COMMUNICATIONS
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[37] 18: [a]2D2
47.2 (c 0.90, H2O). 1H NMR (400 MHz, D2O): d 1.19
(d, J4,3 6.2 Hz, 3H, Thr), 4.55 (d, J1'',2'' 7.6 Hz, 1H, H-1, Gal), 5.06
(d, J1,2 10 Hz, H-1, GlcNAc), 5.16 (d, J1',2' 3.5 Hz, H-1, Ara);
13C NMR (100.6 MHz, D2O, DEPT): d 77.11 (C-1, GlcNAc), 98.82
(C-1 Ara), 99.81 (C-2, Sial), 101.58 (C-1, Gal); Quadrupolar ESI-MS:
[M2Na Li
H ]/2 (m/z): calcd 972.87; found 972.88.
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[39] The syntheses of these compounds will be described elsewhere.
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Monolithic Materials: New High-Performance
Supports for Permanently Immobilized
Metathesis Catalysts
Monika Mayr, Betina Mayr, and
Michael R. Buchmeiser*
Olefin metathesis and variations thereof are among the
most important tools for C C bond formation.[1] Polymer
chemistry and materials sciences have seen the introduction
of new trends by metathesis-based techniques, such as ring-
opening metathesis polymerization (ROMP) or acyclic diene
polymerization (ADMET). Complementary, cross-metathesis
and ring-closing metathesis find ample application in organic
chemistry.[2] Molybdenum- and ruthenium alkylidenes (the
latter based on N-heterocyclic carbenes, NCH ligands) are
used for this purpose but, until recently, only in homogeneous
catalysis.[3] The first heterogeneous ruthenium systems have
already been described by Grubbs et al. but these in particular
turned out to be less suited to polymerization.[4] Meanwhile, a
few non-permanently immobilized Grubbs catalysts have
been reported,[5±7] although the system described by Blechert
et al. basically represents the only recyclable heterogeneous
Grubbs catalyst.[8] Despite the good catalytic data that has
been reported for RCM, we investigated a new method to
reach heterogeneous metathesis catalysts. The final goal was
to combine the advantages of homogeneous and heteroge-
neous catalysis and, simultaneously, eliminate the disadvan-
tages typical for many heterogeneous systems, such as
diffusion-controlled reactions and catalyst bleeding, among
others. Again, NHC ligands appeared highly attractive for
these purposes. On one hand they allow the generation of
highly active ruthenium carbenes,[9±12] on the other hand the
corresponding NHC/phosphane-based systems are quite sta-
[22] P. J. Garegg, H. Hultin, S. Wallin, Carbohydr. Res. 1982, 108, 97.
[23] R. R. Schmidt, J. Michel, Angew. Chem. 1980, 92, 763; Angew. Chem.
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[25] 12: [a]2D2
66.0 (c 1.00, CHCl3); 1H NMR (400 MHz, [1H,1H-
COSY], [1H,13C-COSY], CDCl3): d 2.03 (m, Jgem 12.9, Jvic
5.4 Hz, 1H, H-3a; Sial), 2.71 (dd, Jgem 12.9, Jvic 4.4 Hz, 1H, H-3b;
Sial), 4.18 ± 4.26 (m, Jgem 12.6, J9''',8''' J3'',4'' 2.7, J1,2 8.6 Hz, 3H,
H-9b; Sial, H-1, GlcNAc, H-3, Gal), 4.62 (d, J1'',2'' 7.9 Hz, 1H; H-1,
Gal), 5.25 (d, J1',2' 3.1 Hz, 1H; H-1, Ara).
[26] H. Kunz, W. Pfrengle, K. Rück, W. Sager, Synthesis 1991, 1039.
[27] A. Trzeciak, W. Bannwarth, Tetrahedron Lett. 1992, 33, 4557.
[28] K. Peilstöcker, H. Kunz, Synlett 2000, 820; K. Peilstöcker, H. Kunz,
Synlett 2000, 823.
[29] L. A. Carpino, J. Am. Chem. Soc. 1993, 115, 4397.
[30] M. Ciommer, H. Kunz, Synlett 1991, 583.
[31] 14: [a]2D2
38.80 (c 1.00, CHCl3); 13C NMR (100.6 MHz, DEPT,
CDCl3): d 47.04 (Fmoc-C-9), 49.56 (C-5, Sial), 50.22 (C-2, GlcNAc),
81.35 (C-1, GlcNAc), 97.75 (C-2, Sial), 100.10, 100.24 (C-1, Ara, C-1,
Gal).
[32] O. Seitz, H. Kunz, J. Org. Chem. 1996, 61, 2638.
[33] E. Bayer, W. Rapp, Chem. Pept. Proteins 1986, 3, 3; trademark Rapp-
Polymere, Tübingen, Germany.
[34] S. Keil, C. Claus, W. Dippold, H. Kunz, Angew. Chem. 2001, 113, 379;
Angew. Chem. Int. Ed. 2001, 40, 366.
[*] A. Univ.-Prof. Dr. M. R. Buchmeiser, M. Mayr, Mag. B. Mayr
Institut für Analytische Chemie und Radiochemie
Universität Innsbruck
Innrain 52a, 6020 Innsbruck (Austria)
Fax : (43)512-507-2677
[35] M. Rothe, J. Mazanek, Angew. Chem. 1972, 84, 290; Angew. Chem. Int.
Ed. Engl. 1972, 11, 293.
[36] R. Knorr, A. Trzeciak, W. Bannwarth, D. Gillessen, Tetrahedron Lett.
1989, 30, 1927.
Supporting information for this article is available on the WWW under
Angew. Chem. Int. Ed. 2001, 40, No. 20
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
1433-7851/01/4020-3839 $ 17.50+.50/0
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