Organic Letters
Letter
9292. (d) Motokura, K.; Nakayama, K.; Miyaji, A.; Baba, T.
ChemCatChem 2011, 3, 1419. (e) Nishimura, A.; Ohashi, M.;
Ogoshi, S. J. Am. Chem. Soc. 2012, 134, 15692. (f) Sakai, K.; Kochi,
T.; Kakiuchi, F. Org. Lett. 2013, 15, 1024.
(5) (a) Snider, B. B. J. Org. Chem. 1976, 41, 3061. (b) Snider, B. B.;
Brown, L. A.; Conn, R. S. E.; Killinger, T. A. Tetrahedron Lett. 1977,
18, 2831. (c) Clark, R. D.; Untch, K. G. J. Org. Chem. 1979, 44, 248.
(d) Snider, B. B.; Rodini, D. J.; Conn, R. S. E.; Sealfon, S. J. Am. Chem.
Soc. 1979, 101, 5283. (e) Fienemann, H.; Hoffmann, H. M. R. J. Org.
Chem. 1979, 44, 2802. (f) Rosenblum, M.; Scheck, D. Organometallics
1982, 1, 397. (g) Quendo, A.; Rousseau, G. Tetrahedron Lett. 1988, 29,
6443. (h) Faron, K. L.; Wulff, W. D. J. Am. Chem. Soc. 1988, 110, 8727.
(i) Ishihara, K.; Fushimi, M. J. Am. Chem. Soc. 2008, 130, 7532.
(6) For reviews, see: (a) Hosomi, A. Acc. Chem. Res. 1988, 21, 200.
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(b) Fleming, I.; Dunogues, J.; Smithers, R. Org. React. 1989, 37, 57.
(c) Fleming, I. Comprhensive Organic Synthesis, 2nd ed.; Elsevier: 1991;
Vol. 2, p 56310.1016/B978-0-08-052349-1.00041-X. (d) Miura, K.;
Hosomi, A. Allylsilanes, Allenylsilanes, and Propargylsilanes. In Main
Group Metals in Organic Synthesis; Yamamoto, H., Oshima, K., Eds.;
Wiley-VCH: Weinheim, 2006; pp 489−533.
In summary, we have developed an indium-catalyzed [2 + 2]
cycloaddition of allylsilanes and electron-deficient alkynes, which
would serve as an efficient method for the synthesis of cyclo-
butenones. The selectivity of the cycloaddition mode was switched
by changing the silyl substituents at the β-position of alkynones
and the catalyst. The usefulness of the present reaction was also
demonstrated by the geometry-selective thermal electrocyclic ring-
opening reaction of the cyclobutenones, as well as the oxidative
transformation of the silicon substituents.
(7) (a) Hojo, M.; Tomita, K.; Hirohara, Y.; Hosomi, A. Tetrahedron
Lett. 1993, 34, 8123. (b) Monti, H.; Audran, G.; Monti, J.-P.; Lea
́
ndri,
G. Synlett 1994, 1994, 403. (c) Monti, H.; Audran, G.; Leandri, G.;
́
Monti, J.-P. Tetrahedron Lett. 1994, 35, 3073. (d) Knolker, H.-J.;
̈
Baum, G.; Graf, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1612.
(e) Hojo, M.; Murakami, C.; Nakamura, S.; Hosomi, A. Chem. Lett.
1998, 331. (f) Inanaga, K.; Takasu, K.; Ihara, M. J. Am. Chem. Soc.
2005, 127, 3668. (g) Takasu, K.; Hosokawa, N.; Inanaga, K.; Ihara, M.
Tetrahedron Lett. 2006, 47, 6053.
(8) (a) Okamoto, K.; Tamura, E.; Ohe, K. Angew. Chem., Int. Ed.
2013, 52, 10639. (b) Okamoto, K.; Tamura, E.; Ohe, K. Angew. Chem.,
Int. Ed. 2014, 53, 10195.
ASSOCIATED CONTENT
* Supporting Information
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S
(9) We attempted further cycloaddition of cyclobutenone 3hb with
allylsilane 2a, but failed to obtain the desired product.
The Supporting Information is available free of charge on the
(10) In the reaction of terminal alkynone (R1 = H), complex
mixtures were obtained and the target cycloadduct was not detected.
(11) The reaction of alkynone 1a with less hindered allyltrimethylsi-
lane gave the [2 + 2] cycloadduct in low yield (6%).
Experimental procedures and compound characterization
(12) Simple alkenes such as styrene did not cause the cycloaddition
with alkynones under the present conditions.
(13) [3 + 2]-Cycloaddition of allylsilanes with enones: (a) Knolker,
H.-J.; Jones, P. G.; Pannek, J.-B. Synlett 1990, 1990, 429. (b) Knolker,
H.-J.; Foitzik, N.; Graf, R.; Pannek, J.-B. Tetrahedron 1993, 44, 9955.
AUTHOR INFORMATION
Corresponding Authors
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Notes
(c) Knolker, H.-J.; Foitzik, N.; Goesmann, H.; Graf, R.; Jones, P. G.;
̈
Wanzl, G. Chem. - Eur. J. 1997, 3, 538. (d) Knolker, H.-J. J. Prakt.
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Chem./Chem.-Ztg. 1997, 339, 304. For a review, see: (e) Schmidt, A.
The authors declare no competing financial interest.
W.; Knolker, H.-J. Synlett 2010, 2010, 2207.
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ACKNOWLEDGMENTS
This work was supported by JSPS KAKENHI (Grant-in-Aid for
Scientific Research (C); Grant Number 26410119).
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REFERENCES
■
(1) Anslyn, E. V.; Dougherty, D. A. Strain and Stability. Modern
Physical Organic Chemistry; University Science Books: Sausalito, CA,
2006; pp 65−144.
(2) For reviews on synthetic utilities of cyclobutenes, see:
(a) Namyslo, J. C.; Kaufmann, D. E. Chem. Rev. 2003, 103, 1485.
(b) Murakami, M.; Miyamoto, Y.; Hasegawa, M.; Usui, I.; Matsuda, T.
Pure Appl. Chem. 2006, 78, 415.
(3) (a) Pappas, S. P.; Pappas, B. C.; Portnoy, N. A. J. Org. Chem.
1969, 34, 520. (b) Serve, M. P.; Rosenberg, H. M. J. Org. Chem. 1970,
35, 1237. (c) Bloomfield, J. J.; Owsley, D. C. J. Am. Chem. Soc. 1971,
93, 782. (d) Koft, E. R.; Smith, A. B., III J. Am. Chem. Soc. 1984, 106,
2115. (e) Serebryakov, E. P. Bull. Acad. Sci. USSR, Div. Chem. Sci.
1984, 33, 120.
(4) (a) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49.
(b) Hilt, G.; Paul, A.; Treutwein, J. Org. Lett. 2010, 12, 1536.
(c) Lopez-Carrillo, V.; Echavarren, A. M. J. Am. Chem. Soc. 2010, 132,
́
C
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