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Hz, 1H), 3.69 (dd, J = 5.0 Hz, J = 12.5 Hz, 1H), 3.81 (td, J = 4.0 Electronic Supplementary Information (ESI) available: NMR, EPR and
Hz, J = 9.0 Hz, 1H), 3.86 (dd, J = 2.0 Hz, J = 12.5 Hz, 1H), XPS spectra. See DOI: 10.1039/b000000x/
1
3
DOI: 10.1039/C4NJ01784F
4
.31 (d, J = 19.0 Hz, 1H), 4.35 (d, J = 19.0 Hz, 1H); C NMR
90.6 MHz, CD3OD): δ = 43.80, 59.16, 62.74, 71.66, 75.09,
7.23, 79.47, 81.60, 205.30; (ESI+) m/z = 284.0847, calcd. for
(
1
2
3
4
J. Chen, S. K. Spear, J. G. Huddleston and R. D. Rogers, Green.
Chem., 2005, 7, 64–82.
7
+
-1
C9H15N3O6Na [M+Na] : 284.0853; IR: ν (cm ) = 3349, 2889,
F. E. Bailey Jr. and J. V. Koleske, In Poly(ethylene oxide), Academic
Press, N. York, 1976.
2
104, 1720.
-(1-(C-β-
triazole (9).
1
D
-glucopyranosyl)-2-oxo-propyl)-4-phenyl-1,2,3-
C. C.Tzschucke, C. Markert, W.Bannwarth, S.Roller, A.Hebel,
R.Haag, Angew. Chem. Int. Ed., 2002, 41, 3964-4000.
To a solution of the bromo C-glucoside 7 (0.34 to 0.45 mmol)
in PEG2000 (0.5 g/mmol) at 60 °C was added sodium azide (1.05
eq.) and the mixture was stirred at 60 °C for 1 h.
Phenylacetylene (1.05 eq), catalyst (CuI 5 mol%, Cu2O 5
mol%, CuNP 5 mol%; CuSO4 5 mol%/Na ascorbate 10 mol%;
or Cu turning (CuT) 500 mol%) and water (0.15 mL/mmol)
were added and the mixture was stirred at 60 °C. At reaction
time completion, the mixture was diluted with water (25 mL)
then filtered on PVDF membrane (20 mm, 0.45 µm). The
membrane was washed with water (25 mL) and the filtrate (50
mL) was subjected to ultrafiltration in an Amicon 8050 stirred
cell fitted with Ultracel Ultrafiltration Disk with a molecular
weight cut-off of 1 kDa under 3.5 bar pressure. After the first
ultrafiltration, the retentate (10 mL) was diluted with water (40
mL), and the solution was subjected to ultrafiltration again. The
filtrates were freeze-dryed and the residue was purified by flash
chromatography (AcOEt:MeOH 9.5:0.5 then 9:1) to give 9 as a
white solid (Yields: 93 % (CuI); 92 % (Cu2O); 97 % (CuNP);
(a) T. Okada, J. Chem. Soc., Chem. Commun., 1991, 1209-1210; (b)
R. D. Rogers, M. M. Benning, R. D. Etzenhouser, A. N. Rollins, J.
Coord. Chem., 1992, 26, 299-311; (c) R. D. Rogers, A. H. Bond, J. L.
Wolff, J. Coord. Chem., 1993, 29, 187-217; (d) R. D. Rogers, A. H.
Bond, S. Aguinaga, A. Reyes, J. Am. Chem. Soc., 1992, 114, 2967-
2977; (e) R. D. Rogers, M. L. Jezl, C. B. Bauer, Inorg. Chem., 1994,
33, 5682-5692; (f) R. D. Rogers, A. H. Bond, D. M. Roden, Inorg.
Chem., 1996, 35, 6964-6973; (g) T. Ohki, M. Harada, T. Okada, J.
Phys. Chem. B, 2007, 111, 7245-7252; (h) R. D. Rogers, J. Zhang, C.
B. Bauer, J. Alloys Comp. 1997, 249, 41-48.
5
6
E. Colacino, J. Martinez, F. Lamaty, L. S. Patrikeeva, L. L.
Khemchyan, V. P. Ananikov, and I. P. Beletskaya, Coord. Chem.
Rev., 2012, 256, 2893–2920.
(a) B. Sreedhar, P. S. Reddy, N. S. Kumar, Tetrahedron Lett., 2006,
47, 3055-3058; (b) G. Kumaraswamy, K. Ankamma, A. Pitchaiah, J.
Org. Chem. 2007, 72, 9822-9825; (c) D. Kumar, G. Patel, V. B.
Reddy, Synlett, 2009, 399-402; (d) D. Kumar, V. B. Reddy, R. S.
Varma, Tetrahedron Lett., 2009, 50, 2065-2068; (e) D. Kumar, V. B.
Reddy, Synthesis, 2010, 10, 1687-1691; (f) M. Keshavarz, R. Badri,
Mol. Divers., 2011, 15, 957-962; (g) D. Kumar, V. B. Reddy, A.
Kumar, D. Mandal, R. Tiwari, K. Parang, Biorg. Med. Chem. Lett.,
2011, 21, 449-452.
1
00% (CuSO4/Na ascorbate and 45% (CuT)).
24
1
Mp 130-132 °C; [α]D = -28.4 (c 1, MeOH); H NMR (360
MHz, D2O): δ = 2.92 (dd, J = 9.0 Hz, J = 16.0 Hz, 1H), 3.15
(
dd, J = 4.0 Hz, J = 16.0 Hz, 1H), 3.31 (t, J = 9.0 Hz, 1H), 3.38-
3
1
2
1
.47 (m, 2H), 3.51 (t, J = 8.5 Hz, 1H), 3.72 (dd, J = 5.0 Hz, J =
2.5 Hz, 1H), 3.86 (td, J = 4.0 Hz, J = 9.5 Hz, 1H), 3.89 (dd, J =
.0 Hz, J = 12.5 Hz, 1H), 5.58 (d, J = 19.0 Hz, 1H), 5.60 (d, J =
9.0 Hz, 1H), 7.37-7.45 (m, 1H), 7.45-7.53 (m, 2H), 7-73-7.80
7
8
(a) C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem., 2002,
67, 3057-3064; (b) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B.
Sharpless, Angew. Chem. Int. Ed., 2002, 41, 2596-2599.
(a) M. Meldal, C. W. Tornøe, Chem. Rev., 2008, 108, 2952-3015; (b)
L. Liang, D. Astruc, Coord. Chem. Rev., 2011, 255, 2933-2945; (c)
V. V. Fokin, K. Matyjaszewski, 2012; CuAAC: The Quintessential
13
(
m, 1H), 8.17 (s, 1H); C NMR (90.6 MHz, CD3OD): δ =
4
1
3
9.85, 60.28, 62.85, 71.75, 75.12, 77.40, 79.33, 81.75, 123.95,
26.63, 129.30, 129.93, 131.56, 148.72, 202.84; (ESI+) m/z =
Click Reaction, in Organic Chemistry
Perspectives (eds K. Ding and L.-X. Dai), Wiley-VCH Verlag GmbH
Co. KGaA, Weinheim, Germany.
doi: 10.1002/9783527664801.ch7.
- Breakthroughs and
+
86.1310, calcd. for C17H21N3O6Na [M+Na] : 386.1323; IR:
-1
ν (cm ) = 3313, 3128, 3096, 2923, 2887,1723, 1651, 1616,
64, 689.
Retentate was freeze-dried to recover PEG2000 as a solid (yields:
7 to 100%).
&
7
9
1
C. Boyer, J. Liu, V. Bulmus, T. P. Davis, C. Barner-Kowollik, M. H.
Stenzel, Macromolecules, 2008, 41, 5641-5650.
8
0 Z. P. Demko, K. B. Sharpless, Org. Lett., 2001, 3, 4091-4094.
Acknowledgements
11 (a) I. Jlalia, F. Meganem, J. Herscovici, C. Girard, Molecules, 2009,
14, 528-539; (b) B. S. Lee, M. Yi, S. Y. Chu, J. Y. Lee, H. R. Kwon,
K. R. Lee, D. Kang, W. S. Kim, H. B. Lim, J. Lee, H.-J. Youn, D. Y.
Chi, N. H. Hur, Chem. Commun., 2010, 46, 3935-3937.
We thank the Ministère de l’Enseignement Supérieur et de la
Recherche, the Centre National de la Recherche Scientifique
and the Université Paris-Sud for financial support. We are
grateful to Pascale Jegou and René Brennetot from CEA-Saclay 12 The 1,4-disubstitution pattern of the triazole ring in all compounds
for XPS and ICP-MS analysis, respectively.
was supported by the large and positive Δ(δC4 - δC5) value (17-21
1
3
ppm) in their C NMR spectra in agreement with previous
observations; see: (a) N. A. Rodios, J. Heterocycl. Chem., 1984, 21,
1169-1173; (b) B. Hoffmann, B. Bernet, A. Vasella, Helv. Chim.
Acta, 2002, 85, 265-287. (c) A. Dondoni, A. Marra, J. Org. Chem.,
Notes and references
*
Université Paris Sud, ICMMO, UMR CNRS 8182, Bâtiment 420, 91405
2
006, 71, 7546–7557.
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