COMMUNICATIONS
complexes 2. In the presence of 5 mol% of the best catalyst
c, excellent enantioselectivities of 90±9±% ee and high yields
Observation of a H-Agostic Bond in a Highly
Active Rhenium±Alkylidene Olefin Metathesis
Heterogeneous Catalyst by Two-Dimensional
Solid-State NMR Spectroscopy**
2
were obtained for nine 2-naphthols. Compared with its
structural analogue (R,S)-1c, which contains an optically
pure 1,1’-binaphthyl unit, 2c, despite its conformationally
flexible biphenyl unit, still exhibits comparable or higher
enantioselectivities. This discovery not only provides practical
catalysts for the asymmetric synthesis of 1,1’-binaphthols but
is also of significant fundamental interest.
Anne Lesage, Lyndon Emsley,* Mathieu Chabanas,
Christophe Copÿret,* and Jean-Marie Basset*
Heterogeneous catalysis is still the industrial cornerstone in
the production of basic chemicals, polymers, and in some
instances fine chemicals. One of the key problems in devel-
oping new heterogeneous catalysts has been the low content
of active sites coupled with their diversity, which makes their
characterization very difficult and which often does not allow
a rational understanding of their reactivity and selectivity.
Even in cases where, using approaches such as surface
organometallic chemistry (SOMC), well-defined complexes
are prepared, a detailed structural characterization of the
geometry of such surface species is extremely difficult.
Received: July 12, 2002 [Z19±26]
[
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In molecular chemistry the local geometries can be probed
by NMR spectroscopy, for example, by measuring scalar
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could not be determined. Herein we demonstrate how JC,H
1
3; f) V. Pugh, Q. S. Hu, L. Pu, Angew. Chem. 2000, 112, 3±84; Angew.
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dimensional (2D) J-resolved spectroscopic methods, and how
they are related to the local structure of the well-defined
silica-supported rhenium complex 1. This complex was shown
[
3] For resolution of binaphthols, see a) B. Feringa, H. Wynberg, Bioorg.
Chem. 1978, 7, 39±; b) F. Toda, K. Tanaka, J. Org. Chem. 1988, 53,
3
60±; c) S. Miyano, K. Kawahara, Y. Inoue, H. Hashimoto, Tetrahe-
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1
Aymmetry 1995, 6, 2123; f) D. Cai, D. L. Hughes, T. R. Verhoeven,
P. J. Reider, Tetrahedron Lett. 1995, 36, ±991; for nonoxidative
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to be a highly active heterogeneous catalyst for the metathesis
of a variety of olefins at room temperature. In addition, two
isomers can be obtained upon thermal or photochemical
treatment (referred to as syn and anti, depending on the
position of the tBu fragment on the carbene ligand relative to
the metallocarbyne), which were both characterized by solid-
[1]
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4] a) M. Nakajima, I. Miyoshi, K. Kanayama, S.-I. Hashimoto, J. Org.
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[
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[
*] Prof. L. Emsley, Dr. A. Lesage
Laboratoire de Stÿrÿochimie et des Interactions Molÿculaires (UMR-
[
2
002, 914.
5
(
532 CNRS/ENS), Laboratoire de Recherche Conventionnÿ du CEA
23 V)
Ecole Normale Supÿrieure de Lyon
6 Allÿe d©Italie, 69364 Lyon (France)
[
[
8] H. C. Zhang, W. S. Huang, L. Pu, J. Org. Chem. 2001, 66, 481.
9] For applications of a similar strategy in other reactions, see a) K.
Mikami, T. Korenaga, M. Terada, T. Ohkuma, T. Pham, R. Noyori,
Angew. Chem. 1999, 111, 51 ±;Angew. Chem. Int. Ed. 1999, 38, 495;
b) T. Ooi, Y. Uemastu, M. Kameda, K. Maruoka, Angew. Chem. 2002,
4
Fax : (þ 33)4-±2±2-8384
E-mail: lyndon.emsley@ens-lyon.fr
1
14, 1621; Angew. Chem. Int. Ed. 2002, 41, 1551; c) K. Mikami, K.
Aikawa, Y. Yusa, Org. Lett. 2002, 4, 95.
10] a) L. J. Theriot, G. O. Carlisle, H. J. Hu, J. Inorg. Nucl. Chem. 1969, 31,
841; b) J. J. R. Frausto da Silva, R. Wootton, R. D. Gillard, J. Chem.
Soc. A 1970, 3369.
Dr. C. Copÿret, Prof. J.-M. Basset, Dr. M. Chabanas
Laboratoire de Chimie Organomÿtallique de Surface (UMR-9986
CNRS/CPE Lyon)
[
2
Ecole Supÿrieure de Chimie Physique Electronique de Lyon
4
3, Bd du 11 Novembre 1918, 69616 Villeurbanne Cedex (France)
Fax : (þ 33)4-±243-1±95
E-mail: coperet@cpe.fr
[
**] We thank the C.N.R.S., the ESCPE-Lyon, and ENS-Lyon for financial
support. M.C. is grateful to the French Ministry for Education and
Research for a fellowship (MENRT).
Angew. Chem. Int. Ed. 2002, 41, No. 23
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