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(CH2); 65.7 (CH2); 91.1 (CH); 92.4 (CH); 94.0 (CH); 100.7 (CH); 102.5 (CH); 115.8 (C), 108.2 (C), 234.1 (C).
MS: 452 (2), 451 (2), 450 (9), 449 (4), 448 (7), 447 (3), 446 (4), 406 (4), 366 (14), 364 (11), 338 (11), 320 (12),
307 (11), 306 (14), 305 (11), 304 (12), 291 (10), 225 (16), 253 (13), 225 (15), 223 (12), 188 (10), 186 (10), 172
(21), 158 (22), 157 (100), 53 (12), 52 (98). HR-MS: 447.9622 (M , C15H18O5Cr118Sn ; calc. 447.9576) and
449.9615 (M , C15H18O5Cr120Sn ; calc. 449.958 (1).
Complex (1S)-20 (205 mg, 0.46 mmol) was dissolved in 5 ml of THF. The soln. was cooled to À788, and
1equiv. of BuLi was added. After 1h, 3 equiv. of Me 3SiCl were added. The mixture was left 30 min at À788,
quenched with 1ml of sat. NaHCO 3 soln. and filtered through a plug of silica, affording 149 mg (0.42 mmol,
91%) of ()-(1S)-14.
Complex ()-(1S)-14 (120 mg, 0.34 mmol) was dissolved in 5 ml of THF, and 1 ml of conc. HCl was added.
After 2 h, the reaction was complete (followed by TLC). The mixture was put directly on a column and purified
by FC (silica gel; pentane/Et2O 9 :1to 4 :1), affording 91mg (0.32 mmol, 96%) of ( )-(1S)-18a, [a]2D0 76
(c 0.185, CHCl3), ee 67% (by chiral HPLC).
We thank the Swiss National Science Foundation for financial support. S. P. acknowledges a scholarship
from the Roche Research Foundation. We are grateful to Mr. P. Romanens for technical assistance and to Mr.
J. P. Saulnier, Mr. A. Pinto, and Mrs. D. Klink for NMR and MS measurements. We thank Prof. A. Alexakis and
A. Tomassini for help with the chiral SFC measurements.
REFERENCES
[1] a) H.-G. Schmalz, S. Siegel, ꢀChromium-Arene Complexesꢁ, in ꢀTransition Metals for Fine Chemicals and
Organic Synthesisꢁ, Eds. C. Bolm, M. Beller, VCH, 1998, p. 550; b) S. L. Hegedus, ꢀTransition Metals in the
Synthesis of Complex Organic Moleculesꢁ, 2nd ed., University Science Books, Mill Valley, California, 1999,
p. 287; c) A. R. Pape, K. P. Kaliappan, E. P. Kündig, Chem. Rev. 2000, 100, 2917.
Â
[2] a) A. Solladie-Cavallo, in ꢀAdvances in Metal Organic Chemistryꢁ, Ed. L. S. Liebeskind, JAI Press, London
1989, Vol. 1, p. 99; b) S. G. Davies, T. D. McCarthy, ꢀTransition Metal Arene Complexes: Side-Chain
Activation and Control of Stereochemistryꢁ, in ꢀComprehensive Organometallic Chemistry IIꢁ, Eds. E. W.
Abel, F. G. A. Stone, G. Wilkinson, Pergamon, 1995, Vol. 12, p. 1039.
[3] a) C. Mukai, S. Hirai, I. J. Kim, M. Hanaoka, Tetrahedron Lett. 1996, 37, 5389; b) N. Taniguchi, N. Kaneta,
M. Uemura, J. Org. Chem. 1996, 61, 6088; c) E. P. Kündig, L.-H. Xu, P. Romanens, G. Bernardinelli, Synlett
1996, 3, 270; d) E. P. Kündig, J. Leresche, L. Saudan, G. Bernardinelli, Tetrahedron 1996, 52, 7363; e) A.
Majdalani, H.-G. Schmalz, Tetrahedron Lett. 1997, 38, 4545; f) A. Quattropani, G. Anderson, G.
Bernardinelli, E. P. Kündig, J. Am. Chem. Soc. 1997, 119, 4773; g) D. Schinzer, U. Abel, P. G. Jones, Synlett
1997, 632; h) T. Watanabe, M. Uemura, Chem. Commun. 1998, 871; i) A. J. Pearson, A. V. Gontcharov, J.
Org. Chem. 1998, 63, 152; j) K. Schellhaas, H.-G. Schmalz, J. W. Bats, Chem. Eur. J. 1998, 4, 57; k) D. P.
Hörstermann, H.-G. Schmalz, G. Kociok-Köhn, Tetrahedron 1999, 55, 6905; l) N. Taniguchi, T. Hata, M.
Uemura, Angew. Chem., Int. Ed. 1999, 38, 1232; m) S. G. Nelson, M. A. Hilfiker, Org. Lett. 1999, 1, 1379;
n) H. Ratni, E. P. Kündig, Org. Lett. 1999, 1, 1997; H. Ratni, E. P. Kündig, Org. Lett. 2000, 2, 1983; o) W. H.
Moser, K. E. Endsley, J. T. Colyer, Org. Lett. 2000, 2, 71 7.
[4] a) C. Bolm, K. Muniz, Chem. Soc. Rev. 1999, 28, 51; b) U. Englert, R. Haerter, D. Vasen, A. Salzer, E. B.
Eggeling, D. Vogt, Organometallics 1999, 18, 4390.
Â
Â
[5] a) Solladie-Cavallo, G. Solladie, E. Tsamo, J. Org. Chem. 1979, 44, 4189; b) L. A. Bromley, S. G. Davies,
C. L. Goodfellow, Tetrahedron: Asymmetry 1991, 2, 139; c) A. Alexakis, P. Mangeney, I. Marek, F. Rose-
Munch, E. Rose, A. Semra, F. Robert, J. Am. Chem. Soc. 1992, 114, 8288.
[6] a) D. E. F. Gracey, W. R. Jackson, W. B. Jennings, T. R. B. Mitchell, J. Chem. Soc. C 1969, 1 204; b) M.
Uemura, T. Kobayashi, T. Minami, Y. Hayashi, Tetrahedron Lett. 1986, 27, 2479; c) J. Blagg, S. G. Davies,
C. L. Goodfellow, K. H. Sutton, J. Chem. Soc., Perkin Trans. I 1987, 1805; d) S. G. Davies, C. L. Goodfellow,
J. Organomet. Chem. 1988, 340, 195; e) M. Uemura in ꢀAdvances in Metal Organic Chemistryꢁ, Ed. L. S.
Liebeskind, JAI Press, London 1989, p. 195; f) B. Ohlsson, C. Ullenius, S. Jagner, C. Grivet, E. Wenger, E. P.
Kündig, J. Organomet. Chem. 1989, 365, 243; g) J. Brocard, L. Pelinski, J. Lebibi, M. Mahmoudi, L.
Maciejewski, Tetrahedron 1989, 45, 709; h) H. G. Schmalz, B. Millies, J. W. Bats, G. Dürner, Angew. Chem.,
Â
Int. Ed. 1992, 21, 631; i) J. Aube, J. A. Heppert, M. L. Milligan, M. J. Smith, P. Zenk, J. Org. Chem. 1992, 57,
3563; j) C. Baldoli, S. Maiorana, G. Carrea, S. Riva, Tetrahedron: Asymmetry 1993, 4, 767; k) M. Uemura,
R. Miyake, K. Nakayama, M. Shiro, Y. Hayashi, J. Org. Chem. 1993, 58, 1238.