hz, 1H), 4.04 (d, J = 11.1 Hz, 1H),
3.96 (br s, 1H), 3.82 (br s, 1H), 3.59 (d, J = 6.9 Hz, 1H),
2.63–2.28 (m, 2H), 2.05–1.79 (m, 2H) 1.77–1.60 (m, 2H);
13C NMR (75 MHz, CDCl3) d 172.0, 140.3, 128.5, 128.0,
127.0, 79.4, 77.2, 74.1, 29.6, 24.2, 18.2; HRMS for
C13H16O4+Na calcd 259.0948; found 259.0946. Compound
18: [a]D À93.5 (c 1.1, CHCl3); 1H NMR (300 MHz, CDCl3)
d 7.45–7.22 (m, 5H), 4.87 (d, J = 7.2 Hz, 1H), 4.67–4.60 (m,
1H), 3.65 (d, J = 6.9 Hz, 1H), 3.14 (br s, 1H), 2.66–2.33 (m,
3H), 2.08–1.65 (m, 4H); 13C NMR (75 MHz, CDCl3) d
172.1, 141.1, 128.5, 127.9, 126.7, 79.1, 75.7, 73.6, 29.5, 24.2,
18.3; HRMS for C13H16O4+Na calcd 259.0948; found
259.0946. Compound 21: [a]D +42.9 (c 1.3, CHCl3); 1H
NMR (300 MHz, CDCl3) d 7.48–7.24 (m, 5H), 6.86 (ddd,
J = 9.6, 6.3, 2.4 Hz, 1H), 5.94 (ddd, J = 9.6, 3.0, 0.9 Hz,
1H), 5.07 (d, J = 7.2 Hz, 1H), 4.96 (d, J = 6.9 Hz, 1H), 4.79
(d, J = 6.9 Hz, 1H), 4.58 (d, J = 6.6 Hz, 1H), 4.52 (d,
J = 6.6 Hz, 1H), 4.14 (dt, J = 6.9, 3.3 Hz, 1H), 3.80 (dd,
J = 7.2, 3.3 Hz, 1H) 3.37 (s, 3H), 3.32 (s, 3H), 2.83 (ddt,
J = 18.3, 12.0, 2.7 Hz, 1H), 2.22 (dddd, J = 18.3, 6.6, 3.9,
1.2 Hz, 1H); 13C NMR (75 MHz, CDCl3) d 163.5, 145.4,
138.0, 128.7, 128.3, 127.7, 120.9, 98.8, 94.5, 80.9, 78.4, 76.9,
56.5, 55.8, 26.0; HRMS for C17H22O6+Na calcd 345.1316;
found 345.1314. Compound 22: [a]D À45.4 (c 1.2, CHCl3);
1H NMR (300 MHz, CDCl3) d 7.48–7.21 (m, 5H), 6.95
(ddd, J = 9.6, 6.3, 2.4 Hz, 1H), 6.03 (ddd, J = 9.6, 2.7,
0.9 Hz, 1H), 4.98 (ddd, J = 12.6, 3.6, 2.4 Hz, 1H), 4.94 (d,
J = 8.4 Hz, 1H), 4.62–4.51 (m, 2H), 4.17 (d, J = 6.9 Hz,
1H), 3.82 (d, J = 6.9 Hz, 1H), 3.72 (dd, J = 8.4, 2.1 Hz,
1H), 3.33 (s, 3H), 3.16 (s, 3H), 2.75 (ddt, J = 18.6, 12.6,
Acknowledgements
We thank the Department of Science and Technology,
New Delhi, and the Department of Biotechnology
(DBT), New Delhi, for financial support. S.L.G. thanks
the Council of Scientific and Industrial Research (CSIR)
for a fellowship.
References and notes
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`
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5. For syntheses of goniodiol see: (a) Surivet, J. P.; Vatele, J.
M. Tetrahedron Lett. 1998, 39, 7299–7300; (b) Mukai, C.;
Hirai, S.; Hanaoka, M. J. Org. Chem. 1997, 62, 6619–6626;
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M. G.; Coster, M. J.; Karunaratne, O. P.; Smith, J. A. J.
Chem. Soc., Perkin Trans. 1 2002, 1622–1624; (f) Banwell,
M. G.; Coster, M. J.; Edwards, A. J.; Karunaratne, O. P.;
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2003, 56, 585–595; (g) Ramachandran, P. V.; Chandra, J. S.;
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2003, 44, 8081–8084; (i) Nakashima, K.; Kikuchi, N.;
Shirayama, D.; Miki, T.; Ando, K.; Sono, M.; Suzuki, S.;
Kawase, M.; Kondoh, M.; Sato, M.; Tori, M. Bull. Chem.
Soc. Jpn. 2007, 80, 387–394; For syntheses of 9-deoxy-
goniopypyrone see: (j) Prasad, K. R.; Dhaware, M. G.
Synlett 2007, 1112–1114; (k) Yamashita, Y.; Saito, S.;
Kobayashi, S. J. Am. Chem. Soc. 2003, 125, 3793–3798; (l)
Chen, J.; Lin, G.-Q.; Wang, Z.-M.; Liu, H.-Q. Synlett 2002,
1265–1268; (m) Tsubuki, M.; Kanai, K.; Nagase, H.;
Honda, T. Tetrahedron 1999, 55, 2493–2514; (n) Surivet,
2.7 Hz, 1H), 2.28 (dddd, J = 18.6, 6.0, 3.9, 0.9 Hz, 1H); 13
C
NMR (75 MHz, CDCl3) d 163.8, 145.6, 138.7, 128.4, 128.3,
128.2, 121.1, 97.9, 94.2, 81.5, 76.3, 75.3, 56.3, 56.0, 26.2;
HRMS for C17H22O6+Na calcd 345.1316; found 345.1314.
Goniodiol 1: [a]D +74.1 (c 0.5, CHCl3) [lit.3 [a]D +74.4 (c
1
0.3, CDCl3)]; H NMR (300 MHz, CDCl3) d 7.46–7.24 (m,
5H), 6.93 (ddd, J = 9.3, 6.0, 2.1 Hz, 1H), 6.00 (dd, J = 9.9,
3.0 Hz, 1H), 4.95 (dd, J = 7.5, 5.7 Hz, 1H), 4.80 (ddd,
J = 12.9, 3.9, 2.4 Hz, 1H), 3.73 (td, J = 8.1, 2.1 Hz, 1H),
2.80 (ddt, J = 18.3, 12.9, 2.1 Hz, 1H), 2.63 (d, J = 5.4 Hz,