The Journal of Organic Chemistry
NOTE
and (E)-1-iodohex-1-ene (1.5 equiv) for 5 h. Purification according to
P1 and flash chromatography (pentane/ether 150:1) yielded 8f (128 mg,
65%) as a yellow oil: 1H NMR (CDCl3, 600 MHz) δ (ppm) = 6.69À
6.65 (m, 1H), 6.32À6.29 (m, 1H), 2.23À2.19 (m, 2H), 1.48À1.43 (m,
according to TP4 for 1 h. Flash chromatography (pentane/ether 20:1)
yielded 9d (331 mg, 88%) as a yellow solid: H NMR (CDCl3, 400
1
MHz) δ (ppm) = 8.11À8.08 (m, 2H), 8.03À8.00 (m, 2H), 7.68À7.65
(m, 2H), 7.47À7.42 (m, 3H), 4.38 (q, J = 7.02 Hz, 2H), 1.39 (t, J = 7.12
Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ (ppm) = 166.1, 164.2, 149.0,
136.4, 134.5, 130.3, 130.1, 130.0, 130.0, 129.5, 127.9, 121.5, 61.0, 14.3;
IR (diamond-ATR, neat) ν~/cmÀ1 = 1705 (vs), 1607 (m), 1433 (s), 1364
(m), 1265 (vs), 1101 (vs), 1045 (s), 1028 (m), 1014 (m), 863 (m), 776
(s), 754 (vs), 701 (vs), 691 (vs), 660 (m); MS (EI, 70 eV) m/z (%) =
377 (45), 376 (M+, 100), 371 (48), 57 (33); HRMS (EI) calcd for
C18H14ClNO2S2 375.0154, found 375.0147 (M+); mp (°C) 87À88.
Synthesis of 10: Compound 10 was prepared according to TP5
from 8b (348 mg, 1 mmol). Flash chromatography (pentane/ether
10:1) yielded 10 (220 mg, 80%) as a colorless oil: 1H NMR (CDCl3, 300
MHz) δ (ppm) = 6.90 (t, J = 0.83 Hz, 1H), 6.27À6.26 (m, 1H), 5.61 (q,
J = 1.39 Hz, 1H), 4.16 (q, J = 7.10 Hz, 2H), 3.74À3.73 (m, 2H), 1.23 (t,
J = 7.05 Hz, 3H); 13C NMR (CDCl3, 75 MHz) δ (ppm) = 166.3, 154.4,
137.4, 135.1, 127.3, 118.6, 60.8, 33.9, 14.1; IR (diamond-ATR, neat) ν~/
cmÀ1 = 1698 (s), 1408 (m), 1264 (s), 1218 (s), 1126 (m), 1114 (s),
1054 (m), 1012 (s), 860 (m), 756 (vs), 698 (s), 664 (m); MS (EI, 70 eV)
m/z (%) = 275 (M+, 15), 231 (100), 229 (94), 203 (77), 97 (62);
HRMS (EI) calcd for C9H12BrNO2S 274.9616, found 274.9611 (M+).
Synthesis of 11: Compound 11 was prepared according to TP5
from 9a (414 mg, 1 mmol). Flash chromatography (pentane/ether
10:1) yielded 11 (273 mg, 85%) as a white solid: 1H NMR (CDCl3, 300
MHz) δ (ppm) = 8.09À8.05 (m, 2H), 7.95À7.91 (m, 2H), 7.71À7.65
(m, 2H), 7.47À7.65 (m, 4H), 4.38 (q, J = 7.21 Hz, 2H), 1.40 (t, J = 7.17
Hz, 3H); 13C NMR (CDCl3, 75 MHz) δ (ppm) = 167.3, 166.3, 154.9,
137.9, 134.3, 131.2, 130.1, 130.0, 129.9, 129.9, 126.1, 115.5, 61.0, 14.3;
IR (diamond-ATR, neat) ν~/cmÀ1 = 1698 (s), 1606 (m), 1428 (m), 1266
(vs), 1246 (s), 1198 (m), 1122 (m), 1106 (s), 1046 (s), 1022 (s), 1014
(s), 862 (m), 754 (s), 728 (vs), 710 (s), 692 (s), 664 (m); MS (EI, 70
eV) m/z (%) = 341 (M+, 100), 340 (49), 161 (20); HRMS (EI) calcd for
C18H15NO2S2 341.0544, found 341.0548 (M+); mp (°C) 124À125.
Synthesis of 12a: Compound 12a was prepared according to TP6
from 9c (370 mg, 1 mmol). Flash chromatography (pentane/ether 10:1)
yielded 12a (3.1 g, 92%) as a yellow oil: 1H NMR (DMSO, 400 MHz) δ
(ppm) = 7.91À7.89 (m, 2H), 7.70À7.68 (m, 2H), 7.64À7.60 (m, 1H),
7.55À7.47 (m, 5H); 13C NMR (DMSO, 100 MHz) δ (ppm) = 187.2,
170.2, 153.9, 136.2, 134.3, 133.3, 130.6, 130.3, 130.1, 129.3, 128.3, 82.1;
IR (diamond-ATR, neat) ν~/cmÀ1 = 1642 (m), 1415 (s), 1249 (m), 1179
(s), 1049 (s), 1030 (m), 1012 (m), 959 (m), 791 (m), 753 (s), 721 (s),
705 (s), 689 (vs), 678 (vs), 650 (s), 614 (s); MS (EI, 70 eV) m/z (%) =
423 (M+, 96), 296 (78), 128 (78), 127 (44), 109 (70), 77 (100); HRMS
(EI) calcd for C16H10INOS2 422.9248, found 422.9243 (M+).
2H), 1.39À1.33 (m, 2H), 0.91 (t, J = 7.18 Hz, 3H), 0.34 (s, 9H); 13
C
NMR (CDCl3, 150 MHz) δ (ppm) = 159.6, 138.7, 136.2, 131.1, 122.5,
32.5, 31.1, 22.2, 13.9, 0.2; IR (diamond-ATR, neat) ~ν/cmÀ1 = 1469 (m),
1418(m), 1003(s), 964 (m), 834(vs), 756 (m), 624(m);MS(EI, 70eV)
m/z (%) = 317 (M+ À 79Br, 32), 290 (91), 288 (75), 238 (52), 73 (100);
HRMS (EI) calcd for C12H20BrNSSi 317.0269, found 317.0266 (M+).
Synthesis of 8g: Compound 8g was prepared according to TP2
from 6c (236 mg, 1 mmol) [2 h]. Iodine (2 equiv) was added to 6cb at
25 °C and was stirred for 10 min. Purification according to P2 and flash
chromatography (pentane/ether 20:1) yielded 8g (169 mg, 60%) as a
white solid: 1H NMR (CDCl3, 400 MHz) δ (ppm) = 4.36 (q, J = 7.00
Hz, 2H), 1.37 (t, J = 7.05 Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ
(ppm) = 159.1, 142.8, 131.4, 101.1, 62.3, 14.1; IR (diamond-ATR, neat)
ν~/cmÀ1 = 1711 (vs), 1478 (m), 1466 (s), 1376 (s), 1250 (vs), 1181 (vs),
1120 (m), 1082 (vs), 1027 (vs), 831 (s), 806 (s), 754 (vs); MS (EI, 70
eV) m/z (%) = 363 (100), 361 (M+ - 79Br, 96), 335 (75), 333 (74), 318
(88), 316 (85); HRMS (EI) calcd for C6H5BrINO2S 360.8269, found
360.8257 (M+); mp (°C) 106À109.
Synthesis of 9a: Compound 9a was prepared according to TP2
from 7a (265 mg, 1 mmol) [8 h] and reaction with ethyl 4-iodobenzoate
according to TP4. Flashchromatography (pentane/ether 10:1) yielded9a
(372 mg, 91%) as a yellow solid: 1H NMR (CDCl3, 300 MHz) δ (ppm) =
8.09À8.05 (m, 2H), 7.70À7.64 (m, 3H), 7.63À7.61 (m, 1H), 7.44À7.39
(m, 3H), 4.37 (q, J = 7.00 Hz, 2H), 1.39 (t, J = 7.05 Hz, 3H), 0.14 (s, 9H);
13C NMR (CDCl3, 75 MHz) δ (ppm) = 169.6, 166.2, 161.2, 141.0, 134.1,
131.3, 130.5, 130.0, 129.7, 129.7, 129.2, 128.9, 60.9, 14.2, 0.6; IR
(diamond-ATR, neat) ~ν/cmÀ1 = 1716 (s), 1458 (m), 1408 (m), 1256
(s), 1124 (m), 1044 (m), 1016 (m), 994 (s), 830 (vs), 780 (m), 762 (s),
744 (s), 708 (s), 686(s), 660(m), 632(s);MS(EI, 70 eV) m/z (%) = 413
(M+, 100), 412 (28), 263 (21), 73 (20); HRMS (EI) calcd for
C21H23NO2S2Si 413.0939, found 413.0934 (M+); mp (°C) 69À71.
Synthesis of 9b: Compound 9b was prepared according to TP2
from 7a (265 mg, 1 mmol) [8 h] and reaction with Pd(PPh3)4 (2 mol %)
and benzoyl chloride (1.5 equiv) at 25 °C for 3 h. Purification according
to P1 and flash chromatography (pentane/ether 20:1) yielded 9b (288
mg, 72%) as a yellow oil: 1H NMR (CDCl3, 600 MHz) δ (ppm) = 8.15
(dd, J = 8.35 Hz, 2H), 7.70À7.67 (m, 2H), 7.56À7.53 (m, 1H),
7.47À7.43 (m, 1H), 0.32 (s, 9H); 13C NMR (CDCl3, 150 MHz) δ
(ppm) = 188.1, 168.8, 158.8, 145.9, 137.4, 134.4, 132.7, 131.1, 130.8,
129.9, 129.9, 128.0, À0.25; IR (diamond-ATR, neat) ν~/cmÀ1 = 1648
(m), 1406 (m), 1248 (m), 1214 (s), 1178 (m), 1000 (m), 836 (vs), 812
(s), 746 (s), 728 (s), 686 (vs), 658 (s), 642 (s), 622 (s); MS (EI, 70 eV)
m/z (%) = 369 (M+, 3), 355 (24), 354 (100), 145 (18); HRMS (EI)
calcd for C19H19NOS2Si 369.0677, found 369.0665 (M+).
Synthesis of 12b: Compound 12b was prepared according to TP6
from 9a (2.1 g, 5 mmol). Flash chromatography (pentane/ether 10:1)
yielded 12b (3.1 g, 92%) as a yellow solid: 1H NMR (DMSO, 400 MHz)
δ (ppm) = 8.05À8.02(m, 2H), 7.99À7.96 (m, 2H), 7.74À7.72 (m, 2H),
7.59À7.52 (m, 3H), 4.33 (q, J = 7.15 Hz, 2H), 1.32 (t, J = 7.12 Hz, 3H);
13C NMR (DMSO, 100 MHz) δ (ppm) = 170.6, 165.3, 155.9, 138.0,
134.4, 130.7, 130.4, 129.6, 129.4, 129.2, 128.6, 72.1, 60.9, 14.2; IR
(diamond-ATR, neat) ν~/cmÀ1 = 1694 (s), 1659 (m), 1461 (m), 1412
(m), 1387 (m), 1277 (vs), 1172 (m), 1096 (s), 1068 (m), 1039 (s), 1016
(s), 1004 (m), 838 (m), 774 (s), 755 (s), 710 (s), 696 (m), 688 (s); MS
(EI, 70 eV) m/z (%) = 467 (M+, 100), 205 (94), 160 (27); HRMS (EI)
calcd for C18H14INO2S2 466.9511, found 466.9507 (M+); mp (°C)
112À113.
Synthesis of 9c: Compound 9c was prepared according to TP2
from 7c (297 mg, 1 mmol) [2 h] and reaction with 1-iodo-4-methox-
ybenzene according to TP4 for 3 h. Flash chromatography (pentane/
ether 5:1) yielded 9c (324 mg, 80%) as a white solid: 1H NMR (DMSO,
400 MHz) δ (ppm) = 7.73À7.69 (m, 2H), 7.52À7.48 (m, 3H),
7.37À7.33 (m, 2H), 7.18À7.14 (m, 2H), 6.90À6.84 (m, 4H), 3.72 (s,
3H), 3.72 (s, 3H); 13C NMR (DMSO, 100 MHz) δ (ppm) = 161.9,
159.3, 158.9, 149.1, 133.6, 132.2, 130.6, 130.5, 130.1, 130.0, 129.6, 126.3,
122.8, 114.4, 113.7, 55.1, 55.0; IR (diamond-ATR, neat) ν~/cmÀ1 = 1605
(m), 1439 (m), 1290 (m), 1242 (vs), 1218 (m), 1180 (s), 1048 (s), 1031
(s), 1008 (s), 842 (s), 830 (s), 753 (s), 735 (m), 688 (s), 655 (s), 628
(s); MS (EI, 70 eV) m/z (%) = 405 (M+, 95), 299 (100), 298 (56), 149
(48); HRMS (EI) calcd for C23H19NO2S2 405.0857, found 405.0848
(M+); mp (°C) 100À102.
Synthesis of 13: Ni(acac)2 (2.5 mol %), DPEphos (5 mol %), and
(4-methoxyphenyl)zinc chloride (prepared by adding iPrMgCl LiCl
3
(1.5 mmol) to 1-iodo-4-methoxybenzene (1.5 equiv, 1.0 M in THF) at
25 °C and stirring for 1 h and further transmetalation with ZnCl2 (1
equiv)) were added to a solution of 7a (133 mg, 0.5 mmol) in THF
(0.5 mL) at 25 °C and stirred for 4 h. Purification according to P1 and
Synthesis of 9d: Compound 9d was prepared according to TP2
from 7d (297 mg, 1 mmol) [2 h] and reaction with ethyl 4-iodobenzoate
6977
dx.doi.org/10.1021/jo201250n |J. Org. Chem. 2011, 76, 6972–6978