R. R. Schrock, J. H. Freudenberger, M. L. Listemann and L. G.
McCullough, J. Mol. Catal., 1985, 28, 1; (d ) R. Poli and K. M.
Smith, in Science of Synthesis, Houben-Weyl Methods of Molecu-
lar Transformations, ed. G. F. Herrmann, Georg Thieme Verlag,
Stuttgart, 2000, ch. 2.6, p. 59; (e) R. R. Schrock, J. Chem. Soc.,
Dalton Trans., 2001, 2541; ( f ) R. R. Schrock, Chem. Rev., 2002,
102, 145.
Typical metathesis procedure
A 50 ml Schlenk flask fitted with a reflux condenser was filled
with p-chlorophenol (1.50 g, 11 mmol), diphenoxyethane (0.20
g, 0.93 mmol), decalin as internal standard (300 mL), freshly
activated molecular sieves (6.00 g) and chlorobenzene (25
mL). The solution was refluxed for 3 h under nitrogen. Then,
Mo(CO)6 (0.2 g, 0.76 mmol) was added and the resulting col-
orless suspension was refluxed until complete disappearance of
the characteristic n(CO) IR absorption. The dark orange solu-
tion was then allowed to cool down to 50 ꢀC and 8.33 mmol of
phenylpropyne were added. The metathesis reaction was moni-
tored by gas chromatography. After reaction completion, the
solution was filtered through celite, which was then washed
with THF. The organic filtrate was evaporated to dryness, giv-
ing a dark residue from which diphenylacetylene was isolated
by column chromatography. The yield was determined after
drying under vacuum to constant weight. The product was
characterized by GC and GC/MS (based on comparison with
2
For leading references on applications to organic synthesis, see:
(a) A. Furstner, A.-S. Castanet, K. Radkowski and C. W.
¨
Lehman, J. Org. Chem., 2003, 68, 1521 and references therein;
(b) A. Furstner, C. Mathes and C. W. Lehmann, Chem.-Eur. J.,
¨
Lehmann, J. Am. Chem. Soc., 2000, 122, 11 799; (d ) A. Furstner,
¨
2001, 7, 5299; (c) A. Furstner, K. Grela, C. Mathes and C. W.
¨
F. Steltzer, A. Rumbo and H. Krause, Chem.-Eur. J., 2002,
8, 1856.
3
4
(a) A. Mortreux and M. Blanchard, J. Chem. Soc., Chem. Com-
mun., 1974, 786; (b) A. Mortreux, J. C. Delagrange, M. Blanchard
and B. Lubochinsky, J. Mol. Catal., 1977, 73; (c) D. Villemin and
P. Cadiot, Tetrahedron Lett., 1982, 23, 5139; (d ) A. Bencheik,
M. Petit, A. Mortreux and F. Petit, J. Mol. Catal., 1982, 15, 93;
´
(e) D. Villemin, M. Heroux and V. Blot, Tetrahedron Lett.,
2001, 42, 3701.
1
authentic samples) and H NMR spectroscopy.
(a) N. G. Pschirer and U. H. F. Bunz, Tetrahedron Lett., 1999,
40, 2481; (b) L. Kloppenburg, D. Song and U. H. F. Bunz,
J. Am. Chem. Soc., 1998, 120, 7973; (c) N. G. Pschirer, T.
Miteva, U. Evans, R. S. Roberts, A. R. Marshall, D. Neher,
M. L. Myrick and U. H. F. Bunz, Chem. Mater., 2001, 13,
2691; (d ) N. G. Pschirer and U. H. F. Bunz, Macromolecules,
2000, 33, 3961; (e) P.-H. Ge, W. Fu, W. A. Herrmann, E.
Herdtweck, C. Campana, R. D. Adams and U. H. F. Bunz,
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Chem. Res., 2001, 34, 998.
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C. Godard, S. Frau, C. Lepetit, M. Soleihavoup and R. Chauvin,
Chem.-Eur. J., 2001, 7, 1165; (c) C. Lepetit, B. Silvi and
R. Chauvin, J. Phys. Chem. A, 2003, 107, 464 and references
therein
(a) L. G. McCullough and R. R. Schrock, J. Am. Chem. Soc.,
1984, 106, 4067; (b) L. G. McCullough, R. R. Schrock, J. C.
Dewan and J. C. Murdzek, J. Am. Chem. Soc., 1985, 107, 5987.
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Y. Gao, R. M. Hanson, J. M. Kluder, S. Y. Ko, H. Masamune
and K. B. Sharpless, J. Am. Chem. Soc., 1987, 109, 5765.
(a) R. R. Schrock, J. Sancho and S. F. Pedersen, Inorg. Synth.,
1989, 26, 44; (b) M. A. Stevenson and M. D. Hopkins, Organo-
metallics, 1997, 16, 3572.
=
Metathesis of Ph Si(C CMe) (4)
=
2
2
=
(a) Preparation of Ph Si(C CMe) (4). Ph SiCl (0.81 mL,
=
3.84 mmol) was added to a solution of MeC CMgBr (18
2
2
2
2
=
=
mL, 0.5 M, 9 mmol) in THF (50 mL). After stirring overnight,
a white precipitate appeared and the mixture was treated with
Et2O–aq. NH4Cl. The organic layer was separated and dried
over MgSO4 . The residue was chromatographed over silical
gel (eluent: pentane– CH2Cl2 10 : 1 to 10 : 3). The silane
5
6
=
Ph Si(C CMe) (4) was obtained as a white solid (1.05 g,
=
2
2
quant.). MS (EI) m/z: 260 [M]+, 245 [M ꢁ CH3]+, 183
[M ꢁ Ph]+. 1H NMR (CDCl3 , 200 MHz) d: 2.00 (s, 6 H);
7.37–7.40 (m, 6 H); 7.72–7.76 (m, 4 H). 13C NMR (CDCl3 ,
50 MHz) d: 5.39; 78.01; 107.20; 127.94; 129.98; 133.67; 134.74.
=
7
8
The molecular structure of Ph Si(C CMe) (4) was con-
=
firmed by an X-ray structure analysis (unpublished result).
2
2
9
(b) Analytical data for the metathesis product
=
=
=
=
(MeC C)(Ph) Si-(C C)-Si(Ph) (C CMe) (5a). MS (EI) m/z:
=
=
2
2
466 [M]+, 451 [M ꢁ CH3]+, 389 [M ꢁ C6H5]+, 350 [M ꢁ
10 (a) We see a possible relevance to both the concept of hemi-lability
introduced by Hoveyda et al. in olefin metathesis10b-c and
the concept of ‘‘ligand-accelerated catalysis’’ developed by
Sharpless et al.10d; (b) S. B. Garber, J. S. Kingsbury, B. L. Gray
and A. H. Hoveyda, J. Am. Chem. Soc., 2000, 122, 8168; (c) K.
Grela, S. Harutyunyan and A. Michrowska, Angew. Chem., Int.
Ed., 2002, 41, 4038 and references therein; (d ) D. J. Berrisford,
C. Blom and K. B. Sharpless, Angew. Chem., Int. Ed. Engl.,
1995, 34, 1059.
11 (a) M. L. Listemann and R. R. Schrock, Organometallics, 1985, 4,
74 ; for pyridine-stabilized alkylidyne species, see; (b) T. P. Pollagi,
S. J. Geib and M. D. Hopkins, J. Am. Chem. Soc., 1994,
116, 6051.
12 (a) M. H. Chisholm, B. K. Conroy, J. C. Huffman and N. S.
Marchant, Angew. Chem., Int. Ed. Engl., 1986, 25, 446; (b)
M. H. Chisholm, D. R. Click, J. C. Gallucci, C. M. Hadad and
P. J. Wilson, J. Am. Chem. Soc., 2002, 124, 14 518.
13 (a) T. Woo, E. Olga and T. Ziegler, Organometallics, 1993, 12,
1289; (b) S. F. Vyboishchikov and G. Frenking, Chem.-Eur. J.,
1998, 4, 1439.
C6H5 ꢁ CCCH3]+, 245 [M ꢁ Si(C6H5)2 ꢁ CCCH3]+. H NMR
1
(CDCl3 , 200 MHz) d: 2.01 (s, 6 H); 7.24–7.41 (m; 6 H);
7.75–7.80 (m, 4 H). 13C NMR (CDCl3 , 50 MHz) d: 5.19;
77.17; 107.97; 111.35; 121.11; 130.17; 132.28; 134.86.
Acknowledgements
The authors wish to thank the CNRS and the French Minis-
` ´
tere de l’Enseignement Superieur de la Recherche et de la
Technologie for financial support (specific ACI funding).
References
1
(a) R. R. Schrock, D. N. Clark, J. Sancho, J. H. Wengrovius
and S. F. Pederson, Organometallics, 1982, 1, 1645; (b) M. L.
Listemann and R. R. Schrock, Organometallics, 1985, 4, 74; (c)
14 K. Grela and J. Ignatowska, Org. Lett., 2002, 4, 3747.
1414
New J. Chem., 2003, 27, 1412–1414