10312
S. Raghavan, M. A. Rasheed / Tetrahedron 59 (2003) 10307–10312
24. To the solution of the acetoxyketone (23) (218 mg,
0.4 mmol) in 2,2,2-trifluoroethanol (4 mL) at 08C was
encouragement, to Dr A. C. Kunwar for NMR spectra and
M. Vairamani for the mass spectra. M. A. R. is thankful to
CSIR (New Delhi) for the senior research fellowship.
Financial assistance from DST is gratefully acknowledged.
anhydrous
disodiumhydrogenphosphate
(227 mg,
1.6 mmol), Na–Hg (6% Na atom, 600 mg) and stirred at
rt for 2 h. The reaction mixture was diluted with ether and
washed with water, brine, dried over anhydrous Na2SO4 and
evaporated under reduced pressure. The residue was
purified by column chromatography using 10% EtOAc/
petroleum ether (v/v) as the eluent to yield 24 (137 mg,
0.28 mmol) in 70% yield. Gummy liquid. IR (neat) 2943,
2923, 2665, 1757, 1720, 1428, 1364, 1146 cm21. 1H NMR
(300 MHz, CDCl3) d 7.34 (m, 5H), 5.33 (d, J¼3.6 Hz, 1H),
4.68 (m, 1H), 3.57 (m, 1H), 2.84 (s, 3H), 2.67 (dd, J¼17.0,
6.0 Hz, 1H), 2.58 (dd, J¼17.0, 4.8 Hz, 1H), 2.44 (m, 2H),
1.60 (m, 2H), 1.43 (m, 2H), 1.28 (m, 12H), 0.90 (t, 3H), 0.84
(s, 9H), 0.06 (s, 3H), 0.00 (s, 3H). 13C NMR (75 MHz,
CDCl3) d 207.8, 157.7, 139.9, 128.8, 128.7, 126.0, 75.5,
68.4, 66.9, 44.5, 44.3, 31.8, 30.0, 29.4, 29.2, 29.1, 25.7,
25.4, 23.4, 22.7, 17.9, 14.1, 23.6, 24.0. MS (FAB) 490
[MþH]þ. [a]D25¼215.8 (c 1.0, CHCl3). Anal. calcd for
C28H47NO4Si: C, 68.67; H, 9.67; N, 2.86. Found: C, 68.48;
H, 9.72; N, 2.97.
References
1. (a) Schwartz, R. E.; Leisch, J.; Hensens, O.; Zitano, L.;
Honeycutt, S.; Garitty, G.; Fromtling, R. A.; Onishi, J.;
Monaghan, R. J. Antibiot. 1988, 41, 1774. (b) Johnson, J. H.;
Phillipson, D. W.; Kahle, A. D. J. Antibiot. 1989, 42, 1184.
2. Kasahara, K.; Yoshida, M.; Eishima, J.; Takasako, K.; Beppu,
T.; Horinouchi, S. J. Antibiot. 1997, 50, 267.
3. Achenbach, T. V.; Slater, E. P.; Brummerhop, H.; Bach, T.;
Muller, R. Antimicrob. Agents Chemother. 2000, 44, 2794.
4. For earlier approaches refer: (a) Okue, M.; Watanabe, H.;
Kitahara, T. Tetrahedron 2001, 57, 4107. (b) Lee, K.-Y.; Kim,
Y.-H.; Oh, C.-Y.; Ham, W.-H. Org. Lett. 2000, 2, 4041.
(c) Bach, T.; Brummerhop, H.; Harms, K. Chem. Eur. J. 2000,
6, 3838. (d) Verma, R.; Ghosh, S. K. J. Chem. Soc., Perkin
Trans. 1 1999, 265. (e) Bach, T.; Brummerhop, H. Angew.
Chem., Int. Ed. Engl. 1998, 37, 3400. (f) Veeresa, G.; Dutta, A.
Tetrahedron 1998, 54, 15673. (g) Dong, H. Q.; Lin, G. Q.
Chin. J. Chem. 1998, 16, 458. (h) Kanazawa, A.; Gillet, S.;
Delair, P.; Greene, A. E. J. Org. Chem. 1998, 63, 4660.
(i) deArmas, P.; Garcia-Tellado, F.; Marrero-Tellado, J. J.;
Robles, J. Tetrahedron Lett. 1998, 39, 131. (j) Kadota, I.; Saya,
S.; Yamamoto, Y. Heterocycles 1997, 46, 335. (k) Dong, H. Q.;
Lin, G. Q. Chin. Chem. Lett. 1997, 8, 693. (l) Beier, C.;
Schaumann, E. Synthesis 1997, 1296. (m) Verma, R.; Ghosh,
S. K. J. Chem. Soc., Chem. Commun. 1997, 1601. (n) Kadota,
I.; Yamamoto, Y. J. Synth. Org. Chem. 1997, 55, 619.
(o) Yoda, H.; Yamazaki, H.; Takabe, K. Tetrahedron:
Asymmetry 1996, 7, 373. (p) Overhand, M.; Hecht, S. J. Org.
Chem. 1994, 59, 4721. (q) Deng, W.; Overman, L. E. J. Am.
Chem. Soc. 1994, 116, 11241. (r) Shimazaki, M.; Okazaki, F.;
Nakajima, F.; Ishikawa, T.; Ohta, A. Heterocycles 1993, 36,
1823. (s) McGrane, P. L.; Livinghouse, T. J. Am. Chem. Soc.
1993, 115, 11485. (t) Pak, C. S.; Lee, G. H. J. Org. Chem.
1991, 56, 1128.
3.1.16. (2S,3S,5R)-2-Benzyl-3-tert-butyldimethylsilyloxy-
1-methyl-5-nonylazolidine 26. To the solution of the keto
oxazolidinone (24) (100 mg, 0.2 mmol) in ethanol (0.8 mL)
was added Pd(OH)2 (20% by weight, 20 mg) and stirred
under an atmosphere of hydrogen for 1 h. The catalyst was
filtered through a small pad of celite and the filtrate
evaporated under reduced pressure to afford (26) (78 mg,
0.18 mmol) in 90% yield. Gummy liquid. IR (neat) 2926,
2855, 2675, 1731, 1460, 1378, 1354, 1054, 750, 701 cm21
.
1H NMR (200 MHz, CDCl3) d 7.20 (m, 5H), 4.10 (m, 1H),
3.10–2.68 (m, 2H), 2.50 (m, 1H), 2.30–1.90 (m, 5H), 1.80–
1.0 (m, 16H), 0.9 (m, 12H), 20.05 (s, 3H), 20.13 (s, 3H).
MS (FAB) 432 [MþH]þ. [a]D25¼þ8.8 (c 1.37, CHCl3).
3.1.17. (2S,3S,5R)-2-Benzyl-3-hydroxy-1-methyl-5-
nonylazolidine [(1)-preussin (1)]. To the solution of
compound (26) (50 mg, 0.12 mmol) in dry THF (0.3 mL)
at 08C was added dropwise tetrabutylammonium fluoride
(1 M in THF, 0.14 mL) and stirred at rt for 1 h. The solvent
was evaporated under reduced pressure and the residue was
purified by column chromatography using 20% EtOAc/
petroleum ether (v/v) as eluent to afford (þ)-preussin (1)
(31 mg, 0.1 mmol) in 85% yield. Waxy solid. IR (neat)
3426, 2953, 2890, 2775, 1468, 1455, 1348, 1132, 1030, 966,
5. (a) Raghavan, S.; Rasheed, M. A. Tetrahedron: Asymmetry
2003, 14, 1371. (b) Raghavan, S.; Joseph, S. C. Tetrahedron:
Asymmetry 2003, 14, 101. (c) Raghavan, S.; Ramakrishna
Reddy, S.; Tony, K. A.; Naveen Kumar, Ch.; Varma, A. K.;
Nangia, A. J. Org. Chem. 2002, 67, 5838. (d) Raghavan, S.;
Rasheed, M. A.; Joseph, S. C.; Rajender, A. J. Chem. Soc.,
Chem. Commun. 1999, 1845.
1
743 cm21. H NMR (300 MHz, CDCl3) d 7.20 (m, 5H),
3.73 (m, 1H), 2.83 (dd, J¼13.2, 10.2 Hz, 1H), 2.73 (dd,
J¼13.2, 4.5 Hz, 1H), 2.27 (s, 3H), 2.20–2.08 (m, 4H), 1.59
(m, 1H), 1.40 (m, 1H), 1.20 (m, 16H), 0.85 (t, J¼13.6,
6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3) d 139.4, 129.4,
128.4, 126.2, 74.0, 70.2, 66.3, 39.2, 38.4, 34.2, 33.2, 31.9,
29.8, 29.6, 29.5, 29.3, 26.4, 22.7, 14.1. MS (ESI) 318
[MþH]þ. [a]D25¼þ31.5 (c 0.6, CHCl3), (lit.4a [a]2D5¼þ29.3
(c 1.17, CHCl3). HRMS (FAB) m/z calcd for C21H35NO
318.2797; found 318.2802.
6. Solladie, G.; Demailly, G.; Greck, C. J. Org. Chem. 1985, 50,
1552.
7. (a) Pummerer, R. Chem. Ber. 1909, 42, 2282. (b) Sugihara, H.;
Tanikaga, R.; Kaji, A. Synthesis 1978, 881. (c) Padwa, A.;
Gunn, D. E., Jr.; Osterhout, M. H. Synthesis 1997, 1353.
8. (a) Corey, E. J.; Seebach, D. Angew. Chem., Int. Ed. Engl.
1965, 4, 1075. see also p 1077. (b) For a review refer: Seebach,
D. Angew. Chem., Int. Ed. Engl. 1969, 8, 639.
9. Marshall, J. A.; Belletire, J. L. Tetrahedron Lett. 1971, 871.
10. (a) Stork, G.; Maldonado, L. J. Am. Chem. Soc. 1971, 93,
5286. (b) Hunig, S.; Wehner, G. Synthesis 1975, 180.
11. Stork, G.; Zhao, K. Tetrahedron Lett. 1989, 30, 287.
12. Trost, B. M.; Arndt, H. C.; Strege, P. E.; Verhoeven, T. R.
Tetrahedron Lett. 1976, 3477.
Acknowledgements
S. R. is thankful to Dr J. S. Yadav, Head, Organic Div. I, Dr
K. V. Raghavan, Director, I.I.C.T., for constant support and