C -Symmetric Bis(oxazolinato)lanthanide Catalysts
2
A R T I C L E S
Scheme 1. Simplified Catalytic Cycle for
Organolanthanide-Mediated Hydroamination/Cyclization of
Aminoalkenes
hydroamination was reported for a limited group of substrates
using C1-symmetric chiral organolanthanide complexes (eq 2).8d
Ansa-lanthanocene frameworks were modified by incorporating
a chiral moiety, an R* such as (-)-menthyl, (-)-phenylmenthyl,
or (+)-neomenthyl, to ensure the formation of separable,
diastereomeric complexes of the type Me2Si(Cp′′)(CpR*)LnE-
(TMS)2 (Cp′′ ) η5-Me4C5; Cp ) η5-C5H3; Ln ) La, Sm, Y,
Lu; R* ) (+)-neomenthyl, (-)-menthyl; E ) N, CH; TMS )
SiMe3; A, B).8b-d,17 The bulky nature of R* and the size
differences between the “upper” (C5Me4-) and “lower” (R*-
C5H3-) Cp rings are designed to provide lateral and transverse
(7) For recent examples of base-catalyzed hydroaminations, see: (a) Trost, B.
M.; Tang, W. J. Am. Chem. Soc. 2002, 124, 14542-14543. (b) Hartung,
C. G.; Breindl, C.; Tillack, A.; Beller, M. Tetrahedron 2000, 56, 5157-
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Trauthwein, H. Angew. Chem., Int. Ed. 1998, 37, 3389-3391. For recent
examples of acid-catalyzed hydroaminations, see: (d) Schlummer, B.;
Hartwig, J. F. Org. Lett. 2002, 4, 1471-1474. (e) Miura, K.; Hondo, T.;
Nakagawa, T.; Takahashi, T.; Hosomi, A. Org. Lett. 2000, 2, 385-388.
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2003-2005.
Thus, there has been a growing interest in developing chiral
organolanthanide complexes to combine the unique catalytic
properties of lanthanides with a chiral coordination sphere.16
In the early 1990s, the first enantioselective intramolecular
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(5) For recent examples of hydroamination catalyzed by early transition metals,
see: (a) Castro, I. G.; Tillack, A.; Hartung, C. G.; Beller, M. Tetrahedron
Lett. 2003, 44, 3217-3221. (b) Shi, Y.; Hall, C.; Ciszewski, J. T.; Cao,
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Straub, B. F.; Bergman, R. G. Angew. Chem., Int. Ed. 2001, 40, 4632-
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(6) For recent examples of hydroamination catalyzed by actinide metals, see:
(a) Wang, J.; Dash, A. K.; Kapon, M.; Berthet, J.-C.; Ephritikhine, M.;
Eisen, M. S. Chem.sEur. J. 2002, 8, 5384-5396. (b) Straub, T.; Haskel,
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metallics 2001, 20, 5017-5035. (c) Haskel, A.; Straub, T.; Eisen, M. S.
Organometallics 1996, 15, 3773-3775.
(17) Other asymmetric transformations with these catalysts include: (a) olefin
hydrogenation (up to 96% ee); ref 8b,c. (b) hydrosilylation (up to 78%
ee); Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117,
7157-7168. (c) isospecific methyl methacrylate polymerization (mm up
to 94%); Giardello, M. A.; Yamamoto, Y.; Brard, L.; Marks, T. J. J. Am.
Chem. Soc. 1995, 117, 3276-3277.
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J. AM. CHEM. SOC. VOL. 125, NO. 48, 2003 14769