Communications
and Mn, see: b) K. Ebata, T. Matsuo, T. Inoue, Y. Otsuka, C.
[8] For selected examples of catalytic fulvene syntheses, see: a) G.
1987, 6, 1941; b) G. C. M. Lee, B. Tobias, J. M. Holmes, D. A.
e) G. Dyker, P. Siemsen, S. Sostmann, A. Wiegand, I. Dix, P. G.
2317; j) F. W. Patureau, T. Besset, N. Kuhl, F. Glorius, J. Am.
Keywords: [2+2+1] cross-cyclotrimerization · alkynes ·
cyclopentadienyl complexes · fulvenes · rhodium
.
[1] For a recent review of the transition-metal-catalyzed intermo-
lecular [2+2+2] cross-cyclotrimerization of two and three
b) K. Tanaka, K. Toyoda, A. Wada, K. Shirasaka, M. Hirano,
Komine, Y. Miyauchi, M. Kobayashi, K. Tanaka, Synlett 2010,
3092; f) T. Konno, K. Moriyasu, R. Kinugawa, T. Ishihara, Org.
T. Aizawa, T. Kitahara, Y. Shimizu, S. Kezuka, R. Takeuchi,
Synlett 2008, 755; for Ni, see: i) N. Mori, S. Ikeda, K. Odashima,
Radhakrishnan, A. Takeda, M. Rubina, M. Rubin, Y. Yama-
Sato, M. Shiotsuki, T. Kondo, T.-a. Mitsudo, J. Mol. Catal. A
2004, 209, 35; m) Y. Ura, Y. Sato, H. Tsujita, T. Kondo, M.
Imachi, T.-a. Mitsudo, J. Mol. Catal. A 2005, 239, 166.
[3] E. S. Johnson, G. J. Balaich, P. E. Fanwick, I. P. Rothwell, J. Am.
[4] U. Radhakrishnan, V. Gevorgyan, Y. Yamamoto, Tetrahedron
[5] The palladium(II)-catalyzed [2+2+1] homo-cyclotrimerization
of cyclopropylacetylene was reported, see: U. M. Dzhemilev,
R. I. Khusnutdinov, N. A. Shchadneva, O. M. Nefedov, G. A.
Tolstikov, Izv. Akad. Nauk SSSR Ser. Khim. 1989, 2360.
[6] Syntheses of transition-metal complexes with fulvene derivatives
by the intermolecular stoichiometric reaction of transition-metal
complexes and terminal alkynes have been reported. For Pd,
2000, 616, 67; for Rh, see: b) J. Moreto, K. Maruya, P. M. Bailey,
Moran, M. Green, A. G. Orpen, J. Organomet. Chem. 1983, 250,
C15; d) A. D. Burrows, M. Green, J. C. Jeffery, J. M. Lynam,
Hiibner, R. Merwin, P. K. Gantzel, B. S. Fong, M. Adams, A. L.
Rheingold, J. Am. Chem. Soc. 1997, 119, 3631; i) J. M. OꢀConnor,
A. Closson, K. Hiibner, R. Merwin, P. Gantzel, D. M. Roddick,
Organometallics 2001, 20, 3710; j) J. M. OꢀConnor, A. P. Closson,
R. L. Holland, S. K. Cope, C. L. Velez, C. E. Moore, A. L.
Rheingold, Inorg. Chim. Acta 2010, 364, 220; for Ru, see: k) E.
Becker, K. Mereiter, M. Puchberger, R. Schmid, K. Kirchner, A.
H. S. Rzepa, R. N. Sheppard, G. Wilkinson, A. M. R. Galas,
M. B. Hursthouse, Polyhedron 1982, 1, 441.
[9] Recently, our research group have reported the cationic
rhodium(I) complex catalyzed cross-trimerization of propargyl
esters and two arylacetylenes, leading to substituted dihydro-
pentalenes, see: Y. Shibata, K. Noguchi, K. Tanaka, Org. Lett.
[10] Unfortunately, the use of the alkynyl ketone 3-hexyn-2-one led
to a complex mixture of products.
[11] For the rhodium(I)-catalyzed cross-dimerizations of two differ-
ent alkynes, see: a) J. Ito, M. Kitase, H. Nishiyama, Organo-
Nishimura, X.-X. Guo, K. Ohnishi, T. Hayashi, Adv. Synth.
[12] The reaction of triethylsilylacetylene (1c) and 2a was sluggish
and furnished oligomers of 1c as the major products. No reaction
was observed in the reaction of (tert-butyldiphenylsilyl)acety-
lene (1d) and 2a. In addition, the use of carbon-substituted
terminal alkynes, instead of silicon-substituted ones, was also
investigated. However, the reaction of phenylacetylene with 1a
led to a complex mixture of products, and no reaction was
observed in the case of alkylacetylenes (1-octyne and 3,3-
dimethyl-1-butyne) with 1a.
[13] The formation of fulvene derivatives via metalacyclopentadiene
intermediates (Ref. [6h–j,8g]) or metal vinylidene intermediates
(Ref. [6c,f,g]) has been proposed for the stoichiometric reactions,
but the mechanism shown in Scheme 4 is more plausible because
of the formation of cross-dimerization products 4.
[15] The desilylative complexation of silylcyclopentadienes with
RhCl3 in an alcohol solvent was reported, see: C. H. Winter, S.
[16] We presume that the present reductive complexation proceeds
through the reaction of the desilylated fulvene and the rhodium
hydride species, generated by the reaction of RhCl3 and EtOH.
For the generation of the rhodium hydride species by the
reaction of RhCl3 and EtOH, see: a) E. G. Thaler, E. G.
reductive complexations of fulvenes and metal hydride species
to produce the corresponding cyclopentadienyl complexes have
been reported, for Zr, see: b) J. J. Eisch, F. A. Owuor, X. Shi,
for Y, see: d) W. J. Evans, B. L. Davis, T. M. Champagne, J. W.
e) S. K. S. Tse, T. Guo, H. H.-Y. Sung, I. D. Williams, Z. Lin, G.
[7] Syntheses of transition-metal complexes with fulvenes by intra-
molecular stoichiometric reactions of transition-metal com-
plexes and cyclic triynes have also been reported. For Cr, Mo,
and W, see: a) H. Sakurai, Y. Nakadaira, A. Hosomi, Y. Eriyama,
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2011, 50, 10917 –10921