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G. Sabitha et al.
PAPER
1H NMR (300 MHz, CDCl3): d = 7.30–7.22 (m, 5 H), 7.14 (d,
J = 8.6 Hz, 2 H), 6.77 (d, J = 8.6 Hz, 2 H), 4.60–4.53 (m, 3 H),
4.48–4.33 (m, 3 H), 3.81–3.62 (m, 4 H), 3.77 (s, 3 H), 3.49–3.41
(m, 2 H), 3.22 (s, 3 H), 3.30–3.24 (m, 1 H), 2.13–1.90 (m, 2 H),
1.83–1.56 (m, 2 H), 1.14–0.96 (m, 27 H), 0.92 (d, J = 7.0 Hz, 3 H),
0.88 (d, J = 7.0 Hz, 3 H).
Acknowledgment
R.S. thanks CSIR, New Delhi for the award of a fellowship.
References
13C NMR (75 MHz, CDCl3): d = 158.7, 139.4, 131.7, 128.7, 128.2,
127.2, 113.5, 96.6, 84.9, 82.2, 75.0, 74.1, 72.8, 69.8, 68.9, 55.2,
55.1, 38.5, 37.8, 36.7, 36.0, 31.9, 29.0, 17.9, 16.4, 16.0, 12.1, 11.8,
1.0.
(1) Currently a Visiting Professor at King Saud University, P.O.
Box 2455, Riyadh 11451, Saudi Arabia.
(2) (a) Gräfe, U.; Schade, W.; Roth, M.; Radics, L.; Incze, M.;
Ujszaszy, K. J. Antibiot. 1984, 37, 836. (b) Radics, L.
J. Chem. Soc., Chem. Commun. 1984, 599.
ESIMS: m/z = 703 [M]+, 725 [M + Na]+.
(3) Brooks, H. A.; Gardner, D.; Poyser, J. P.; King, T. J.
J. Antibiot. 1984, 37, 1501.
(2R,3R,6S,7S,8R,9S,10S)-9-(Benzyloxy)-11-(methoxymethoxy)-
2,6,8,10-tetramethyl-1-[(1,1,1-triisopropylsilyl)oxy]undecane-
3,7-diol (19)
(4) (a) Gräfe, U.; Tonew, E.; Schade, W.; Reinhardt, G.; Härtl,
A. East German Patent DD 231793, 1986. (b) Tonew, E.;
Tonew, M.; Gräfe, U.; Zopel, P. Pharmazie 1988, 43, 717.
(5) (a) Danishefsky, S. J.; Selnick, H. G.; DeNinno, M. P.; Zelle,
R. E. J. Am. Chem. Soc. 1987, 109, 1572. (b) Danishefsky,
S. J.; Selnick, H. G.; Zelle, R. E.; DeNinno, M. P. J. Am.
Chem. Soc. 1988, 110, 4368. (c) Cossy, J.; Meyer, C.;
Defosseux, M.; Blanchard, N. Pure Appl. Chem. 2005, 77,
1131. (d) Defosseux, M.; Blanchard, N.; Meyer, C.; Cossy,
J. J. Org. Chem. 2004, 69, 4626. (e) Defosseux, M.;
Blanchard, N.; Meyer, C.; Cossy, J. Org. Lett. 2003, 5,
4037. (f) Komatsu, K.; Tanino, K.; Miyashita, M. Angew.
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Lett. 2007, 9, 2199. (h) Cossy, J.; Blanchard, N.; Defosseux,
M.; Meyer, C. Angew. Chem. Int. Ed. 2002, 41, 2144.
(i) Guindon, Y.; Murtagh, L.; Caron, V.; Landry, S. R.; Jung,
G.; Bencheqroun, M.; Faucher, A.-M.; Guerin, B. J. Org.
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J. A.; Alberti, M. J. J. Org. Chem. 1998, 63, 3160.
(k) Marshall, J. A.; Palovich, M. R. J. Org. Chem. 1998, 63,
3701. (l) Chemler, S. R.; Roush, W. R. J. Org. Chem. 1998,
63, 3800. (m) Booysen, J. F.; Holzapfel, C. W. Synth.
Commun. 1995, 25, 1473. (n) Cywin, C. L.; Kallmerten, J.
Tetrahedron Lett. 1993, 34, 1103. (o) Balestra, M.;
Wittman, M. D.; Kallmerten, J. Tetrahedron Lett. 1988, 29,
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Danishefsky, S. J. J. Org. Chem. 1986, 51, 5032.
(6) (a) Yadav, J. S.; Abraham, S.; Reddy, M. M.; Sabitha, G.;
Sankar, A. R.; Kunwar, A. C. Tetrahedron Lett. 2001, 42,
4713. (b) Yadav, J. S.; Reddy, K. B.; Sabitha, G.
Tetrahedron Lett. 2004, 45, 6475. (c) Yadav, J. S.; Reddy,
K. B.; Sabitha, G. Tetrahedron 2008, 64, 1971. (d) Sabitha,
G.; Yadagiri, K.; Bhikshapathi, M.; Chandrashekhar, G.;
Yadav, J. S. Tetrahedron: Asymmetry 2010, 21, 2524.
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S. Synthesis 2010, 4307.
To a solution of 16 (2.1 g, 2.9 mmol) in CH2Cl2–H2O (10:1, 20 mL)
was added dichlorodicynoquinone (DDQ; 1.0 g, 4.4 mmol) at 0 °C
and the reaction was stirred for 1 h. When the reaction was com-
plete, the solution was filtered through a pad of Celite and washed
with CH2Cl2 (2 × 25 mL). The combined filtrate was concentrated
and purified by column chromatography (EtOAc–hexane, 12%) to
provide diol 19.
Yield: 0.87 (50%); yellow liquid; Rf 0.3 (EtOAc–hexane, 10%);
[a]D25 –22 (c = 0.025, CHCl3).
IR (neat): 3450, 2934, 2867, 1460, 1101, 1047, 683 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.33–7.24 (m, 5 H), 4.66–4.55 (m,
4 H), 3.82–3.72 (m, 2 H), 3.69–3.61 (m, 1 H), 3.61–3.44 (m, 4 H),
3.33 (s, 3 H), 1.97–1.64 (m, 2 H), 1.62–1.38 (m, 2 H), 1.11–1.02
(m, 24 H), 0.98 (d, J = 6.8 Hz, 3 H), 0.92 (d, J = 7.0 Hz, 3 H), 0.79
(d, J = 6.6 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.9, 128.5, 127.8, 127.6, 96.7,
87.2, 76.0, 75.2, 74.0, 69.9, 69.1, 55.3, 38.2, 36.6, 35.8, 34.5, 30.6,
29.1, 17.9, 15.4, 14.8, 11.8, 11.4, 9.8.
ESIMS: m/z = 583 [M]+.
({(2R)-2-(2S,5S,6R)-6-[(1S,2S,3S)-2-(benzyloxy)-4-(methoxy-
methoxy)-1,3-dimethylbutyl]-5-methyltetrahydro-2H-2-pyr-
anylpropyl}oxy)(triisopropyl)silane (3)
To a solution of diol 19 (0.8 g, 1.3 mmol) in anhydrous toluene (10
mL) was added Ph3P (1.8 g, 6.8 mmol), followed by dropwise addi-
tion of diethyl azodicarboxylate (DEAD; 1.0 mL, 6.8 mmol) at 0 °C
and the reaction was stirred at r.t. for 12 h. After completion of the
reaction, H2O (20 mL) was added and the two layers were separat-
ed. The aqueous layer was extracted with EtOAc (2 × 20 mL) and
the combined organic layers were washed with brine (2 × 5 mL),
dried over Na2SO4, concentrated under vacuum, and the residue was
purified by column chromatography (EtOAc–hexane, 8%) to fur-
nish the cyclized product 3.
(7) (a) Heathcock, C. H.; Hadley, C. R.; Rosen, T.; Theisen, P.
D.; Hecker, S. J. J. Med. Chem. 1987, 30, 1858.
Yield: 0.271 g (37%); colorless liquid; TLC: Rf 0.6 (EtOAc–hexane,
10%); [a]D25 –20 (c = 0.025, CHCl3).
IR (neat): 2925, 2858, 1742, 1460, 1379, 1047, 968, 761 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.35–7.17 (m, 5 H), 4.64–4.53 (m,
4 H), 3.77–3.39 (m, 7 H), 3.34 (s, 3 H), 2.50–2.04 (m, 2 H), 2.01–
1.65 (m, 3 H), 1.63–1.45 (m, 2 H), 1.44–1.34 (m, 1 H), 1.11–0.92
(m, 30 H), 0.79 (d, J = 6.8 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.9, 128.5, 127.8, 127.7, 96.8,
87.3, 76.1, 74.3, 73.9, 70.0, 68.7, 55.3, 36.7, 31.9, 31.6, 31.4, 30.2,
29.4, 18.0, 14.9, 14.1, 12.1, 12.0, 11.4.
(b) Yasuda, N.; Hsiao, Y.; Jensen, M. S.; Rivera, N. R.;
Yang, C.; Wells, K. M.; Yau, J.; Palucki, M.; Tan, L.;
Dormer, P. G.; Volante, R. P.; Hughes, D. L.; Reider, P. J.
J. Org. Chem. 2004, 69, 1959.
(8) (a) Alvarez-Ibarra, C.; Arias, S.; Banon, G.; Fernandez, M.;
Rodriguez, V.; Sinisterra, V. J. Chem. Soc., Chem. Commun.
1987, 1509. (b) Paterson, I.; Yeung, K. S.; Smail, J. B.
Synlett 1993, 774.
(9) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C.-P.; Singh,
V. K. J. Am. Chem. Soc. 1987, 109, 7925.
(10) Mitsunobu, O. Synthesis 1981, 1.
(11) Mulzer, J.; Sieg, A.; Brucher, C.; Müller, D.; Martin, H. J.
Synlett 2005, 685.
ESIMS: m/z = 565 [M + H]+.
HRMS (ESI): m/z [M + H]+ calcd for C33H61O5Si: 565.4283; found:
565.4284.
Synthesis 2011, No. 9, 1484–1488 © Thieme Stuttgart · New York