S.L. Gaonkar, H. Shimizu / Tetrahedron 66 (2010) 3314–3317
3317
Mp 197–198 ꢀC (lit.1 mp 196–198 ꢀC); 1H NMR (d6-DMSO):
(Standard) to SLG. This research was supported by JSPS KAKENHI
d
3.04 (s, 3H, NCH3), 3.92 (2H, t, J¼5.7 Hz, CH2CH2), 4.23 (2H, t,
(20$08620), Grant-in-Aid for JSPS Fellows.
J¼5.7 Hz, CH2CH2), 6.56 (1H, m, ArH), 6.63 (1H, d, J¼8.4 Hz, ArH),
7.12 (2H, d, J¼8.4 Hz, ArH), 7.49–7.55 (3H, m, ArH), 7.82 (1H, s,
C6H4CH]C), 8.09 (1H, d, J¼4.8 Hz, ArH), 12.46 (1H, br s, NH, ex-
References and notes
changes with D2O); 13C NMR (DMSO-d6):
d 37.0, 48.3, 65.7, 105.7,
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111.5, 115.3, 120.3, 125.5, 131.7, 132.0, 137.2, 147.4, 157.9, 160.1, 167.4,
167.9; Anal. Calcd for C18H17N3O3S: C, 60.83; H, 4.82; N, 11.82%.
Found: C, 60.72; H, 4.80; N, 11.75%.
4.6. 5-{4-[2-(Methyl-pyridin-2-ylamino)ethoxy]benzyl}-
thiazolidine-2,4-dione; rosiglitazone (3)1
To a stirred suspension of alkene 11 (495 mg, 1.39 mmol) in
methanol (10 mL) were added magnesium turnings (20 mg) and
a pinch of iodine at rt, and the mixture was stirred and warmed to
initiate the reaction. Magnesium (50 mg) was added portion wise
for 30 min. On completion of the addition, the reaction mixture was
stirred for 3 h at rt and quenched on ice water (10 mL). The pH was
adjusted to 7.0–7.5 using 1 M hydrochloric acid and the mixture
was extracted with dichloromethane (10 ml) twice. The combined
organic extracts were washed with water (10 mL), dried over anhyd
Na2SO4 and concentrated in vacuo. The residue was crystallized
from boiling methanol to give 3 (470 mg, 95%) as a white solid.
Mp 154–155 ꢀC (lit.1 mp 153–155 ꢀC); 1H NMR (DMSO-d6):
d
3.05 (1H, dd, J¼9.2, 14.0 Hz, C6H4CH2CH), 3.09 (3H, s, NCH3), 3.28
(1H, dd, J¼3.6, and 14.0 Hz, C6H4CH2CH), 3.92 (2H, t, J¼5.6 Hz,
CH2CH2), 4.20 (2H, t, J¼5.6 Hz, CH2CH2), 4.88 (1H, dd, J¼4.2, 9.2 Hz,
C6H4CH2CH), 6.55–6.80 (2H, m, ArH), 6.85 (2H, d, J¼8.4 Hz, ArH),
7.18 (2H, d, J¼8.4 Hz, ArH), 7.49 (1H, m, ArH), 8.05 (1H, d, J¼4.8 Hz,
ArH), 12.05 (1H, br s, NH, exchanges with D2O); 13C NMR (DMSO-
d6): 37.1, 37.2, 48.9, 53.1, 65.5, 105.3, 111.1, 114.0, 127.2, 129.7, 136.8,
146.9, 157.5, 157.6, 170.6, 174.4; Anal. Calcd for C18H19N3O3S: C,
60.49; H, 5.36; N, 11.57%. Found: C, 60.40; H, 5.29; N, 11.50%.
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Acknowledgements
The authors thank the JSPS (Japan Society for the Promotion of
Science) for Postdoctoral Fellowships for Foreign Researchers