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Preparation of 2-Iodo Allylic Alcohols from 2-Butyn-1,4-diol

2008, The Journal of Organic Chemistry

Supporting Information for Preparation of 2-Iodo Allylic Alcohols from 2-Butyn-1,4-diol. Douglass F. Taber*, M. Inthikhab Sikkander, James F. Berry and Kevin J. Frankowski Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 E-mail: [email protected] Table of Contents S-1 Experimental Procedure S-6 1H-NMR for compound 2 S-7 13C-NMR for compound 2 S-8 nOe for compound 2 S-9 1H-NMR for compound 3b S-10 13C-NMR for compound 3b S-11 1H-NMR for compound 3a S-12 13C-NMR for compound 3a S-13 nOe for compound 3a S-14 1H-NMR for compound 3e S-15 13C-NMR for compound 3e S-16 1H-NMR for compound 3c S-17 13C-NMR for compound 3c S-18 1H-NMR for compound 3d S-19 13C-NMR for compound 3d S-20 1H-NMR for compound 4 S-21 13C-NMR for compound 4 S-1 S-22 1H-NMR for compound 5 S-23 13C-NMR for compound 5 S-24 1H-NMR for compound 6 S-25 13C-NMR for compound 6 S-26 1H-NMR for compound 7 S-27 13C-NMR for compound 7 S-28 1H-NMR for compound 8 S-29 13C-NMR for compound 8 S-30 1H-NMR for compound 9 S-31 13C-NMR for compound 9 S-32 1H-NMR for compound 10 S-33 13C-NMR for compound 10 S-34 nOe for compound 10 S-2 Experimental Procedure General Procedure: 1H-NMR and 13C-NMR measured at 400 MHz for 1H, 90 MHz and 100 MHz for 13 C in CDCl3.13C multiplicities were determined with the aid of a JVERT pulse sequence, differentiating the signals for methyl and methine carbons as "d", from methylene and quaternary carbon as "u". The infrared (IR) spectra were determined as neat oil. Mass spectra (MS) were obtained by electron impact (EI) or chemical ionization (CI). Rf values indicated refer to thin layer chromatography (TLC) on 2.5 x10 cm, 250 micron analytical plates coated with silica gel GF, developed in the solvent system indicated. Flash chromatography was performed using silica gel 60 (230-400 mesh). Solvents are referred as volume/volume mixtures. All air and moisture sensitive reactions were performed in oven dried glassware under a positive pressure of nitrogen. Cu powder was added to reactions employing diiodide 2 as the starting material in order to stabilize the diiodide. All solvents were purified immediately prior to use. Tetrahydrofuran (THF) and diethyl ether (Et2O) were distilled from sodium metal/benzophenone under nitrogen. Dichloromethane, toluene and methanol were distilled from CaH2 under nitrogen. All reaction mixtures were stirred magnetically under nitrogen atmosphere. MTBE is t-butyl methyl ether, PE is petroleum ether, TMSCl is chlorotrimethylsilane. (2Z)-2-Iodo-2-penten-1-ol (3b) (Method A). (Yellow oil, 73 mg, 53% yield). TLC Rf = 0.83 (MTBE/PE, 50:50); 1H-NMR δ 5.88 (t, 1H, J = 7.2 Hz), 4.24 (d, 2H, J = 6.0 Hz), 2.17 (quint, 2H, J = 7.2 Hz), 1.95 (bs, 1H), 1.02 (t, 3H, J = 7.2 Hz); 13C-NMR δ u 107.4, 71.6, 29.2; d 137.3, 12.7; IR (film): 3320, 2965, 1642, 1457, 1090 cm-1; MS: 212(100), S-3 183(9), 127(16), 94(4), 85(16), 67(60); HRMS Calcd for C5H9OI (M+): 211.9694, Obsd: 211.9694. (2Z)-2-Iodohexa-2, 5-dien-1-ol (3c) (MethodA). (Yellow oil, 106 mg, 30%). TLC Rf = 0.48 (MTBE/PE, 30:70); 1H-NMR δ 5.94 (t, 1H, J = 7.2 Hz), 5.80 (m, 1H), 5.12 (dq, 1H, J = 17.2 Hz, J = 1.6 Hz), 5.07 (dq, 1H, J = 10 Hz, J = 1.6 Hz), 4.27 (d, 2H, J = 7.2 Hz), 2.94 (t, 2H, J = 6.8 Hz), 1.93 (t, 1H, J = 6.8 Hz); 13C-NMR δ u 116.2, 109.2, 71.6, 39.9; d 134.0, 133.4; IR (film): 3331, 1637, 1425, 1078 cm-1; MS: 224(54), 170(12), 127(21), 97(15), 79(100); HRMS Calcd for C6H9OI (M+): 223.9698, Obsd: 223.9699. (2Z)-2-Iodo-2-octen-1-ol (3e) (Method A). (Yellow oil, 132 mg, 51%). TLC Rf = 0.55 (MTBE/PE, 30:70), 1H-NMR δ 5.80 (t, 1H, J = 6.8 Hz), 4.23 (s, 2H), 2.13 (q, 2H, J = 7.2 Hz), 2.19 (bs, 1H), 1.41 (quint, 2H, J = 7.2 Hz), 1.30 (m, 4H), 0.88 (t, 3H, J = 6.0 Hz); 13 C-NMR δ u 107.9, 71.6, 35.5, 31.3, 27.8, 22.5; d 136.5, 13.9; IR (film): 3311, 2955, 1643, 1457, 1377, 1222 cm-1; MS: 254(33), 184(26), 57(100), 124(15), 109(43), 95(33), 81(40), 67(68); HRMS Calcd for C8H15OI (M+): 254.0168, Obsd: 254.0160. (Z)-2-Iodo-4-(4-methoxyphenoxy)-2-buten-1-ol (5). (Clear oil, 118 mg, 60%). TLC Rf = 0.29 (MTBE/PE, 15:85); 1H-NMR δ 6.83 (s, 4H), 6.33 (tt, 1H, J = 5.2 Hz, J = 1.2 Hz), 4.58 (dt, 2H, J = 5.2 Hz, J = 1.6 Hz), 4.25 (d, 2H, J = 1.6 Hz), 3.76 (s, 3H), 2.51 (s, 1H); 13 C-NMR δ u 154.1, 152.2, 108.6, 72.2, 71.1; d 131.4, 115.7, 114.7, 55.7; IR (film): 3376, 1649, 1511, 1035, 809 cm-1; MS: 338(59), 210(35), 194(37), 177(87), 139(100), 124(98); HRMS Calcd for C11H17NO3I (M+NH4): 338.0253, Obsd: 338.0250. (Z)-2-Iodo-4-(2-methoxyphenylamino)-2-buten-1-ol (6): (Light brown oil, 136 mg, S-4 68% yield). TLC Rf = 0.25 (MTBE/PE, 15:85); 1H-NMR (d6-Acetone) δ 6.79 (dd, 1H, J = 8 Hz, J = 1.2 Hz), 6.77 (td, 1H, J = 7.6 Hz, J = 1.2 Hz), 6.58 (td, 1H, J = 7.6 Hz, J = 1.6 Hz), 6.52 (dd, 1H, J = 8 Hz, J = 1.2 Hz), 6.14 (tt, 1H, J = 5.6 Hz, J = 2 Hz), 4.92 (bt, 1H, J = 6.8 Hz), 4.60 (t, 1H, J = 6 Hz), 4.20 (dq, 2H, J = 6.4 Hz, J = 1.6 Hz), 3.89 (dt, 2H, J = 6 Hz, J = 1.2 Hz), 3.80 (s, 3H); 13C-NMR (d6-Acetone) δ u 147.9, 138.9, 109.9, 71.4, 49.6; d 133.2, 122.0, 117.2, 110.7, 110.5, 55.8; IR (film): 3406, 1643, 1455, 1248, 1128 cm-1; MS: 320(M+H, 100), 319(29), 194(14), 192(33), 174(25), 123(24); HRMS Calcd for C11H14NO2I (M+): 319.0069, Obsd: 319.0056. (Z)-4-Azido-2-iodo-2-buten-1-ol (7). (Yellow oil, 130 mg, 88% yield). TLC Rf = 0.47 (MTBE/PE, 15:85), 1H-NMR δ 6.15 (tt, 1H, J = 6.4 Hz, J = 1.6 Hz), 4.30 (d, 2H, J = 1.2 Hz), 3.96 (d, 2H, J = 6.4 Hz), 2.24 (s, 1H); 13C-NMR δ u 112.0, 71.0, 55.1; d 128.5; IR (film): 3348, 2101, 1646, 1443, 1251 cm-1; MS: 239(11), 211(100), 210(26), 179(25), 155(14), 127(13); HRMS Calcd for C4H6N3OI (M+): 238.9556, Obsd: 238.9545. S-5 S-6 S-7 S-8 S-9 S-10 S-11 S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 S-23 S-24 S-25 S-26 S-27 S-28 S-29 S-30 S-31 S-32 S-33 S-34