COMMUNICATIONS
graphic mismatch branching mechanism, rather than molec-
ular self-assembly.
Exceptional Rate Enhancements and Improved
Diastereoselectivities through Chelating
Diamide Coordination in Intramolecular
Alkene Hydroaminations Catalyzed by Yttrium
and Neodymium Amido Complexes**
Received: February 19, 2002 [Z18736]
[1]a) M. J. Mio, J. S. Moore, MRS Bull. 2000, 25, 36 41; b) D. Derossi, K.
Kajiwara, Y. Osada, A. Yamauchi, Polymer Gels: Fundamentals and
Biomedical Applications, Plenum, New York, 1991; c) J. M. Guenet,
Thermoreversible Gelation of Polymers and Biopolymers, Academic
Press, London, 1992; d) D. Kremer, G. Lagaly, Prog. Colloid. Polym.
Sci. 1996, 102 107; e) R. J. R. Corriu, D. Leclercq, Angew Chem.
1996, 108, 1524 1540; Angew. Chem. Int. Ed. Engl. 1996, 35, 1420
1436; f) M. I. Reetz, Adv. Mater 1997, 9, 943 954.
[2]a) P. Terech, R. G. Weiss, Chem. Rev. 1997, 97, 3133 3159; b) U.
Beginn, S. Keinath, M. Mˆller, Macromol. Chem. Phys. 1998, 199,
2379 2348.
[3]L. Brunsveld, B. J. B. Folmer, E. W. Meijer, MRS Bull. 2000, 25, 49
53.
[4]J. H. van Esch, B. L. Feringa, Angew. Chem. 2000, 112, 2351 2354;
Angew. Chem. Int. Ed. 2000, 39, 2263 2266.
[5]T. Oya, T. Enoki, A. U. Grosberg, S. Masamune, T. Sakiyma, Y.
Tekeoka, K. Tanaka, G. Wang, Y. Tilmaz, M. S. Feld, R. Dasari, T.
Tanaka, Science 1999, 286, 1543 1545.
[6]P. C. Hiemenz, and R. Rajagopalan, Principles of Colloid and Surface
Chemistry, Marcel Dekker, New York, 1997, pp. 145 192.
[7]P. Terech, D. Pasquier, V. Bordas, C. Rossat, Langmuir 2000, 16, 4485
4494.
[8]J. R. Ilzhoefer, R. J. Spontak, Langmuir 1995, 11, 3288 3291.
[9]P. Meakin, Phys. Rev. A 1983, 27, 1495 1507.
Young Kwan Kim and Tom Livinghouse*
The catalyzed intramolecular hydroamination of carbon
carbon multiple bonds is one of the most important methods
for the synthesis of nitrogen heterocycles.[1] Of the variety of
metal-based catalysts for this transformation, complexes of
the lanthanides appear uniquely well suited for effecting
chemoselective alkene hydroaminations under mild reaction
conditions.[2,3] The vast majority of the complexes that have
found utility for this purpose are comparatively air- and
moisture-sensitive metallocene derivatives. We recently dis-
closed that simple amido derivatives of the Group 3 metals
corresponding to the formula [Ln{N(TMS)2}3] (1; Ln ¼ lan-
thanide, TMS ¼ trimethylsilyl) are competent catalysts for
intramolecular alkene hydroamination.[4] Herein we show
that catalytic activity can be dramatically increased and
cyclization diastereoselectivity improved by coordination of
the active metal center to simple chelating diamide ligands
(Scheme 1).
[10]D. S. Graff, L. M. Sander, Phys. Rev. E 1993, 47, R2273–R2276.
[11]O. van Cantfort, A. Brasseur, B. Michaux, R. Pirard, J. P. Pirard, A. J.
Lecloux, Faraday Discuss. 1995, 101, 265 274.
[12]W. H. Shih, W. Y. Shih, S. I. Kim, J. Liu, I. A. Aksay, Phys. Rev. A 1990,
42, 4772 4779.
As part of our previous study,[4] we noted that the addition
of representive amino alkenes to catalytic quantities
[13]a) X. Y. Liu, J. Chem. Phys. 2000, 112, 9949 9955; b) X. Y. Liu,
Langmuir 2000, 16, 7337 7345; c) X. Y. Liu in Advances in Crystal
Growth Research (Eds.: K. Sato, K. Nakajima, Y. Furukawa), Elsevier,
Amsterdam, 2001.
[14]a) X. Y. Liu, P. D. Sawant, Appl. Phys. Lett. 2001, 79, 3518 3520;
b) X. Y. Liu, P. D. Sawant, Adv. Mater. 2002, 14, 421 426.
[15]A. A. Chernov, Modern Crystallography III Crystal Growth, Spring-
er, Berlin, 1984.
[16]a) X. Y. Liu, C. S. Strom, J. Chem. Phys. 2000, 112, 4408 4411; b) C. S.
Strom, X. Y. Liu, M. Wang, J. Phys. Chem. B 2000, 104, 9638 9646.
[17]P. Bennema, X. Y. Liu, K. Lewtas, R. D. Tack, J. J. M. Rijpkema, K. J.
Roberts, J. Cryst. Growth 1992, 121, 679 696.
[18]a) X. Y. Liu, E. S. Boek, W. J. Briels, P. Bennema, Nature 1995, 374,
342 345; b) X. Y. Liu, E. S. Boek, W. J. Briels, P. Bennema, J. Chem.
Phys. 1995, 103, 3747 3754; c) X. Y. Liu, Phys. Rev. B 1999, 60, 2810
2817.
[19]X. Y. Liu, P. D. Sawant, unpublished results.
[20]Y. Otsubo, Adv. Colloid Interface Sci. 1994, 53, 1 32.
[21]X. Y. Liu, K. Maiwa, K. Tsukamoto, J. Chem. Phys. 1997, 106, 1870
1879.
[22]D. A. Kessler, J. Koplik, H. Levine, Adv. Phys. 1988, 37, 255 339.
Scheme 1. Ligands for lanthanide complexes 1 employed in this study.
[*]Prof. Dr. T. Livinghouse, Y. K. Kim
Department of Chemistry
Montana State University
Bozeman, MT 59717 (USA)
Fax : (þ 1)406-994-5407
E-mail: livinghouse@chemistry.montana.edu
[**]Financial support for this research was provided by the National
Science Foundation. T.L. would like to thank Professor John E.
Bercaw for technical advice during the early phases of this program.
Supporting information for this article is available on the WWW under
Angew. Chem. Int. Ed. 2002, 41, No. 19
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0044-8249/02/4119-3645 $ 20.00+.50/0
3645