The Journal of Organic Chemistry
Article
(
(
KBr) (Figure S13, Supporting Information) 2957 (w), 1755 (s), 1358
m), 1339 (m), 1230 (s), 1035 (s), 898 (w), 810 (w), 712 (w) cm ;
Chem. 2010, 18, 922−929. (c) Meenakshisundaram, G.; Eteshola, E.;
Blank, A.; Lee, S. C.; Kuppusamy, P. Biosens. Bioelectron. 2010, 25,
2283−2289. (d) Takeshita, K.; Okazaki, S.; Kansui, H. Chem. Pharm.
Bull. 2011, 59, 624−628.
−1
UV−vis (CHCl ) λ (ε) 384 (38 600), 503 (1000), 562 (1160) nm;
ESIHRMS calcd for C H O Cl (M) 1358.7391, found
3
max
+
4
5
35 18 14
1
358.7403.
Bis(2,3,4,5,6-pentachlorophenyl)[2,3,5,6-tetrachloro-4-
2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-
(3) Torres, J. L.; Varela, B.; Brillas, E.; Julia,
74−75.
4) Torres, J. L.; Carreras, A.; Jimen
Rius, J.; Julia,
5) (a) Jimen
583−4586. (b) Tourin
C.; Lizarraga, D.; Cascante, M.; Torres, J. L. J. Agric. Food Chem. 2005,
53, 4728−4735. (c) Lozano, C.; Torres, J. L.; Julia, L.; Jimenez, A.;
Centelles, J. J.; Cascante, M. FEBS Lett. 2005, 579, 4219−4225.
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Cascante, M.; Torres, J. L. FEBS J. 2006, 273, 2475−2486.
e) Tourino, S.; Lizarraga, D.; Carreras, A.; Lorenzo, S.; Ugartondo,
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Chem. Res. Toxicol. 2008, 21, 696−704. (f) Tourino, S.; Lizarraga, D.;
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Zhou, B. Chem.Eur. J. 2010, 16, 12808−12813.
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290−4302.
8) Mesa, J. A.; Velaz
Julia, L. Tetrahedron 2011, 67, 3119−3123.
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41, 1266−1281.
10) Jensen, K. J. J. Chem. Soc., Perkin Trans. 1 2002, 2219−2233.
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Lett. 1994, 35, 6529−6532.
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(13) Armet, O.; Veciana, J.; Rovira, C.; Riera, J.; Castan
́
L. Chem. Commun. 2003,
[
(
́
ez, A.; Brillas, E.; Torrelles, X.;
acetyl-β-D-glucopyranosyloxy]phenyl]methane (2H). To a sol-
ution of 2 (0.60 g; 0.37 mmol) in THF/water (10:1 v/v, 20 mL) was
added ascorbic acid (1.30 g, 7.40 mmol). The reaction mixture was
stirred at room temperature (3 h) and then evaporated at reduced
pressure. The residue in CH Cl was washed with water, dried with
anhydrous MgSO , and filtered and the solvent evaporated under
reduce pressure. The residue was chromatographed in silica gel with
́
L. J. Org. Chem. 2007, 72, 3750−3756.
ez, A.; Selga, A.; Torres, J. L.; Julia, L. Org. Lett. 2004, 6,
o, S.; Selga, A.; Jimenez, A.; Julia, L.; Lozano,
(
́
́
4
̃
́
́
́
2
2
́
́
4
(
́
́
̃
hexane−ethyl acetate mixture (2:1 v/v) as eluent to give 2H (0.59 g;
9
1
1
(
(
8%): R = 0.63; IR (KBr) 2993−2952, 1756.4, 1368.9, 1339.1, 1229.2,
f
(
̃
́
−1 1
034.9 cm ; H NMR (400 MHz, CDCl ) δ 1.94 s (2), 1.96 s (4),
3
́
.97 s (2), 1.98 s (1), 1.99 s (1), 2.01 s (1), 2.03 s (2), 2.04 s (1)
̃
́
CH CO); 3.65 m (0.55H, H-5A); 3.70 m (0.45H, H-5B); 3.93 m
3
1H, H-5′); 4.049, 4.054 dd (J6′A‑6′B,6′A‑5′ = 12.5, 2.6 Hz, 1H, H-6′A);
́
4
6
4
.07−4.15 m (1.57H, H-4B, H-6A , H-4A); 4.19−4.28 m (1.41H, H-
A
B , H-6′A); 4.38 dd (J
A
= 12.0, 2.8 Hz, 0.41H, H-6B );
6BB‑6BA,6BB‑5B
B
(
.50 dd (J6AB‑6AA,6AB‑5A = 12.2, 2.7 Hz, 0.50H, H-6A ); 4.85 dd (J2′‑3′,2′‑1′
B
=
10.6, 4.0 Hz, 1H, H-2′); 5.04, 5.05 dd, (J4′‑3′,4′‑5′ = 9.9, 9.9 Hz, 1H, H-
′); 5.24, 5.25 dd (J2−3,2−1 = 9.2, 7.6 Hz, 1H, H-2); 5.30−5.37 m
2.41H, H-3, H-3′, H-1B); 5.38 d (J1A‑2 = 7.5, 0.52H, H-1A); 5.42 d
J1′B‑2′ = 4.0, 0.46H, H-1′B); 5.44 d (J = 4.0, 0.53H, H-1′A); 6.975,
(
4
4
(
(
(
́
quez-Palenzuela, A.; Brillas, E.; Torres, J. L.;
1′A‑2′
́
6
2
(
9
1
.978 s (0.54, 0.46H, α-H); 13C NMR (100 MHz, CDCl ) 20.59−
3
(
0.31 (CH CO), 56.56 (αH), 61.5 (C-6), 61.7 (C-6′), 68.0 (C-4), 68.6
3
3
(
C-5), 69.3 C-3), 72.7 (C-5′), 72.8 (C-4′), 75.1 (C-3′), 77.4 (C-2),
5.6, 95.7 (C-1′), 99.7, 102.0 (C-1), 129.5 (C-1ArO), 133.3 (C-1Ar),
(
́
68.7 (C-4ArO) 169.7−170.4 (CH -CO)
3
(
̃
er, J.; Rodríguez, A.; Rovira, C.;
er, J.; Molins,
ASSOCIATED CONTENT
■
*
S
Supporting Information
̃
Infrared and EPR spectra and cyclic voltammograms for
E.; Rius, J.; Miravitlles, C.; Olivella, S.; Brichfeus, J. J. Phys. Chem.
1987, 91, 5608−5616.
1
radicals 1 and 2. H and HSQC NMR spectra of diamagnetic
(
14) Ballester, M.; Riera, J.; Castan
Am. Chem. Soc. 1971, 93, 2215−2225.
15) The spectrum was simulated following the WINSIM by: Dulog,
̃
́
er, J.; Badía, C.; Monso, J. M. J.
compounds 1H and 2H. Graphics for kinetics of radical 2 with
(
D. Public EPR Software Tools; National Institute of Environmental
Health Sciences: Bethesda, MD, 1996.
AUTHOR INFORMATION
■
NOTE ADDED AFTER ASAP PUBLICATION
■
*
Scheme 2 was published with errors on January 4, 2012; it was
corrected in the version reposted on January 6, 2012.
ACKNOWLEDGMENTS
■
Financial support for this research from the MCI (Spain)
through projects AGL2009-12374-C03-03/ALI and CTQ2009-
3797 is gratefully acknowledged. J.A.M. gratefully acknowl-
1
edges the Spanish Foreign Office Department for a predoctoral
grant (AECI). We also thank the EPR service of the Institute
for Advanced Chemistry of Catalonia-CSIC (Spain) for
recording the EPR spectra and the scientific-technical services
of the University of Barcelona for recording the mass spectra.
REFERENCES
■
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