10.1002/ejoc.201701058
European Journal of Organic Chemistry
FULL PAPER
d, J = 8.5 Hz), 6.95 (2H, d, J = 8.5 Hz), 6.87 (2H, d, J = 8.5 Hz), 5.17-
5.06 (1H, m), 4.97 (1H, br s), 4.78 (2H, br s), 3.83 (3H, s), 3.79 (3H, s),
3.51-3.36 (2H, m), 3.03 (1H, dd, J = 11.1 and 3.2 Hz), 2.80-2.69 (1H, m),
2.34 (1H, br ddd, J = 14.2, 11.3 and 3.0 Hz), 2.09-1.39 (43H, br m); 3C
NMR (75 MHz, CDCl3): δ (ppm) = 170.9 (Cq), 168.5 (Cq), 168.3 (Cq),
167.3 (Cq), 160.6 (Cq), 159.3 (Cq), 130.5 (Cq), 130.0 (Cq), 129.9 (2CH),
129.3 (2CH), 114.6 (2CH), 114.5 (2CH), 84.9 (2CH), 79.3 (CH), 78.4
(2CH), 55.4 (CH3), 55.3 (CH3), 52.9 (2CH), 50.7 (CH), 45.8 (CH), 37.5
(CH2), 37.4 (CH2), 37.3 (CH2), 36.5 (2CH2), 36.4 (2CH2), 36.3 (CH2), 36.3
(CH2), 33.4 (CH2), 32.1 (CH), 32.0 (CH), 31.8 (4CH2), 31.8 (2CH), 31.7
(2CH), 31.7 (2CH2), 27.3 (2CH), 27.2 (CH), 27.1 (2CH), 26.9 (CH); IR
3051-3060. (e) F. De Nanteuil, F. De Simone, R. Frei, F. Benfatii, E.
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(neat) νmax
= 2908, 2856, 1776, 1724, 1612, 1514, 1452, 1346, 1254,
+
1155, 1099, 1038 cm-1; HRMS (ESI) m/z calcd for C54H66O10+NH4
:
892.4994 [M+NH4]+, found 892.4996.
Compound 10 (white crystals recrystallized in MeOH, 37 mg, 84%
yield): m.p. = 126 °C; Rf = 0.20 (petroleum ether/ EtOAc, 60/40); 1H
NMR (400 MHz, CDCl3): δ (ppm) = 7.45 (2H, d, J = 8.7 Hz), 7.02 (2H, d,
J = 8.7 Hz), 6.98 (2H, d, J = 8.7 Hz), 6.86 (2H, d, J = 8.7 Hz), 5.12-5.09
(1H, m), 4.79 (1H, br s), 3.84 (3H, s), 3.78 (3H, s), 3.70 (3H, s), 3.53 (3H,
s), 3.47-3.67 (2H, m), 3.06 (1H, dd, J = 10.4 and 4.2 Hz), 2.74 (1H, br
ddd, J = 11.2, 7.2 and 3.4 Hz), 2.27 (1H, ddd, J = 14.0, 10.4 and 3.4 Hz),
2.08-1.97 (2H, m), 1.94 (1H, ddd, J = 14.0, 11.7 and 4.2 Hz), 1.94-1.66
(10H, m), 1.61-1.48 (2H, m); 13C NMR (75 MHz, CDCl3): δ (ppm) = 170.9
(Cq), 169.4 (Cq), 169.3 (Cq), 167.3 (Cq), 160.6 (Cq), 159.3 (Cq), 130.5
(Cq), 130.1 (Cq), 129.9 (CH), 129.2 (CH), 114.6 (CH), 84.8 (CH), 79.3
(CH), 55.5 (CH3), 55.4 (CH3), 52.9 (CH), 52.7 (CH3), 52.6 (CH), 49.6 (CH)
46.0 (CH), 37.5 (CH2), 36.5 (CH2), 36.4 (CH2), 33.2 (CH2), 31.9 (CH2),
31.8 (CH2), 31.7 (2CH) 27.3 (CH), 27.0 (CH); IR (neat) νmax = 2910,
2856, 1776, 1729, 1612, 1585, 1513, 1436, 1346, 1301, 1247, 1153,
1101, 1033 cm-1; HRMS (ESI) m/z calcd for C36H42O10+NH4+: 652.3116
[M+NH4]+, found 652.3121.
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Procedure for the copper catalyzed version: To a stirred solution of
cyclopropane 1 (50 mg, 0.188 mmol, 1 equiv) in anhydrous 1,2-DCE (1
mL, c = 0.2M) were consecutively added TFA (5.7 µL, 0.075 mmol, 0.4
equiv) and Cu(OTf)2 (27.1 mg, 0.075 mmol, 0.4 equiv) at 20 °C. The
reaction mixture was stirred until completion as followed by TLC and then
quenched with the addition of water. The layers were partitioned. The
aqueous layer was extracted with diethyl ether twice. The combined
organic layers were dried over Na2SO4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography over silica gel
(petroleum ether/Et2O, 50/50) to give lactone 2, as a pale yellow oil (34
mg, 70% yield).
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Acknowledgements
[7]
The CNRS and Aix-Marseille Université are gratefully
acknowledged for financial support. The authors wish to thank
Michel Giorgi for X-Ray analysis.
Keywords: Donor-Acceptor cyclopropane, butyrolactone, 1,2-
zwitterion, DFT calculations.
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