Angewandte
Chemie
[
7] a) J. O. Krause, M. T.
Zarka, U. Anders, R.
Weberskirch, O.
Nuyken, M. R. Buchme-
iser, Angew. Chem. 2003,
1
15, 6147 – 6151; Angew.
Chem. Int. Ed. 2003, 42,
965 – 5969; b) J. O.
Krause, O. Nuyken,
M. R. Buchmeiser,
Chem. Eur. J. 2004, 10,
029 – 2035; c) L. Yang,
M. Mayr, K. Wurst,
M. R. Buchmeiser,
Chem. Eur. J. 2004, 10,
761 – 5770.
5
2
Scheme 3. Plausible mechanism of olefin RCH=CH metathesis with 3c.
2
5
[
8] a) J. J. Van Veldhuizen,
D. G. Gillingham, S. B.
[
3]
platform for generating new greener metathesis catalysts,
[
11]
Garber, O. Kataoka, A. H. Hoveyda, J. Am. Chem. Soc. 2003,
25, 12502 – 12508; b) J. J. Van Veldhuizen, J. E. Campbell,
R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2005, 127,
877 – 6882.
for example, through reaction with supported, polyethy-
1
[
9]
lene-glycolated, ionically tagged, or perfluorinated carbox-
ylic and sulfonic acids. Such studies are underway and will be
reported in due course.
6
[9] Boehringer Ingelheim International WO 2004/089974A1, 2004.
10] M. Bieniek, R. Bujok, M. Cabaj, N. Lugan, G. Lavigne, D. Arlt,
K. Grela, J. Am. Chem. Soc. 2006, 128, 13652 – 13653.
[
Received: March 24, 2007
Published online: July 27, 2007
[11] For a recent example, see: A. Michrowska, K. Mennecke, U.
Kunz, A. Kirschning, K. Grela, J. Am. Chem. Soc. 2006, 128,
1
3261 – 13267.
Keywords: carbenes · carboxylate ligands ·
homogeneous catalysis · olefin metathesis · ruthenium
.
[12] a) Typically, ruthenium complexes of type 1b–1g and 1i–1m are
obtained by reaction of silver, thallium, or lead carboxylates,
sulfonates, and phenolates with corresponding dichloro-Ru
complexes; see Refs. [2,4–7] and K. Tanaka, V. P. W. Bohm, D.
Chadwick, M. Roeper, D. C. Braddock, Organometallics 2006,
25, 5696 – 5698. b) For a silica gel mediated rearrangement of
neutral ligands in a second-generation Ru alkylidene, see S.
Prühs, C. W. Lehmann, A. Fürstner, Organometallics 2004, 23,
280 – 287. c) A crude product of the reaction between 1a and 2b
isolated without the use of a silica gel column chromatography
shows in NMR spectroscopy a benzylidene signal at d =
16.73 ppm and a broad singlet at d = 10.55 ppm, which suggest
that this reaction leads to the dichloro complex 3b rather than to
cyclized 3c.
[13] a) M. Barbasiewicz, A. Szadkowska, A. Makal, K. Wo z´ niak, K.
Grela, unpublished results; b) see: M. Barbasiewicz, M. Bieniek,
A. Michrowska, A. Szadkowska, A. Makal, K. Wo z´ niak, K.
Grela, Adv. Synth. Catal. 2007, 349, 193 – 203, and Ref. [33]
therein.
[14] For related examples from one of our laboratories, see Ref. [11]
and L. Gulajski, A. Michrowska, R. Bujok, K. Grela, J. Mol.
Catal. A 2006, 254, 118 – 123.
[
1] For reviews on metathesis, see: a) T. M. Trnka, R. H. Grubbs,
Acc. Chem. Res. 2001, 34, 18 – 29; b) Handbook of Metathesis
(
Ed.: R. H. Grubbs), Wiley-VCH, Weinheim, 2003, p. 1204;
c) R. R. Schrock, A. H. Hoveyda, Angew. Chem. 2003, 115,
740 – 4782; Angew. Chem. Int. Ed. 2003, 42, 4592 – 4633; d) S. J.
4
Connon, S. Blechert, Angew. Chem. 2003, 115, 1944 – 1968;
Angew. Chem. Int. Ed. 2003, 42, 1900 – 1923; e) D. Astruc, New J.
Chem. 2005, 29, 42 – 56.
[
2] a) J. C. Conrad, D. Amoroso, P. Czechura, G. P. A. Yap, D. E.
Fogg, Organometallics 2003, 22, 3634 – 3636; b) S. Monfette,
D. E. Fogg, Organometallics 2006, 25, 1940 – 1944; c) J. C.
Conrad, H. H. Parnas, J. L. Snelgrove, D. E. Fogg, J. Am.
Chem. Soc. 2005, 127, 11882 – 118830.
[
3] For a recent review stressing these problems, see: H. Clavier, K.
Grela, A. Kirschning, M. Mauduit, S. P. Nolan, Angew. Chem.,
DOI: 10.1002/ange.200605099; Angew. Chem. Int. Ed., DOI:
10.1002/anie.200605099.
[
[
4] P. Nieczypor, W. Buchowicz, W. J. N. Meester, F. P. J. T. Rutjes,
J. C. Mol, Tetrahedron Lett. 2001, 42, 7103 – 7105.
[15] a) J. A. Love, J. P. Morgan, T. M. Trnka, R. H. Grubbs, Angew.
Chem. 2002, 114, 4207 – 4209; Angew. Chem. Int. Ed. 2002, 41,
4035 – 4037, and references therein; b) J. S. Kingsbury, A. H.
Hoveyda, J. Am. Chem. Soc. 2005, 127, 4510 – 4517.
5] a) J. O. Krause, O. Nuyken, K. Wurst, M. R. Buchmeiser, Chem.
Eur. J. 2004, 10, 777 – 784; b) T. S. Halbach, S. Mix, D. Fischer, S.
Maechling, J. O. Krause, C. Sievers, S. Blechert, O. Nuyken,
M. R. Buchmeiser, J. Org. Chem. 2005, 70, 4687 – 4694; c) M.
Mayr, D. Wang, R. Kröll, N. Schuler, S. Prhs, A. Fürstner, M. R.
Buchmeiser, Adv. Synth. Catal. 2005, 347, 484 – 492; d) J. O.
Krause, S. H. Lubbad, O. Nuyken, M. R. Buchmeiser, Macro-
mol. Rapid Commun. 2003, 24, 875 – 878; e) J. O. Krause, S.
Lubbad, O. Nuyken, M. R. Buchmeiser, Adv. Synth. Catal. 2003,
[16] For other latent catalysts, see: a) C. Slugovc, D. Burtscher, F.
Stelzer, K. Mereiter, Organometallics 2005, 24, 2255 – 2258;
b) P. A. van der Schaaf, R. Kolly, H.-J. Kirner, F. Rime, A.
Mühlebach, A. Hafner, J. Organomet. Chem. 2000, 606, 65 – 74;
c) T. Ung, A. Hejl, R. H. Grubbs, Y. Schrodi, Organometallics
2004, 23, 5399 – 5401; d) M. Barbasiewicz, A. Szadkowska, R.
Bujok, K. Grela, Organometallics 2006, 25, 3608 – 3613; e) X.
Gstrein, D. Burtscher, A. Szadkowska, M. Barbasiewicz, F.
Stelzer, K. Grela, C. Slugovc, J. Polym Sci. Part A: Polym.
Chem., 2007, 45, 3494 – 3500.
345, 996 – 1004.
[
6] a) K. Grela, S. Harutyunyan, A. Michrowska, Angew. Chem.
2002, 114, 4210 – 4212; Angew. Chem. Int. Ed. 2002, 41, 4038 –
4040; b) K. Grela, M. Kim, Eur. J. Org. Chem. 2003, 963 – 966.
Angew. Chem. Int. Ed. 2007, 46, 7206 –7209
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim