1026
Acknowledgements
Financial support by CNRS, MENRT and DFG is gratefully acknowledged for grants respectively to
R.B. and A.S. Dr. R. Grée is thanked for helpful discussions.
References
1. (a) Evans, D. A.; Woerpel, K. A.; Hinman, M. M.; Faul, M. M. J. Am. Chem. Soc. 1991, 113, 726–728. (b) Evans, D. A.;
Woerpel, K. A.; Scott, M. J. Angew. Chem. 1992, 104, 439–441; Angew. Chem. Int. Ed. Engl. 1992, 31, 430–432. (c) Müller,
D.; Umbricht, G.; Weber, B.; Pfaltz, A. Helv. Chim. Acta 1991, 74, 232–240. (d) Nishiyama, H.; Sakaguchi, H.; Nakamura,
T.; Horihata, M.; Kondo, M.; Itoh, K. Organometallics 1989, 8, 846–848. (e) Nishiyama, H.; Yamaguchi, S.; Kondo, M.;
Itoh, K. J. Org. Chem. 1992, 57, 4306–4309. (f) For reviews, see: Pfaltz, A. Acc. Chem. Res. 1993, 26, 339–345, Doyle,
M. P.; Protopopova, M. N. Tetrahedron 1998, 54, 7919–7946 and Ghosh, A. K.; Mathivanan, P.; Cappiello, J. Tetrahedron:
Asymmetry 1998, 9, 1–45.
2. The first uses of this new type of ligands were achieved for hydrosilylation: Lee, S.-g.; Lim, C. W.; Song, C. E.; Kim, I. O.;
Jun, C.-H. Tetrahedron: Asymmetry 1997, 8, 2927–2932.
3. Ebinger, A.; Heinz, T.; Umbricht, G.; Pfaltz, A. Tetrahedron 1998, 54, 10469–10480.
4. All new compounds afforded satisfactory spectroscopic data as well as HRMS and/or combustion analysis. Selected data for
3e: 1H NMR (400 MHz, CDCl3): δ 4.55–4.46 (m, 2H), 4.12 (pseudo dd, 2H, J=10.1, 9.0 Hz), 3.89 (pseudo dd, 2H, J=9.0,
6.5 Hz), 2.01 (broad s, 6H), 1.94–1.79 (m, 12H), 1.78–1.64 (m, 12H); 13C NMR (100 MHz, CDCl3): δ 175.27, 67.70,
67.67, 39.73, 36.54, 35.34, 27.91; [α]2D4=−25.1 (c=1.7, CHCl3); MS (FAB, m-nitrobenzylic alcohol matrix) m/z (%): 817
(2) [2M+H]+, 409 (100) [M+H]+, 273 (2) [M−C10H15]+; Anal. calcd for C26H36N2O2: C, 76.41; H, 8.90; N, 6.86. Found: C,
76.31; H, 8.96; N, 6.82.
5. Scheurer, A.; Mosset, P.; Saalfrank, R. W. Tetrahedron: Asymmetry 1997, 8, 1243–1251 and 3161.
6. Congreve, M. S.; Davison, E. C.; Fuhry, M. A. M.; Holmes, A. B.; Payne, A. N.; Robinson, R. A.; Ward, S. E. Synlett 1993,
663–664.
7. Denmark, S. E.; Nakajima, N.; Nicaise, O. J.-C.; Faucher, A.-M.; Edwards, J. P. J. Org. Chem. 1995, 60, 4884–4892.
8. No surface effect was observed. For an example of a surface effect with molecular sieves, see: Gothelf, K. V.; Hazell, R. G.;
Jørgensen K. A. J. Org. Chem. 1998, 63, 5483–5488.
9. A typical experimental procedure for the asymmetric cyclopropanation: CuOTf.1/2 C6H6 (0.02 mmol, purchased from Fluka)
was complexed by a bi(oxazoline) 3 (0.03 mmol) in anhydrous CH2Cl2 (3.4 mL) (1 h, rt). The resulting filtered solution was
transferred to alkene 8 or 11 (7.9 mmol) and additive (1 g) in CH2Cl2 (1 mL). A solution of ethyl diazoacetate (1 mmol) in
CH2Cl2 (1 mL) was added during 5 h at 0°C and stirring was continued for 16 h at ca. 20°C.
10. Very recently, the first example of a catalyst which gives predominantly the cis-isomer was reported: Uchida, T.; Irie, R.;
Katsuki, T. Synlett 1999, 1163–1165.