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Experimental
General
All manipulations were carried out under a nitrogen at-
mosphere using standard Schlenk techniques. The chemicals
were purchased and used without purification. The complexes
[TpmXCu(NCMe)]BF4 and sulfonyl azides48 were prepared ac-
47
cording to literature procedure. H and 13C NMR spectra were
1
recorded on a 400 (1H)/100 (13C) MHz spectrometer. Chemical
shifts (d) are reported relatively to tetramethylsilane as internal
standard in ppm. Assignments of some 1H and 13C signals rely on
g-COSY and/or g-HSQC experiments. Elemental Analysis were
performed at Unidad de Ana´lisis Elemental of the Universidad de
Huelva.
26 M. Se´verac, L. L. Pleux, A. Scarpaci, E. Blart and F. Odobel,
Tetrahedron Lett., 2007, 48, 6518.
27 B. Gerard, J. Ryan, A. B. Beeler and J. A. Porco, Tetrahedron, 2006, 62,
6405.
General catalytic procedure for [3 + 2] cycloaddition of alkynes
and sulfonyl azides catalyzed by [Tpm*,BrCu(NCMe)]BF4
The catalyst (18.2 mg, 0.025 mmol, 5 mol%) and sulfonyl azide
(0.5 mmol) were dissolved in anhydrous chloroform (1 mL) in an
ampoule. The alkyne (0.6 mmol) was added to the solution under
a nitrogen atmosphere. The reaction mixture was stirred at a given
temperature (40 or 50 ◦C) for a given time (24–72 h) (see Scheme 3).
The reaction crude was diluted with dichloromethane and filtered
through a plug of silica to remove the copper catalyst. The solvent
was evaporated under reduce pressure and the residue was purified
by flash chromatography on silica gel with ethyl acetate to afford
the desired product.
28 W. G. Lewis, F. G. Magallon, V. V. Fokin and M. G. Finn, J. Am. Chem.
Soc., 2004, 126, 9152.
29 (a) F. Pe´rez-Balderas, M. Ortega-Mun˜oz, J. Morales-Sanfrutos, F.
Herna´ndez-Mateo, F. G. Calvo-Flores, J. A. Calvo-As´ın, J. Isac-Garc´ıa
and F. Santoyo-Gonza´lez, Org. Lett., 2003, 5, 1951; (b) K. Kamata, Y.
Nakagawa, Y. Zazuya and N. Mizuno, J. Am. Chem. Soc., 2008, 130,
15304.
30 S.-Q. Bai, L. L. Koh and T. S. A. Hor, Inorg. Chem., 2009, 48, 1207.
31 S. D´ıez-Gonza´lez and S. P. Nolan, Angew. Chem., Int. Ed., 2008, 47,
8881.
32 P. S. Donnelly, S. D. Zanatta, S. C. Zammit, J. M. White and S. J.
Williams, Chem. Commun., 2008, 2459.
33 N. Candelon, D. Laste´coure´s, A. K. Diallo, J. R. Aranzaes, D. Astruc
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34 S. D´ıez-Gonza´lez, A. Correa, L. Cavallo and S. P. Nolan, Chem.–Eur. J.,
2006, 12, 7558.
Acknowledgements
35 T. R. Chan, R. Hilgraf, K. B. Sharpless and V. V. Fokin, Org. Lett.,
2004, 6, 2853.
36 V. Aucagne, K. D. Ha¨nni, D. A. Leigh, P. J. Lusby and D. B. Walker,
J. Am. Chem. Soc., 2006, 128, 2186.
37 J. Raushel, S. M. Pitram and V. V. Fokin, Org. Lett., 2008, 10,
3385.
We thank the MEC (Proyecto CTQ2008-00042/BQU) and the
Junta de Andaluc´ıa (Proyecto P07-FQM-02745) for financial
support. IC thanks MEC for a research fellowship.
38 M. Whiting and V. V. Fokin, Angew. Chem., Int. Ed., 2006, 45, 3157.
39 M. P. Cassidy, J. Raushel and V. V. Fokin, Angew. Chem., Int. Ed., 2006,
45, 3154.
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538 | Org. Biomol. Chem., 2010, 8, 536–538
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