ORGANIC
LETTERS
2
006
Vol. 8, No. 18
011-4014
Nickel-Catalyzed [3+1+1] Cycloaddition
Reactions of Alkenyl Fischer Carbene
Complexes with
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Methylenecyclopropanes
Ken Kamikawa,* Yasunori Shimizu, Shin Takemoto, and Hiroyuki Matsuzaka
Department of Chemistry, Graduate School of Science, Osaka Prefecture UniVersity,
Sakai, Osaka 599-8531, Japan
Received June 25, 2006
ABSTRACT
Methylenecyclopentanones were synthesized by the nickel-catalyzed [3+1+1] cycloaddition reactions of alkenyl Fischer carbene complexes
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with methylenecyclopropanes. The methylenecyclopropane was transformed into the C -symmetric bis-cyclopentapyridazine derivative by
reacting with p-toluenesulfonyl hydrazine.
The Fischer carbene complex is one of the most versatile
organometallic reagents for organic synthesis, and a number
of novel reactions involving this complex have been re-
expected to have great potential for the syntheses of highly
functionalized organic molecules. However, so far, the
reactions of these reactive species under photochemical and
thermal conditions have appeared in only two reports.6
Recently, de Meijere et al. reported the synthesis of cyclo-
pentenone derivatives via cyclization reactions of MCPs with
Fischer carbene complexes in thermal reaction conditions.6b
As a transition metal is expected to catalyze reactions with
MCPs at different reaction sites, we report herein the
transition metal catalyzed [3+1+1] cycloaddition reactions
of Fischer carbene complexes with MCPs.
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ported. There is increasing interest in transition metal
mediated or catalyzed reactions of Fischer carbene complexes
2
3
with alkynes, allenes leading to new forms of reactivity.
On the other hand, methylenecyclopropanes (MCPs) have
been widely utilized as useful building blocks in organic
4
synthesis. In particular, transition metal catalyzed reactions
of MCPs have been used for the synthesis of complex organic
5
molecules. Thus, the reactions of Fischer carbene complexes
with MCPs mediated or catalyzed by transition metals are
Initially, pentacarbonyl[(1-methoxy-(2-phenyl)ethenylcar-
bene)]chromium(0) (1) was treated with phenylmethylenecy-
(1) (a) Special Issue: Carbene Chemistry: Bertrand, G., Ed. J. Orga-
clopropane (2) in the presence of 1.1 equiv of Ni(cod)
2
nomet. Chem. 2005, 690, 5397. (b) D o¨ tz, K. H.; Minatti, A. In Transition
Metals for Organic Synthesis; Matthias, B., Bolm, C., Eds.; Wiley-VCH:
Weiheim, Germany, 2004; p 397. (c) Sierra, M. A. Chem. ReV. 2000, 100,
(5) (a) Binger, P.; B u¨ ch, H. M. Top. Curr. Chem. 1987, 135, 77. (b)
Ohta, T.; Takaya, H. In ComprehensiVe Organic Synthesis; Trost, B. M.,
Ed.; Pergamon: Oxford, UK, 1991; Vol. 5, p 1185. (c) Nakamura, I.;
Yamamoto, Y. AdV. Synth., Catal. 2002, 344, 111. (d) Shi, M.; Liu, L.-P.;
Tang, J. J. Am. Chem. Soc. 2006, 128, 7430. (e) Kurahashi, T.; de Meijere,
A. Angew. Chem., Int. Ed. 2005, 44, 7881. (f) Saito, S.; Masuda, M.;
Komagawa, S. J. Am. Chem. Soc. 2004, 126, 10540. (g) Suginome, M.;
Matsuda, T.; Ito, Y. J. Am. Chem. Soc. 2000, 122, 11015. (h) Lautens, M.;
Ren, Y. J. Am. Chem. Soc. 1996, 118, 9597.
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591. (d) Harvey, D. F.; Sigano, D. M. Chem. ReV. 1996, 96, 271.
(
2) (a) Barluenga, J.; Vicente, R.; L o´ pez, L. A.; Rubio, E.; Tom a´ s, M.;
AÄ lvarez-R u´ a, C. J. Am. Chem. Soc. 2004, 126, 470. (b) Barluenga, J.; Barrio,
P.; L o´ pez, L. A.; Tom a´ s, M.; Garc ´ı a-Granda, S.; Alvarez-R u´ a, C. Angew.
Chem., Int. Ed. 2003, 42, 3008. (c) G o¨ ttker-Schnetmann, I.; Aumann, R.
Organometallics 2001, 20, 346. (d) G o¨ ttker-Schnetmann, I.; Aumann, R.;
Bergander, K. Organometallics 2001, 20, 3574.
(3) (a) Barluenga, J.; Vicente, R.; Barrio, P.; L o´ pez, L. A.; Tom a´ s, M.
J. Am. Chem. Soc. 2004, 126, 5974. (b) Barluenga, J.; Vicente, R.; Barrio,
P.; L o´ pez, L. A.; Tom a´ s, M.; Borge, J. J. Am. Chem. Soc. 2004, 126, 14354.
(6) (a) Hegedus, L. S.; Bates, R. W.; S o¨ derberg, B. C. J. Am. Chem.
Soc. 1991, 113, 923. (b) Kurahashi, T.; Wu, Y.-T.; Meindl, K.; R u¨ hl, S.;
de Meijere, A. Synlett 2005, 805.
(4) Brandi, A.; Goti, A. Chem. ReV. 1998, 98, 589.
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0.1021/ol061559s CCC: $33.50
© 2006 American Chemical Society
Published on Web 07/27/2006