P. Srihari et al. / Tetrahedron Letters 48 (2007) 6977–6981
6981
eesh Babu, R.; Yadav, J. S. Tetrahedron Lett. 2005, 46,
6145–6148; (f) Yadav, J. S.; Sridhar Reddy, M.; Prasad, A.
R. Tetrahedron Lett. 2005, 46, 2133–2136; (g) Sabitha, G.;
Rajkumar, M.; Shashi Kumar Reddy, M.; Yadav, J. S.;
Ramakrishna, K. V. S.; Kunwar, A. C. Tetrahedron Lett.
2005, 46, 1659–1661; (h) Sudhakar, K.; Sabitha, G.;
Mallikarjuna Reddy, N.; Rajkumar, M.; Yadav, J. S.
Tetrahedron Lett. 2005, 46, 6567–6570; (i) Yadav, J. S.;
Bhaskar Reddy, K.; Sabitha, G. Tetrahedron Lett. 2004,
45, 6475–6476; (j) Yadav, J. S.; Srihari, P. Tetrahedron:
Asymmetry 2004, 15, 81–89.
2H), 5.22–5.35 (m, 1H), 4.94 (p, 1H, J = 6.2 Hz), 4.66–
4.79 (m, 1H), 4.04–4.23 (m, 4H), 2.73–3.03 (m, 2H), 2.04
(s, 3H), 2.00 (s, 3H), 1.34 (s, 3H), 1.28 (s, 3H), 1.23 (t, 3H,
J = 7.4 Hz), 1.26 (d, 3H, J = 6.2 Hz), 0.85 (s, 9H), 0.08 (s,
3H), 0.01 (s, 3H). 13C NMR (75 MHz, CDCl3): d 170.34,
169.67, 166.33, 146.38, 139.57, 123.82, 121.21, 108.88,
78.43, 77.69, 69.08, 68.17, 67.60, 59.86, 38.12, 27.06, 25.94,
25.32, 21.55, 21.07, 18.19, 16.94, 14.45, ꢀ4.38, ꢀ4.99.
20
LCMS: m/z 542 (M+). ½aꢁD +14.0 (c 0.04 CHCl3). HRMS
for C27H46O9NaSi: Calcd 565.2815; found, 565.2808.
Compound 22: white solid; mp 175–177 °C. 1H NMR
(200 MHz, DMSO-d6): d 7.01–7.16 (m, 1H), 5.99 (d, 1H,
J = 10.6 Hz), 5.58–5.78 (m, 2H), 5.23–5.43 (m, 1H), 5.01
(d, 1H, J = 4.8 Hz), 4.87 (d, 1H, J = 4.8 Hz), 4.42–4.58
(m, 3H), 3.75–3.92 (m, 1H), 3.09–3.22 (m, 1H), 2.34–2.58
(m, 3H), 1.04 (d, 3H, J = 6.4 Hz). 13C NMR (75 MHz,
DMSO-d6): d 163.57, 147.16, 133.70, 127.75, 120.13, 74.78,
10. Leven, P. A.; Tipson, R. S. J. Biol. Chem. 1936, 115, 731.
11. Kinoshita, M.; Arai, M.; Tomooka, K.; Nakata, M.
Tetrahedron Lett. 1986, 27, 1811–1814.
12. Sharpless, K. B.; Katsuki, T. J. Am. Chem. Soc. 1980, 102,
5974–5976.
13. (a) Yadav, J. S.; Deshpande, P. K.; Sharma, G. V. M.
Tetrahedron Lett. 1990, 31, 4495–4496; (b) Yadav, J. S.;
Deshpande, P. K.; Sharma, G. V. M. Tetrahedron 1990,
46, 7033–7046.
14. We anticipated that the stereochemistry of the resulting
alcohol would be exclusively anti and proceeded further
with the synthesis. The stereochemistry of the newly
generated center was studied later by NMR techniques.
15. McEwen, A. B.; Guttieri, M. J.; Maier, W. F.; Laine, R.
M.; Shvo, Y. J. Org. Chem. 1983, 48, 4436–4438.
16. Ando, K. J. Org. Chem. 1997, 62, 1934–1939.
17. Coleman, M. T. D.; English, R. B.; Rivett, D. E.
Phytochemistry 1987, 26, 1497–1499.
20
74.72, 73.93, 67.78, 67.24, 29.16, 17.10. ½aꢁD ꢀ26.0 (c 0.5
MeOH). LCMS: m/z 257 (M+H). HRMS for C12H17O6:
Calcd 257.1033; found, 257.1025. Compound 23: colorless
1
solid, mp 98–100 °C. H NMR (300 MHz, CDCl3): d 6.89
(ddd, 1H, J = 9.7, 5.3, 3.0 Hz), 6.03–6.10 (m, 1H), 5.77–
5.89 (m, 2H), 5.41–5.46 (m, 1H), 5.30 (dd, 1H, J = 7.9,
3.5 Hz), 5.21 (ddd, 1H, J = 7.7, 3.4, 1.3 Hz), 4.89–5.06 (m,
2H), 2.34–2.55 (m, 2H), 2.17 (s, 3H), 2.12 (s, 3H), 2.06 (s,
3H), 2.01 (s, 3H), 1.22 (d, 3H, J = 6.6 Hz). 13C NMR
(50 MHz, CDCl3): d 170.00, 169.93, 169.90, 169.88,
163.66, 144.67, 132.85, 126.34, 121.79, 72.26, 72.14,
71.11, 71.06, 71.02, 68.87, 29.58, 21.28, 21.15, 21.07,
20
18. Spectroscopic data of 19: Colorless liquid; IR (neat) 3426,
2986, 2932, 2857, 1742, 1645, 1465, 1372, 1174, 1058, 941,
14.35. ½aꢁD ꢀ10.7 (c 0.05 CHCl3). LCMS: m/z 426 (M+).
HRMS for C20H26O10Na: Calcd 449.1421; found,
449.1423.
1
836, 778 cmꢀ1. H NMR (200 MHz, CDCl3): d 6.28–6.43
(m, 1H), 5.81 (dt, 1H, J = 1.5, 11.7 Hz), 5.49–5.71 (m,