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34447544528
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I- catalyst precursors.
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I- catalyst precursors.
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37
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34447527731
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6 (30 mol%) was degassed and stirred at r.t. in 14% aq dioxane or in the corresponding alcohol (1.75 mL solvent/mmol of 1). The mixture was filtered through a short pad of Florisil® or silica gel (cyclohexane-EtOAc, 50:50) and the solvents were evaporated under reduced pressure. The crude product was purified if necessary by silica gel flash chromatography (cyclohexane-EtOAc, 90:10) to give the corresponding alcohol or ether.
-
6 (30 mol%) was degassed and stirred at r.t. in 14% aq dioxane or in the corresponding alcohol (1.75 mL solvent/mmol of 1). The mixture was filtered through a short pad of Florisil® or silica gel (cyclohexane-EtOAc, 50:50) and the solvents were evaporated under reduced pressure. The crude product was purified if necessary by silica gel flash chromatography (cyclohexane-EtOAc, 90:10) to give the corresponding alcohol or ether.
-
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38
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34447506534
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Dimethyl 4-(1-Ethoxyphenylmethyl)-3-methylenecyclopentane-1,1- dicarboxylate (2h) Rf, 0.51 (cyclohexane-EtOAc, 80:20, 1H NMR (300 MHz, CDCl3, δ, 1.13 (t, J, 7.0 Hz, 3 H, 2.31-2.44 (m, 2 H, 2.84-3.00 (m, 3 H, 3.24-3.45 (m, 2 H, 3.68 (s, 3 H, 3.74 (s, 3 H, 4.25 (d, J, 6.0 Hz, 1 H, 4.48 (br s, 1 H, 4.91 (br s, 1 H, 7.25-7.34 (m, 5 H, 13C NMR (300 MHz, CDCl3, δ, 15.2 (CH3, 35.4 (CH2, 42.1 (CH2, 49.4 (CH, 52.6 (2 CH3, 58.7 (C, 64.6 (CH2, 83.7 (CH, 108.5 (CH2, 127.2 (2 CH ar, 127.4 (CH ar, 128.1 (2 CH ar, 141.4 (C, 148.6 (C, 172.1 (C, 172.2 (C, MS (DCI/NH3, m/z, 350 [M, NH4, 333 [M, H, HRMS (DCI/CH4, m/z calcd for C19H25O3: 333.1702; found: 333.1703. 3-(1-Ethoxymethylethyl)-4-methylene-N
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2: 478.1722; found: 478.1715.
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39
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33747175365
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Nieto-Oberhuber, C.; Lopez, S.; Jimenez-Nunez, E.; Echavarren, A. M. Chem. Eur. J. 2006, 12, 5916.
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Nieto-Oberhuber, C.1
Lopez, S.2
Jimenez-Nunez, E.3
Echavarren, A.M.4
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40
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34447500530
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Dimethyl 3-Hydroxy-4-methyl-5-methylenecyclohexane-1,1-dicarboxylate (31H) Rf, 0.13 (cyclohexane-EtOAc, 80:20. 1H NMR (300 MHz, CDCl3, δ, 1.14 (d, J, 6.7 Hz, 3 H, 1.81 (dd, J, 13.3, 9.8 Hz, 1 H, 1.95-2.10 (m, 2 H, 2.53-2.61 (m, 2 H, 2.86 (dd, J, 13.6, 9.8 Hz, 1 H, 3.30-3.50 (m, 1 H, 3.47 (s, 3 H, 3.70 (s, 3 H, 4.82 (br s, 1 H, 4.88 (br s, 1 H, 13C NMR (300 MHz, CDCl3, δ, 14.0 (CH3, 38.6 (CH2, 39.7 (CH2, 44.6 (CH, 52.5 (CH3, 52.9 (CH3, 55.9 (C, 73.0 (CH, 111.4 (CH2, 145.0 (C, 170.7 (C, 171.6 (C, MS (DCI/NH3, m/z, 260 [M, NH 4, 243 [M, H, 228 [M, MeOH, NH 4, 211 [M, MeOH, H, HRMS DCI/CH 4, m/z calcd for C12H19O5: 243.1232; found: 24
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+.
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41
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0348047259
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