J.-C. Kizirian et al. / Tetrahedron Letters 44 (2003) 8893–8895
8895
Table 4. Enantioselective addition of MeLi to imine 7
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with ligands substituted by an aromatic chain
Entry
Ligand
Yield (%)
Ee (%)a
1
2
3
4
5
6
7
1g (1 equiv.)
1g (20%)
1h (20%)
1h (5%)
1h (1%)
1i (20%)
1j (20%)
78
94
98
72
62
93
95
48 (R)
40 (R)
68 (R)
43 (R)
32 (R)
58 (R)
0
a Determined by supercritical fluid chromatography.
ity disappears completely. This last result is consistent
with the behavior of the ligands of the b series.
The amount of ligand 1h was decreased from 100% to
5 mol% and 1 mol%. The product was still obtained
with good conversion (Table 4, entries 4 and 5) but
with significant erosion of selectivity (respectively 43%
and 32%).
2. (a) Li, X.; Yang, J.; Kozlowski, M. Org. Lett. 2001, 8,
1137; (b) Nakajima, M.; Miyoshi, I.; Kanayama, K.;
Hashimoto, S. I.; Noji, M.; Koga, K. J. Org. Chem. 1999,
64, 2264; (c) Oriyama, T.; Taguchi, H.; Terakado, D.;
Sano, T. Chem. Lett. 2002, 26; (d) Tanner, D.; Johansson,
F.; Harden, A.; Andersson, P. G. Tetrahedron 1998, 54,
15731; (e) Gamez, P.; Fache, F.; Lemaire, M. Tetrahedron:
Asymmetry 1995, 3, 705.
3. (a) Andersson, P. G.; Johansson, F.; Tanner, D. Tetra-
hedron 1998, 54, 11549; (b) Denmark, S. E.; Nakajima, N.;
Nic¸aise, O. J. Am. Chem. Soc. 1994, 116, 8797; (c) Inoue,
I.; Shindo, M.; Koga, K.; Tomioka, K. Tetrahedron:
Asymmetry 1993, 7, 1603.
4. Larrow, J. F.; Jacobsen, E. Org. Syn. 1998, 75, 1.
5. (a) Hanessian, S.; Delorme, D.; Beaudoin, S.; Leblanc, Y.
J. Am. Chem. Soc. 1984, 106, 5754; (b) Alexakis, A.;
Mutti, S.; Mangeney, P. J. Org. Chem. 1992, 57, 1224; (c)
Alexakis, A.; Chauvin, A.-S.; Stouvenel, R.; Vrancken, E.;
Mutti, S.; Mangeney, P. Tetrahedron: Asymmetry 2001, 12,
1171.
In conclusion, we have prepared a new class of diamine
ligands that give interesting levels of enantioselectivity
in the addition of methyllithium to an imine. We have
checked that substoichiometric amounts of this type of
ligand are sufficient to catalyze the reaction without
large loss of selectivity. The improved results with our
new ligands compared to the classic one, 1a, demon-
strate the validity of our initial hypothesis concerning
the stereogenicity of the nitrogens when they bear dif-
ferent substituents. These results are very promising
and the study of other reactions of the new ligands is in
progress in our laboratory as well as the examination of
the scope and limitations of this concept.
Acknowledgements
The authors wish to thank PPG-SIPSY for financial
support.
6. All novel compounds gave satisfactory spectroscopic and
analytical data. For compound 1d, see: Hoffman, R. W.;
Klute, W. Chem. Eur. J. 1996, 2, 694.
7. (a) Inoue, I.; Shindo, M.; Koga, K.; Kanai, M.; Tomioka,
K. Tetrahedron: Asymmetry 1995, 10, 2527; (b) Denmark,
S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875; (c)
Arrasate, S.; Lete, E.; Sotomayor, N. Tetrahedron: Asym-
metry 2001, 12, 2077.
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