576
M. Laurent et al.
PAPER
1H NMR (CDCl3, 200 MHz): δ = 7.1–7.6 (m, 10 Harom), 5.18 (br s,
1 H, OH), 4.72 (d, 1 H, J = 2.2 Hz, H-4), 4.30 (dq, 1 H, J = 6.0, 6.3
Hz, MeCHOR), 2.78 (dd, 1 H, J = 6.0, 2.2 Hz, H-3), 1.33 (d, 3 H,
J = 6.3 Hz, CH3), 0.96 (s, 9 H, t-C4H9 ), 0.80 [s, 9 H, SiC(CH3)3],
0.16, 0.15 [2 s, 6 H, Si(CH3)2].
13C NMR (CDCl3, 75 MHz): δ = 216.2, 166.8, 142.1, 141.5, 126.2–
129.9, 87.4, 66.6, 62.0, 56.6, 43.8, 26.2, 25.7, 25.3, 18.1, –3.6, –4.5.
(5) (a) Berks, A. H. Tetrahedron 1996, 52, 331; and references
cited therein. (b) Oh, C.-Y.; Ham, W.-H. Chem. Commun.
1999, 2365; and references cited therein. (c) Pyun, D. K.;
Jeong, W. J.; Jung, H. J.; Kim, J. H.; Lee, J. S.; Lee, C. H.;
Kim, B. J. Synlett 2001, 1950; and references cited therein.
(6) Deng, B.-L.; Demillequand, M.; Laurent, M.; Touillaux, R.;
Belmans, M.; Kemps, L.; Cérésiat, M.; Marchand-Brynaert,
J. Tetrahedron 2000, 56, 3209.
(7) Hanessian, S.; Bedeschi, A.; Battistini, C.; Mongelli, N. J.
Am. Chem. Soc. 1985, 107, 1438.
(3S,4S,5R)-3-(1′-tert-Butyldimethylsilyloxyethyl)-4-pivaloylaze-
tidin-2-one (10a)
Starting from 8a (0.13 g, 0.27 mmol, 1 equiv) and following the
general procedure for the deprotection, a white solid (0.066 g, 95%)
was obtained.
(8) (a) Kronenthal, D. R.; Han, C. Y.; Taylor, M. K. J. Org.
Chem. 1982, 47, 2765. (b) Adam, W.; Groer, P.; Humpf, H.-
U.; Saha-Möller, C. R. J. Org. Chem. 2000, 65, 4919.
(c) Gordon, K. H.; Balasubramanian, S. Org. Lett. 2001, 3,
53; and references cited therein.
(9) Kocienski, P. J. Protecting Groups, 1st Ed.; Georg Thieme
Verlag: Stuttgart, 2000.
(10) Demillequand, M.; Cérésiat, M.; Belmans, M.; Kemps, L.;
Marchand-Brynaert, J. J. Chromatogr. A 1999, 832, 259;
and references cited therein.
(11) (a) Anson, M. S.; Montana, J. G. Synlett 1994, 219.
(b) Baker, S. R.; Parsons, A. F.; Wilson, M. Tetrahedron
Lett. 1998, 39, 331. (c) Riess, R.; Schön, M.; Laschat, S.;
Jäger, V. Eur. J. Org. Chem. 1998, 473.
(12) (a) Tinant, B.; Declercq, J.-P.; Cérésiat, M.; Marchand-
Brynaert, J. Z. Kristallogr. NCS 2001, 216, 51. (b) Tinant,
B.; Declercq, J.-P.; Cérésiat, M.; Marchand-Brynaert, J. Z.
Kristallogr. NCS 2001, 216, 53.
O-Protection of 7a
To a solution of 7a (1.35 g, 6.8 mmol, 1 equiv) in DMF (70 mL)
were added tert-butyldimethylsilyl chloride (2.04 g, 14 mmol, 2.1
equiv) and imidazole (2.31 g, 34 mmol, 5 equiv). The mixture was
stirred under argon at r.t. for 16 h and then diluted with EtOAc (50
mL). The organic phase was washed with brine (3 × 50 mL) and
dried (MgSO4). Concentration of the organic extract and flash chro-
matography of the residue obtained on silica gel (eluent: CH2Cl2–
EtOAc, 10:1) gave a white solid (1.47 g, 69%); Rf 0.36; mp 108.0–
109.0 °C; [α]D20 +32.5 (c = 0.815, CHCl3).
IR (KBr): 3158 (NH), 1767 (C=O), 1723 (C=O), 1472 cm–1.
1H NMR (CDCl3, 200 MHz): δ = 5.96 (br s, 1 H, NH), 4.59 (d, 1 H,
J = 2.1 Hz, H-4), 4.27 (dq, 1 H, J = 6.3, 4.5 Hz, MeCHOR), 3.17
(m, 1 H, H-3), 1.26 (d, 3 H, J = 6.3 Hz, CH3), 1.22 (s, 9 H, t-C4H9),
0.89 [s, 9 H, SiC(CH3)3], 0.10, 0.09 [s, 6 H, Si(CH3)2].
(13) Blythin, D. J.; Green, M. J.; Lauzon, M. J. R.; Shue, H.-J. J.
Org. Chem. 1994, 59, 6098.
(14) (a) Perosa, A.; Selva, M.; Tundo, P. J. Chem. Soc., Perkin
Trans. 2 1999, 2485. (b) Perosa, A.; Selva, M.; Tundo, P.
Tetrahedron Lett. 1999, 40, 7573.
(15) (a) Shiozaki, M.; Maruyama, H.; Ishida, N. Heterocycles
1984, 22, 1725. (b) Kugelman, M.; Gala, D.; Jaret, R. S.;
Nyce, P. L.; McPhail, A. T. Synlett 1990, 431.
(16) Encyclopedia of Reagents for Organic Synthesis, Vol. 1;
Paquette, L. A., Ed.; Wiley: New York, 1995, 765.
(17) Shaw, H.; Perlmutter, H. D.; Gu, C.; Arco, S. D.; Quibuyen,
T. O. J. Org. Chem. 1997, 62, 236.
(18) Tinant, B.; Laurent, M.; Marchand-Brynaert, J. Z.
Kristallogr. NCS 2002, submitted.
(19) (a) Bussolari, J. C.; Beers, K.; Lalan, P.; Murray, W. V.;
Gauthier, D.; McDonnell, P. Chem. Lett. 1998, 787. (b) Yu,
C.; Hu, L. J. Org. Chem. 2002, 67, 219. (c) Umezawa, H.;
Kondo, S.; Iinuma, H.; Kunimoto, S.; Ikeda, Y.; Iwasawa,
H.; Ikeda, D.; Takeuchi, T. J. Antibiotics 1981, 34, 1622.
(d) Troast, D. M.; Porco, J. A. Jr. Org. Lett. 2002, 4, 991.
(20) Oldham, K.; Betts, M. J.; Denerley, P. M. Eur. Patent.
304208, 1988; Chem. Abstr. 1989, 111, 57409.
(21) (a) Chackalamannil, S.; Fett, N.; Kirkup, M.; Afonso, A.;
Ganguly, A. K. J. Org. Chem. 1988, 53, 450. (b) Tschaen,
D. M.; Fuentes, L. M.; Lynch, J. E.; Laswell, W. L.; Volante,
R. P.; Shinkai, I. Tetrahedron Lett. 1988, 29, 2779.
(c) Altamura, M.; Ricci, M. Synth. Commun. 1988, 18, 2129.
(22) Shiozaki, M.; Ishida, N.; Hiraoka, T.; Maruyama, H.
Tetrahedron 1984, 40, 1795.
13C NMR (CDCl3, 75 MHz): δ = 212.8, 168.6, 65.6, 64.5, 51.3,
44.1, 26.4, 25.8, 23.0, 18.0, –4.4, –4.7.
MS (CI, CH4–N2O): m/z (%) = 627.5 ([2 M + H]+, 3), 342.3 (23),
314.3 ([M + H]+, 100), 298.2 (17).
Anal. Calcd for C16H31NO3Si: C, 61.30; H, 9.97; N, 4.47. Found: C,
61.49; H, 10.10; N, 4.41.
Acknowledgment
The authors gratefully acknowledge Tessenderlo Chemie for finan-
cial support, and Sonia Gharbi and Sébastien Colle for experimental
assistance. J. M.-B. is a senior research associate of FNRS (Fonds
National de la Recherche Scientifique), Belgium.
References
(1) (a) The Chemistry of β-Lactams; Page, M. I., Ed.; Blackie:
London, 1992. (b) The Organic Chemistry of β-Lactams;
Georg, G. I., Ed.; VCH: New York, 1992.
(2) (a) Southgate, R.; Elson, S. Prog. Chem. Org. Nat. Prod.
1985, 47, 1. (b) Dürckheimer, W.; Blumbach, J.; Lattrell, R.;
Scheinemann, K. H. Angew. Chem., Int. Ed. Engl. 1985, 24,
180. (c) McGregor, D. N. Comp. Heterocycl. Chem. 1987, 7,
299. (d) Holden, K. G. Comp. Heterocycl. Chem. 1987, 7,
285.
(23) Bhattarai, K.; Cainelly, G.; Panunzio, M. Synlett 1990, 229.
(24) Corley, E. G.; Karady, S.; Abramson, N.-L.; Ellison, D.;
Weinstock, L. M. Tetrahedron Lett. 1988, 29, 1497.
(25) Amblard, M.; Rodriguez, M.; Martinez, J. Tetrahedron
1988, 44, 5101.
(26) Ruzza, P.; Calderan, A.; Borin, A. Tetrahedron Lett. 1996,
37, 5191.
(27) (a) Hirai, K.; Iwano, Y.; Fujimoto, K. Tetrahedron Lett.
1982, 39, 4025. (b) Shiozaki, M. Synthesis 1990, 691.
(c) De Risi, C.; Pollini, G. P.; Veronese, A. C.; Bertolasi, V.
Tetrahedron Lett. 1999, 40, 6995.
(3) (a) Ojima, I.; Delaloge, F. Chem. Soc. Rev. 1997, 26, 377.
(b) Freihammer, P. M.; Detty, M. R. J. Org. Chem. 2000, 65,
7203; and references cited therein. (c) Palomo, C.;
Aizpurua, J. M.; Ganboa, I.; Oiarbide, M. Synlett 2001,
1813; and references cited therein.
(4) (a) Kidwai, M.; Sapra, P.; Bhushan, K. R. Curr. Med. Chem.
1999, 6, 195. (b) Magriotis, P. A. Angew. Chem., Int. Ed.
2001, 40, 4377; and references cited therein.
Synthesis 2003, No. 4, 570–576 ISSN 0039-7881 © Thieme Stuttgart · New York