4528
L. Severa et al. / Tetrahedron Letters 50 (2009) 4526–4528
Chan, T.-H. Comprehensive Organic Reactions in Aqueous Media; Wiley: Hoboken,
OH
TMS
OH
TMS
1
5 mol%
2007; (f) Li, C.-J. Chem. Rev. 2005, 102, 3095; (g) Rostovtsev, V. V.; Green, L. G.;
Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2596; (h) Link, A. J.;
Tirrell, D. A. J. Am. Chem. Soc. 2003, 125, 11164; (i) Lipshutz, B. H.; Ghorai, S.
Aldrichimica Acta 2008, 41, 59; (j) Villalobos, J. M.; Srogl, J.; Liebeskind, L. S. J.
Am. Chem. Soc. 2007, 129, 15734.
ð3Þ
2
N2
TMS
82%
1,4-dioxane, air
60 ºC, 6 h
32
33
34
3. (a) Streu, C.; Meggers, E. Angew. Chem., Int. Ed. 2006, 45, 5645; (b) Boren, B. C.;
Narayan, S.; Rasmussen, L. K.; Zhang, L.; Zhao, H.; Lin, Z.; Jia, G.; Fokin, V. V. J.
Am. Chem. Soc. 2008, 130, 8923; (c) Li, C.-J.; Wand, D.; Chen, D. J. Am. Chem. Soc.
1995, 117, 12867; (d) Li, C.-J. In Ruthenium Catalysts and Fine Chemistry;
Bruneau, C., Dixneuf, P. H., Eds.; Topics in Organometallic Chemistry; Springer:
Berlin, 2004; Vol. 11, p 321; e see also 1g.
We then focused on C–C bond forming air-tolerant ruthenium
catalysis devoid of Cp and Cp ligands. It has been shown by the
*
groups of Murahashi et al.16a and Echavarren and co-workers16b that
carbon pronucleophiles can be activated at room temperature by
[(PPh3)4RuH2] in MeCN. We observed that theMichael-type addition
leading to substituted malonate 36 was compatible with the
straightforward set-up of an open-flask experiment6 (Eq. 4, 91%
yield of 36, cf. 96% yield of 36 under anhydrous conditions with
exclusion of air16b). This transformation is postulated to proceed
viaa Ru(0) species,16 andthereforetheair-compatibility camerather
unexpectedly as both [(PPh3)4RuH2] and the Ru(0) catalyst [Ru(-
4. For
a note on oxygen-tolerance of ruthenium-catalyzed alkene-alkyne
coupling, see: (a) Trost, B. M.; Pinkerton, A. B.; Toste, F. D.; Sperrle, M. J. Am.
Chem. Soc. 2001, 123, 12504; For accounts on air-tolerant alkene metathesis,
see: (b) Lin, Y. A.; Chalker, J. M.; Floyd, N.; Bernardes, G. J.; Davis, B. G. J. Am.
Chem. Soc. 2008, 130, 9642; (c) Binder, J. B.; Blank, J. J.; Raines, R. T. Org. Lett.
2007, 9, 4885; (d) Lipshutz, B. H.; Ghorai, S.; Aguinaldo, G. T. Adv. Synth. Catal.
2008, 350, 953; (e) Foltynowicz, Z.; Pietraszuk, C.; Marciniec, B. Appl.
Organomet. Chem. 1993, 7, 539. For ruthenium-catalyzed oxidative coupling
of alkenes with arenes, see:; (f) Weissman, H.; Song, X.; Milstein, D. J. Am. Chem.
Soc. 2001, 123, 337; For ruthenium-catalyzed oxidative coupling of phenols
leading to biaryls in the presence of molecular oxygen, see: (g) Irie, R.;
Masutani, K.; Katsuki, T. Synlett 2000, 1433; (h) Yadav, J. S.; Reddy, B. V. S.;
Gayathri, K. U.; Prasad, A. R. New J. Chem. 2003, 27, 1684; (i) Matsushita, M.;
Kamata, K.; Yamaguchi, K.; Mizuno, N. J. Am. Chem. Soc. 2005, 127, 6632.
5. (a) Trost, B. M.; Indolese, A. F.; Müller, T. J. J.; Treptow, B. J. Am. Chem. Soc. 1995,
117, 615; (b) Trost, B. M.; Indolese, A. F. J. Am. Chem. Soc. 1993, 115, 4361; (c)
Dérien, S.; Jan, D.; Dixneuf, P. H. Tetrahedron 1996, 52, 5511; (d) Trost, B. M.;
Toste, F. D. Tetrahedron Lett. 1999, 40, 7739; (e) Trost, B. M.; Surivet, J. P. Angew.
Chem., Int. Ed. 2001, 40, 1468.
cod)(g
6-C8H10)] failed in our allylation study (Table 1, entries 9 and
10).
O
O
1.2 eq
MeO2C
MeO2C
MeO2C
ð4Þ
[(PPh3)4RuH2] 3 mol%
MeO2C
MeCN, air, r.t., 10 h
35
36
91%
6. See Supplementary data for experimental details.
7. For reviews, see: (a) Yamamoto, Y.; Itoh, K. In Ruthenium in Organic Synthesis;
In summary, drawing inspiration from mechanistic analogies
we found that air tolerance of transformations catalyzed by ruthe-
nium organometallics is not restricted to the rare appearances in
the literature. Notably diverse catalytic manifolds, mainly those
Murahashi, S.-I., Ed.; Wiley-VCH: Weinheim, 2004;
p 95; (b) Dérien, S.;
Monnier, F.; Dixneuf, P. H. Ruthenium Catalysts and Fine Chemistry. In Topics in
Organometallic Chemistry; Bruneau, C., Dixneuf, P. H., Eds.; Springer: Berlin,
2004; Vol. 11, p 1; For an overview of the versatility of the [Cp*Ru(cod)Cl]
catalyst, see: (c) Dérien, S.; Dixneuf, P. H. J. Organomet. Chem. 2004, 689, 1382.
8. (a) Zhang, L.; Chen, X. G.; Xue, P.; Sun, H. H. Y.; Williams, I. D.; Sharpless, K. B.;
Fokin, V. V.; Jia, G. J. Am. Chem. Soc. 2005, 127, 15998; (b) Rasmussen, L. K.;
Boren, B. C.; Fokin, V. V. Org. Lett. 2007, 9, 5337; (c) Majireck, M. M.; Weinreb, S.
M. J. Org. Chem. 2006, 71, 8680.
9. (a) Yamamoto, Y.; Arakawa, T.; Ogawa, R.; Itoh, K. J. Am. Chem. Soc. 2003, 125,
12143; (b) Yamamoto, Y.; Ogawa, R.; Itoh, K. Chem. Commun. 2000, 549; (c)
Kondo, T.; Kaneko, Y.; Tsunawaki, F.; Okada, T.; Shiotsuki, M.; Morisaki, Y.;
Mitsudo, T. Organometallics 2002, 21, 4564; (d) Yamamoto, Y.; Kitahara, H.;
Ogawa, R.; Kawaguchi, H.; Tatsumi, K.; Itoh, K. J. Am. Chem. Soc. 2000, 122,
4310; (e) Yamamoto, Y.; Kinpara, K.; Ogawa, R.; Nishiyama, H.; Itoh, K. Chem.
Eur. J. 2006, 12, 5618.
*
involving Cp Ru and CpRu fragments, remain supported under con-
ditions generally regarded as prohibitive. Indeed, we recently took
advantage of this air tolerance for the synthesis of the novel heli-
cene-viologen hybrid (helquat).17 Our study indicates that catalytic
*
pathways based on Cp Ru-derived species are potentially good
candidates for the unveiling of robust, air-tolerant processes which
will be of practical interest for organic chemistry.
Acknowledgments
10. For leading references on metal-catalyzed [2+2+2] cycloadditions, see: (a)
Vollhardt, K. P. C. Acc. Chem. Res. 1977, 10, 1; (b) Schore, N. E.. In Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1992;
Vol. 5, p 1129; (c) Kotha, S.; Brahmachary, E.; Lahiri, K. Eur. J. Org. Chem. 2005,
4741. and references cited therein; For rare examples of [2+2+2] cycloaddition
in the presence of O2, see: (d) Yokota, T.; Sakurai, Y.; Sakaguchi, S.; Ishii, Y.
Tetrahedron Lett. 1997, 38, 3923; (e) Ardizzoia, G. A.; Brenna, S.; LaMonica, G.;
Maspero, A.; Masciocchi, N. J. Organomet. Chem. 2002, 649, 173.
Support of this work by the IOCB under Grant No. Z4 055 0506
´
is gratefully acknowledged. We thank Dr. I. Stary, and Dr. D. Schrö-
ˇ
der for critical reading of the manuscript. We also thank Dr. I. Cer-
ˇ
vená and Mr. M. Hrebícek for their experimental help in the initial
ˇ
phase of this project, the group of Dr. J. Cvacka for mass spectra,
and Dr. P. Fiedler for IR spectra.
11. We note that processes 16+14?17 and 16+21?23 in DCE are not stopped in
the presence of strongly acidic or basic environments (i.e., 34 mM TFA, and
17 mM DBU, respectively).
Supplementary data
12. For C–C bond formation via p-allylruthenium intermediates, see: (a) Kondo, T.;
Mitsudo, T. In Ruthenium in Organic Synthesis; Murahashi, S.-I., Ed.; Wiley-VCH:
Weinheim, 2004; p 129; (b) Bruneau, C.; Renaud, J. L.; Demerseman, B. Chem.
Eur. J. 2006, 12, 5178; For seminal work on ruthenium-catalyzed allylations,
see: (c) Minami, I.; Shimizu, I.; Tsuji, J. J. Organomet. Chem. 1985, 296, 269; (d)
Zhang, S.-W.; Mitsudo, T.; Kondo, T.; Watanabe, Y. J. Organomet. Chem. 1993,
450, 197; (e) Trost, B. M.; Fraisse, P. L.; Ball, Z. T. Angew. Chem., Int. Ed. 2002, 41,
1059; For recent examples of air-stable CpRu catalysts for Carroll
rearrangements, see: (f) Constant, S.; Tortoioli, S.; Müller, J.; Lindner, D.;
Buron, F.; Lacour, J. Angew. Chem., Int. Ed. 2007, 46, 8979.
Supplementary data (detailed experimental procedures and
characterization data for all products) associated with this article
References and notes
13. Yamamoto, Y.; Nakagai, Y.; Itoh, K. Chem. Eur. J. 2004, 10, 231.
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A. M. J. Am. Chem. Soc. 1996, 118, 8553; c of note is the discussion of air stability
relating to isolated ruthenium complexes in 16a.
ˇ
17. Adriaenssens, L.; Severa, L.; Šálová, T.; Císarová, I.; Pohl, R.; Šaman, D.; Rocha, S.
ˇ
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