9
0.42 in 3% MeOH in CH Cl , KMnO stain; IR (neat, cm–1) 3168,
HRMS (EI+) m/z calc'd for C H BrO [M]+: 287.9997, found
11 13 4
288.001.
ACCEPTED MANUSCRIPT
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2956, 2791, 2670, 2601, 1595, 1497, 1478, 1446, 1408, 1306,
1244, 1148, 1120, 1049, 1035, 981, 884, 847, 804, 756, 706, 657,
638; δH (500 MHz, CDCl3) 7.17 (d, J = 8.6 Hz, 1H), 6.54 (d, J =
2.8 Hz, 1H), 6.42 (dd, J = 8.6, 2.8 Hz, 1H), 5.91 (br. s, 1H), 2.75
(s, 6H); δC (126 MHz, CDCl3) 155.2, 151.0, 131.1, 119.3, 110.3,
107.6, 43.6; HRMS (EI+) m/z calc'd for C8H10ClNO [M+H]+:
172.0526, found 172.0529.
5.2.12. 2-Bromo-5-hydroxyphenyl pivalate (3g). 191 mg, 70%
and 197 mg, 72%; White solid, mp 71–72 °C. Purified by flash
chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.42 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3394, 2977, 2932, 1727, 1609, 1583, 1494, 1472, 1454,
1420, 1393, 1369, 1340, 1285, 1266, 1198, 1156, 1129, 1112,
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5.2.7. 6-Chloro-2'-methoxy-[1,1'-biphenyl]-3-ol (2q). 87 mg, 37% 1027, 967, 903, 857, 792, 765, 749, 702, 650, 597, 573; δH (500
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and 91 mg, 39%; Light yellow oil. Purified by flash
chromatography, (SiO2, 5% EtOAc in hexane), TLC (SiO2) Rf =
0.38 in 10% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3508, 2935, 2834, 1597, 1582, 1566, 1476, 1462, 1424,
1306, 1260, 1241, 1179, 1120, 1049, 1025, 900, 875, 812, 788,
751, 712, 639, 586, 561; δH (500 MHz, CDCl3) 7.34 (m, 2H),
7.30 (dd, J = 7.5, 1.5 Hz, 1H), 7.23 (d, J = 2.0Hz, 1H), 7.04
(m, 2H), 6.99 (d, J = 8.2 Hz, 1H), 5.53 (s, 1H), 3.82 (s, 3H);
δC (125 MHz, CDCl3) 156.3, 150.7, 139.1, 130.6, 129.2, 129.0,
128.3, 122.7, 120.8, 117.3, 111.2, 109.5, 55.5; HRMS (EI+) m/z
calc'd for C13H11ClO2 [M]+: 234.0448, found 234.0449.
MHz, CDCl3) 7.44 (d, J = 8.7 Hz, 1H), 6.77 (d, J = 2.5 Hz, 1H),
6.57 (dd, J = 8.7, 2.6 Hz, 1H), 5.57 (s, 1H), 1.34 (s, 9H); δC (126
MHz, CDCl3) 176.6, 152.8, 151.6, 131.9, 115.2, 109.8, 106.6,
39.1, 27.0; HRMS (EI+) m/z calc'd for C11H13BrO3 [M]+:
272.0048, found 272.0056.
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5.2.13. 4-Bromo-3-ethoxy-2-methylphenol (3h). 196 mg, 85%
and 182 mg, 79%; White solid, mp 92–93 °C. Purified by flash
chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.42 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3321, 2977, 2924, 1584, 1452, 1474, 1388, 1361, 1318,
1290, 1218, 1175, 1074, 1020, 943, 878, 836, 813, 712, 676, 642,
600; δH (500 MHz, CDCl3) 7.22 (d, J = 8.6 Hz, 1H), 6.48 (d, J =
8.6 Hz, 1H), 5.06 (s, 1H), 3.96 (q, J = 7.0 Hz, 2H), 2.21 (s, 3H),
1.45 (t, J = 7.0 Hz, 3H); δC (126 MHz, CDCl3) 155.0, 154.2,
129.9, 119.9, 112.1, 108.2, 69.0, 15.5, 9.6; HRMS (EI+) m/z
calc'd for C9H11BrO2 [M]+: 229.9942, found 229.9946.
5.2.8. 4-Bromo-3-methoxyphenol (3b). 178 mg, 88% and 175 mg,
86%; White solid, mp 85–86 °C. Purified by flash
chromatography, (SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.35 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3455, 2930, 1608, 1583, 1481, 1457, 1421, 1315, 1296,
1261, 1225, 1192, 1157, 1129, 1041, 1021, 947, 821, 791, 728,
622; δH (500 MHz, CDCl3) 7.35 (d, J = 8.5 Hz, 1H), 6.46 (d, J =
2.7 Hz, 1H), 6.33 (dd, J = 8.5, 2.7 Hz, 1H), 4.92 (s, 1H), 3.86 (s,
3H); δC (126 MHz, CDCl3) 156.6, 156.0, 133.3, 108.4, 102.2,
5.2.14. 8-Bromo-4H-benzo[d][1,3]dioxin-5-ol (3i). 199 mg, 86%
and 203 mg, 88%; White solid, mp 158–159 °C. Purified by flash
chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.36 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3349, 2949, 2922, 2870, 1615, 1599, 1487, 1470, 1455,
1443, 1407, 1338, 1287, 1260, 1225, 1197, 1158, 1122, 1063,
1030, 973, 917, 892, 779, 725, 700, 671, 601; δH (500 MHz,
DMSO-d6) 9.99 (s, 1H), 7.21 (d, J = 8.7 Hz, 1H), 6.39 (d, J = 8.7
Hz, 1H), 5.27 (s, 2H), 4.71 (s, 2H); δC (126 MHz, DMSO-d6)
153.8, 150.0, 130.9, 111.2, 109.2, 98.5, 91.5, 63.0; HRMS (EI+)
m/z calc'd for C8H7BrO3 [M]+: 229.9579, found 229.9579.
27 100.3, 56.2; HRMS (EI+) m/z calc'd for C7H7BrO2 [M]+:
201.9629, found 201.9631.
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5.2.9. 4-Bromo-3-isopropoxyphenol (3c). 202 mg, 88% and 204
mg, 88%; Light yellow oil. Purified by flash chromatography,
SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf = 0.50 in 20%
EtOAc in hexane, p-anisaldehyde stain; IR (neat, cm–1) 3374,
2977, 2925, 1582, 1481, 1449, 1384, 1373, 1291, 1264, 1185,
1104, 1035, 996, 918, 827, 796, 738, 698, 623, 607; δH (500 MHz,
CDCl3) 7.34 (d, J = 8.6 Hz, 1H), 6.46 (d, J = 2.5 Hz, 1H), 6.32
(dd, J = 8.5, 2.6 Hz, 1H), 4.84 (s, 1H), 4.50 (hept, J = 6.1 Hz,
1H), 1.38 (d, J = 6.1 Hz, 6H); δC (126 MHz, CDCl3) 155.7, 155.3,
133.4, 108.7, 104.1, 103.3, 72.0, 22.0; HRMS (EI+) m/z calc'd for
C9H11BrO2 [M]+: 229.9942, found 229.9951.
5.2.15. 4-Bromo-5-ethoxy-2-methylphenol (3j). 203 mg, 88% and
212 mg, 92%; White solid, mp 95–96 °C. Purified by flash
chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.48 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3339, 2984, 2926, 2877, 1616, 1577, 1507, 1470, 1444,
1403, 1384, 1353, 1244, 1199, 1155, 1137, 1050, 1013, 907, 877,
838, 819, 795, 610; δH (500 MHz, CDCl3) 7.25 (s, 1H), 6.40 (s,
1H), 4.90 (br. s, 1H), 4.00 (q, J = 6.9 Hz, 2H), 2.15 (s, 3H), 1.43
(t, J = 6.7 Hz, 3H); δC (126 MHz, CDCl3) 154.1, 153.7, 134.3,
117.0, 102.2, 101.7, 65.0, 14.6; HRMS (EI+) m/z calc'd for
C9H11BrO2 [M]+: 229.9942, found 229.9949
5.2.10. 3-(Benzyloxy)-4-bromophenol (3d). 245 mg, 88% and 234
mg, 84%; White solid, mp 50–52 °C. Purified by flash
chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2) Rf =
0.44 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3253, 2920, 2856, 1582, 1498, 1440, 1383, 1362, 1292,
1270, 1236, 1210, 1119, 1078, 1051, 1026, 975, 903, 821, 793,
731, 693, 636, 620; δH (500 MHz, CDCl3) 7.47 (d, J = 7.6 Hz,
2H), 7.36 (m, 4H), 6.48 (d, J = 2.6 Hz, 1H), 6.34 (dd, J = 8.5, 2.5
Hz, 1H), 5.12 (s, 2H), 4.90 (s, 1H); δC (126 MHz, CDCl3);
HRMS (EI+) m/z calc'd for C13H11BrO2 [M]+: 277.9942, found
277.9948.
5.2.16. 4-Bromo-3-(pyrrolidin-1-yl)phenol (3m). 211 mg, 87%
and 206 mg, 85%; White solid, mp 101–102 °C. Purified by flash
chromatography, SiO2, 3% MeOH in CH2Cl2), TLC (SiO2) Rf =
0.36 in 5% MeOH in CH2Cl2, KMnO4 stain; IR (neat, cm–1) 3249,
2964, 2867, 2510, 1588, 1567, 1501, 1486, 1460, 1420, 1348,
1300, 1272, 1214, 1175, 1156, 1052, 1034, 994, 912, 876, 814,
793, 780, 665, 629; δH (500 MHz, CDCl3) 7.22 (d, J = 8.8 Hz,
1H), 6.23 (d, J = 2.7 Hz, 1H), 6.06 (dd, J = 8.8, 2.7 Hz, 1H), 5.40
(s, 1H), 3.23 (br. s, 4H), 2.00 (br. s, 4H); δC (126 MHz, CDCl3)
152.6, 148.9, 131.7, 106.1, 98.8, 95.4, 47.7, 25.4; HRMS (EI+)
m/z calc'd for C10H12BrNO [M+H]+: 242.0174, found 242.0181.
5.2.11. 2-Bromo-5-hydroxyphenyl tert-butyl carbonate (3f). 211
mg, 73% and 217 mg, 75%; White solid, mp 106–107 °C.
Purified by flash chromatography, SiO2, 10% EtOAc in hexane),
TLC (SiO2) Rf = 0.46 in 20% EtOAc in hexane, p-anisaldehyde
stain; IR (neat, cm–1) 3411, 2999, 2968, 2926, 1731, 1607, 1587,
1487, 1452, 1437, 1395, 1373, 1367, 1283, 1256, 1239, 1206,
1146, 1059, 949, 875, 851, 776, 754, 728, 687, 591; δH (500 MHz,
CDCl3) 7.37 (d, J = 8.7 Hz, 1H), 6.64 (d, J = 2.5 Hz, 1H), 6.54
(dd, J = 8.7, 2.5 Hz, 1H), 5.67 (s, 1H), 1.58 (s, 9H); δC (126 MHz,
CDCl3) 156.0, 151.2, 148.5, 133.4, 115.1, 106.4, 84.8, 27.6;
5.2.17. 6-Bromo-2'-methoxy-[1,1'-biphenyl]-3-ol (3n). 128 mg,
46% and 123 mg, 44%; White solid, mp 67–68 °C. Purified by
flash chromatography, SiO2, 10% EtOAc in hexane), TLC (SiO2)
Rf = 0.52 in 20% EtOAc in hexane, p-anisaldehyde stain; IR (neat,
cm–1) 3499, 2935, 2834, 1702, 1582, 1561, 1498, 1473, 1435,