G. Haberhauer and C. Tepper
Bruker Avance DMX 300 and Avance DRX 500 spectrometers. All
chemical shifts (d) are given in ppm relative to TMS. The spectra were
referenced to deuterated solvents indicated in brackets in the analytical
data. HRMS spectra were recorded using a Bruker BioTOF III instru-
ment. IR spectra were measured using a Varian 3100 FTIR Excalibur
Series spectrometer. UV/Vis absorption spectra were obtained using
Jasco J-815 and V-550 spectrophotometers. CD absorption spectra were
recorded using a Jasco J-815 spectrophotometer.
[1] V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines:
A Journey into the Nanoworld, Wiley-VCH, Weinheim, 2003.
[2] See the following literature: a) E. R. Kay, D. A. Leigh, F. Zerbetto,
72–191; b) Y. Shirai, J.-F. Morin, T. Sasaki, J. M. Guerrero, J. M.
C. Dietrich-Buchecker, P. GaviÇa, M. C. Jimenez-Molero, J. P. Sauv-
[3] For examples see: a) Z. Zhou, C. Cao, Z. Yin, Q. Liu, Org. Lett.
lecular Switches (Ed.: B. L. Feringa), Wiley-VCH, Weinheim, 2001.
[4] For examples see: a) M. M. Pollard, M. Klok, D. Pijper, B. L. Ferin-
17612–17613; c) S. P. Fletcher, F. Dumur, M. M. Pollard, B. L. Ferin-
[5] For examples see: a) F. Durola, J. Lux, J.-P. Sauvage, Chem. Eur. J.
Merino, Curr. Org. Chem. 2009, 13, 448–481; c) S. Silvi, M. Venturi,
Constable, C. E. Housecroft, J. E. Beves, E. L. Dunphy, M. Tomasu-
515; c) T. Muraoka, K. Kinbara, Y. Kobayashi, T. Aida, J. Am.
[7] For examples see: a) A. Martinez, V. Robert, H. Gornitzka, J.- P.
[8] a) S. Ernst, G. Haberhauer, Chem. Eur. J. 2009, 15, 13406–13416;
b) G. Haberhauer, C. Kallweit, Angew. Chem. 2010, 122, 2468–2471;
Angew. Chem. Int. Ed. 2010, 49, 2418–2421; c) G. Haberhauer,
[9] For examples see: a) G. Vives, H.-P. Jacquot de Rouville, A. Carelle,
b) U. Darbost, V. Penin, E. Jeanneau, C. Fꢅlix, F. Vocanson, C.
6776; c) K. A. McNitt, K. Parimal, A. I. Share, A. C. Fahrenbach,
E. H. Witlicki, M. Pink, D. K. Bediako, C. L. Plaisier, N. Le, L. P.
Redox switch 9: Compound 8 (27 mg, 0.02 mmol) was dissolved in ethyl
acetate (1 mL). HCl in ethyl acetate (5 mL) was added. The mixture was
stirred for four days at room temperature. The solution was poured into
an ethyl acetate/water mixture. The organic phase was separated, dried
over magnesium sulphate and the solvent was removed in vacuo. The res-
idue was purified by column chromatography over silica gel (CH2Cl2/
AcOEt: 75:25). The product was obtained as a yellow solid (20 mg,
100%). M.p.>2508C; 1H NMR (500 MHz, CDCl3, 258C): d=11.62 (s,
2H; HO-Ph), 7.64 (d, 4J
2.3 Hz, 2H; Har), 7.50 (d, 3J
Har; NH), 6.92–6.88 (m, 6H; Har), 6.86 (d, 3J
5.41 (d, 2J
(H,H)=16.1 Hz, 2H; CH2-Ph), 5.00–4.94 (m, 2H; NH-CH-
CO), 4.69 (d, 2J
(H,H)=16.2 Hz, 2H; CH2-Ph), 4.41–4.36 (m, 2H; NH-
CH-CH(CH3)2), 2.17–2.14 (m, 4H; CH(CH3)2), 2.03 (s, 6H; imidazole-
CH3), 1.17 (d, 3J (CH3)2), 1.12 (d, 3J
(H,H)=6.8 Hz, 12H; CH (H,H)=
6.8 Hz, 6H; CH (H,H)=6.7 Hz, 6H; CH(CH3)2);
(CH3)2), 0.93 ppm (d, 3J
A
ACHTUNGTRNE(NUNG H,H)=
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
13C NMR (125 MHz, CDCl3, 258C): d=201.9 (C=O), 171.7 (C=O), 163.1
(C=O), 162.2 (Car), 147.8 (Cimidazole), 137.9 (Car), 137.7 (Car), 134.7 (Car),
132.6 (Car), 131.8 (Car), 131.4 (Cimidazole), 130.3 (Cimidazole), 129.3 (Car), 127.4
(Car), 120.2 (Car), 118.9 (Car), 60.6 (CH-CH
47.7 (CH2-Ph), 35.0 (CH(CH3)2), 30.2 (CH
(CH(CH3)2), 19.41 (CH(CH3)2), 19.1 (CH(CH3)2), 10.2 ppm (imidazole-
CH3); IR (ATR): n˜ =3386, 2961, 2923, 2853, 1668, 1591, 1470, 1257 cmÀ1
A
ACHTUGNRTNE(NUNG CH3)2),
A
R
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
;
UV/Vis (CH2Cl2): lmax (loge)=250 (4.54), 359 nm (3.60); CD (CH2Cl2): l
(De)=226 (+0.6), 239 (+14.6), 256 (À32.2), 282 (+2.3), 327 (+3.0),
387 nm (À0.9 molÀ1 m3 cmÀ1); HRMS (ESI): m/z calcd for C56H62N8O8
[M+H]+: 975.4763; found 975.4806; [M+Na]+: 997.4583; found 997.4597.
Redox switch 10: Redox switch 9 (18 mg, 18.5 mmol) was dissolved in di-
chloromethane (3 mL). A mixture of bromine (3.5 mL, 65.6 mmol) in di-
chloromethane (2 mL) was added dropwise. The mixture was stirred for
18 h at room temperature. Afterwards, the reaction solution was poured
into a saturated sodium sulfite solution. The organic phase was separated,
dried over magnesium sulfate, and the solvent was removed in vacuo.
The product was obtained as a yellow solid (21 mg, 100%). M.p.>
2508C; 1H NMR (500 MHz, CDCl3, 258C): d=12.22 (s, 2H; OH-Ph),
7.88 (d, 4J
7.16 (d, 3J(H,H)=8.3 Hz, 2H; NH), 6.90 (d, 3J
6.84 (d, 4J(H,H)=2.2 Hz, 2H; Har), 6.78 (d, 3J
(H,H)=8.0 Hz, 2H; NH),
5.40 (d, 2J
(H,H)=16.2 Hz, 2H; CH2-Ph), 4.96–4.93 (m, 2H; NH-CH-
CO), 4.70 (d, 2J
(H,H)=16.3 Hz, 2H; CH2-Ph), 4.39–4.36 (m, 2H; NH-
CH-CH(CH3)2), 2.36–2.24 (m, 4H; CH(CH3)2), 2.01 (s, 6H; imidazole-
CH3), 1.16 (d, 3J (CH3)2), 1.11 (d, 3J
(H,H)=6.8 Hz, 12H; CH (H,H)=
6.8 Hz, 6H; CH (H,H)=6.7 Hz, 6H; CH(CH3)2);
(CH3)2), 0.92 ppm (d, 3J
A
ACHTUNGTREN(UNNG H,H)=8.3 Hz, 4H; Har),
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
13C NMR (125 MHz, CDCl3, 258C): d=201.3 (C=O), 171.7 (C=O), 163.2
(C=O), 158.9 (Car), 147.8 (Cimidazole), 138.5 (Car), 137.6 (Car), 137.0 (Car),
132.3 (Car), 131.1 (Car), 131.0 (Cimidazole), 130.4 (Cimidazole), 129.4 (Car), 127.5
(Car), 120.9 (Car), 112.9 (Car), 60.5 (CH-CH
47.6 (CH2-Ph), 34.9 (CH(CH3)2), 30.2 (CH
(CH(CH3)2), 19.1 (CH(CH3)2), 10.1 ppm (imidazole-CH3); IR (ATR): n˜ =
3396, 3058, 2963, 2932, 2873, 1668, 1593, 1498, 1434, 1338, 1239 cmÀ1
A
ACHTUGNRTNE(NUNG CH3)2),
A
R
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
;
UV/Vis (CH2Cl2): lmax (loge)=252 (5.19), 360 nm (4.33); HRMS (ESI):
m/z calcd for C56H60Br2N8O8 [M+H]+: 1133.2961; found 1133.3005.
Acknowledgements
[10] For examples, see: a) J. M. Spruell, W. F. Paxton, J.-C. Olsen, D. Be-
nꢆtez, E. Tkatchouk, C. L. Stern, A. Trabolsi, D. C. Friedman, W. A.
11580; b) M. A. Olson, A. B. Braunschweig, L. Fang, T. Ikeda, R.
This work was generously supported by the Deutsche Forschungsgemein-
schaft.
8064
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 8060 – 8065