Ruthenium-Catalyzed [2+2] Cycloadditions of Alkynyl Sulfides and
Alkynyl Sulfones
Nicole Riddell and William Tam*
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry,
UniVersity of Guelph, Guelph, Ontario N1G 2W1, Canada
ReceiVed NoVember 4, 2005
Ruthenium-catalyzed [2+2] cycloadditions of bicyclic alkenes with alkynyl sulfides and alkynyl sulfones
were investigated. The sulfide and sulfone moieties were found to be compatible with the Ru-catalyzed
cycloadditions, giving the corresponding cyclobutene cycloadducts in good yields. The sulfonyl-containing
cycloadducts can be transformed into a variety of products that are difficult to obtain via direct
cycloaddition.
Introduction
reactions have provided efficient methods for the construction
of 5-8-membered rings. We and others have studied various
aspects of transition-metal-catalyzed [2+2] cycloadditions of
an alkene and an alkyne for the synthesis of cyclobutenes,
including development of novel catalysts, study of the intramo-
lecular variant of the reaction, investigation of the chemo- and
We have studied various types of cycloaddition reactions of
bicyclic alkenes and are especially interested in those catalyzed
by transition metals.1,2 Transition-metal-catalyzed cycloadditions
have demonstrated their usefulness in the formation of rings
and complex molecules.3 The use of transition-metal catalysts
provides new opportunities for highly selective cycloaddition
reactions, because complexation of the metal to an unactivated
alkene, alkyne, or diene significantly modifies the reactivity of
this moiety, opening the way for enhanced reactivity and novel
reactions. Recent developments in transition-metal-catalyzed
[2+2+1],4 [4+2],5 [5+2],6 [4+4],7 and [6+2]8 cycloaddition
(4) For recent reviews on transition-metal-catalyzed [2+2+1] cycload-
ditions, see: (a) Pericas, M. A.; Balsells, J.; Castro, J.; Marchueta, I.;
Moyano, A.; Riera, A.; Vazquez, J.; Verdaguer, X. Pure Appl. Chem. 2002,
74, 167. (b) Sugihara, T.; Yamaguchi, M.; Nishizawa, M. Chem.sEur. J.
2001, 7, 1589. (c) Brummond, K. M.; Kent, J. L. Tetrahedron 2000, 56,
3263. (d) Buchwald, S. L.; Hicks, F. A. In ComprehensiVe Asymmetric
Catalysis I-III; Jabosen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-
Verlag: Berlin, 1999; Vol. 2, pp 491-510. (e) Keun Chung, Y. Coord.
Chem. ReV. 1999, 188, 297.
(1) For our recent contibutions on non-metal-catalyzed cycloaddition
reactions of bicyclic alkenes, see: (a) Yip, C.; Handerson, S.; Jordan, R.;
Tam, W. Org. Lett. 1999, 1, 791. (b) Tranmer, G. K.; Keech, P.; Tam, W.
Chem. Commun. 2000, 863. (c) Mayo, P.; Hecnar, T.; Tam, W. Tetrahedron
2001, 57, 5931. (d) Yip, C.; Handerson, S.; Tranmer, G. K.; Tam, W. J.
Org. Chem. 2001, 66, 276. (e) Tranmer, G. K.; Tam, W. J. Org. Chem.
2001, 66, 5113. (f) Tranmer, G. K.; Tam, W. Org. Lett. 2002, 4, 4101.
(2) For our recent contibutions on Ru-catalyzed [2+2] cycloadditions,
see: (a) Jordan, R. W.; Tam, W. Org. Lett. 2000, 2, 3031. (b) Jordan, R.
W.; Tam, W. Org. Lett. 2001, 3, 2367. (c) Jordan, R. W.; Tam, W.
Tetrahedron Lett. 2002, 43, 6051. (d) Villeneuve, K.; Jordan, R. W.; Tam,
W. Synlett 2003, 2123. (e) Villeneuve, K.; Tam, W. Angew. Chem., Int.
Ed. 2004, 43, 610. (f) Jordan, R. W.; Khoury, P. K.; Goddard, J. D.; Tam,
W. J. Org. Chem. 2004, 69, 8467. (g) Villeneuve, K.; Riddell, N.; Jordan,
R. W.; Tsui, G. C.; Tam, W. Org. Lett. 2004, 6, 4543. (h) Riddell, N.;
Villeneuve, K.; Tam, W. Org. Lett. 2005, 7, 3681.
(5) (a) Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432.
(b) Jolly, R. S.; Luedtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem.
Soc. 1990, 112, 4965. (c) Wender, P. A.; Jenkins, T. E.; Suzuki, S. J. Am.
Chem. Soc. 1995, 117, 1843. (d) O’Mahoney, D. J. R.; Belanger, D. B.;
Livinghouse, T. Synlett 1998, 443. (e) Murakami, M.; Ubukata, M.; Itami,
K.; Ito, Y. Angew. Chem., Int. Ed. 1998, 37, 2248. (f) Paik, S.-J.; Son, S.
U.; Chung, Y. K. Org. Lett. 1999, 1, 2045. (g) Hilt, G.; Smolko, K. I. Angew.
Chem., Int. Ed. 2003, 42, 2795. (h) Witulski, B.; Lumtscher, J.; Bergstra¨ber,
U. Synlett 2003, 708. (i) Hilt, G.; Lu¨ers, S.; Harms, K. J. Org. Chem. 2004,
69, 624.
(6) (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc.
1995, 117, 4720. (b) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc.
1998, 120, 10976. (c) Trost, B. M.; Shen, H. Angew. Chem., Int. Ed. 2001,
40, 2313. (d) Wender, P. A.; Williams, T. J. Angew. Chem., Int. Ed. 2002,
41, 4550.
(7) (a) Wender, P. A.; Ihle, N. C. J. Am. Chem. Soc. 1986, 108, 4678.
(b) Wender, P. A.; Nuss, J. M.; Smith, D. B.; Suarez-Sobrino, A.; Vagberg,
J.; Decosta, D.; Bordner, J. J. Org. Chem. 1997, 62, 4908.
(8) Wender, P. A.; Correa, A. G.; Sato, Y.; Sun, R. J. Am. Chem. Soc.
2000, 122, 7815.
(3) For reviews on transition-metal-catalyzed cycloadditions, see: (a)
Lautens, M.; Klute, W.; Tam, W. Chem. ReV. 1996, 96, 49. (b) Hegedus,
L. S. Coord. Chem. ReV. 1997, 161, 129. (c) Wender, P. A.; Love, J. A.
AdVances in Cycloaddition; JAI Press: Greenwich, 1999; Vol. 5, pp 1-45.
10.1021/jo052295a CCC: $33.50 © 2006 American Chemical Society
Published on Web 02/03/2006
1934
J. Org. Chem. 2006, 71, 1934-1937