The Journal of Organic Chemistry
Page 6 of 11
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7.84 (ddd, J = 7.9, 1.7, 1.0 Hz, 1H), 7.66 (ddd, J = 7.9, 2.0, 1.0 Hz,
14.8. HRMS (ESI) m/z: [M + H]+ Calcd for C10H13O4S2 261.0250;
1H), 7.54 (t, J = 7.9 Hz, 1H), 4.14 (s, 2H), 3.73 (s, 3H).
13C1H NMR (126 MHz, CDCl3): 162.7, 140.4, 135.7, 134.7,
130.7, 128.8, 126.9, 60.8, 53.3. HRMS (ESI) m/z: [M + H]+ Calcd
for C9H10ClO4S 248.9983; Found 248.9996. IR (neat, cm⁻1): 3005,
2952, 1740 (C=O), 1579, 1436, 1327 (SO2), 1295, 1279, 1151
(SO2), 1103, 1076.
Found 261.0225. IR (neat, cm⁻1): 2925, 1738 (C=O), 1577, 1434,
1396, 1318 (SO2), 1277, 1149 (SO2), 1094, 1076.
Methyl 2-((4-acetamidophenyl)sulfonyl)acetate (3mb). Prepared
according
to
the
general
procedure
A
from
(4-acetamidophenyl)boronic acid and methyl 2-bromoacetate;
yield 72% (75.6 mg). Recrystallized from CHCl3. Yellowish solid.
Rf = 0.46 (EtOAc). 1H NMR (500 MHz, DMSO-d6): 10.43 (br s,
1H), 7.947.69 (m, 4H), 4.55 (s, 2H), 3.59 (s, 3H), 2.10 (s, 3H).
13C1H NMR (126 MHz, DMSO-d6): 169.2, 163.3, 144.3,
132.2, 129.4, 118.5, 59.9, 52.6, 24.2. HRMS (ESI) m/z: [M + H]+
Calcd for C11H14NO5S 272.0587; Found 272.0574. IR (neat, cm⁻1):
3373 (NH), 2933, 1738 ((OMe)C=O), 1693 ((NH)C=O), 1587,
1524, 1435, 1400, 1371, 1311 (SO2), 1286, 1248, 1146 (SO2),
1084.
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Methyl 2-((4-fluorophenyl)sulfonyl)acetate (3hb). Prepared
according to the general procedure A from (4-fluorophenyl)boronic
acid and methyl 2-bromoacetate; yield 88% (78.4 mg). Yellowish
1
oil. Rf = 0.25 (EtOAc/hexanes 3:7). H NMR (500 MHz, CDCl3):
8.047.92 (m, 2H), 7.327.20 (m, 2H), 4.13 (s, 2H), 3.72 (s, 3H).
13C1H NMR (126 MHz, CDCl3): 166.3 (d, J = 259 Hz), 162.9,
134.8 (d, J = 3 Hz), 131.7 (d, J = 10 Hz), 116.7 (d, J = 23 Hz),
60.9, 53.3. HRMS (ESI) m/z: [M + H]+ Calcd for C9H10FO4S
233.0278; Found 233.0285. IR (neat, cm⁻1): 2958, 1737 (C=O),
1590, 1494, 1437, 1324 (SO2), 1292, 1271, 1229, 1146 (SO2),
1084.
Methyl 2-((2-fluorophenyl)sulfonyl)acetate (3ib). Prepared
according to the general procedure A from (2-fluorophenyl)boronic
acid and methyl 2-bromoacetate; reaction time 16 h; yield 58%
(51.5 mg). Yellowish oil. Rf = 0.41 (EtOAc/hexanes 2:3).
1H NMR (500 MHz, CDCl3): 7.95 (dt, J = 8.1, 1.7 Hz, 1H),
7.747.65 (m, 1H), 7.36 (dt, J = 7.8, 1.2 Hz, 1H), 7.27 (ddd,
J = 10.1, 8.2, 1.2 Hz, 1H), 4.31 (s, 2H), 3.69 (s, 3H). 13C1H NMR
(126 MHz, CDCl3): 162.7, 159.7 (d, J = 256 Hz), 136.9 (d,
J = 9 Hz), 131.0, 126.7 (d, J = 14 Hz), 124.9 (d, J = 4 Hz), 117.3
(d, J = 21 Hz), 60.0 (d, J = 3 Hz), 53.3. HRMS (ESI) m/z: [M + H]+
Calcd for C9H10FO4S 233.0278; Found 233.0260. IR (neat, cm⁻1):
2955, 1741 (C=O), 1599, 1474, 1437, 1330 (SO2), 1265,
1149 (SO2), 1119, 1070.
Methyl
2-((3-(dimethylamino)phenyl)sulfonyl)acetate
(3nb).
Prepared according to the general procedure
A
from
3-(dimethylamino)phenylboronic acid and methyl 2-bromoacetate;
yield 20% (19.8 mg). Ruby red oil. Rf = 0.39 (EtOAc/hexanes 2:3).
1H NMR (500 MHz, CDCl3): 7.38 (dd, J = 8.5, 7.6 Hz, 1H), 7.20
(ddd, J = 7.6, 1.8, 0.8 Hz, 1H), 7.16 (dd, J = 2.7, 1.8 Hz, 1H), 6.93
(ddd, 8.5, 2.7, 0.8 Hz, 1H), 4.10 (s, 2H), 3.72 (s, 3H), 3.01 (s, 6H).
13C1H NMR (126 MHz, CDCl3): 163.1, 150.7, 139.5, 130.0,
117.4, 115.2, 110.8, 61.1, 53.2, 40.4. HRMS (ESI) m/z: [M + H]+
Calcd for C11H16NO4S 258.0795; Found 258.0800. IR (neat, cm⁻1):
2950, 1739 (C=O), 1597, 1499, 1433, 1312 (SO2), 1278, 1144
(SO2), 1092.
Methyl
2-((3-((2-methoxy-2-oxoethyl)(methyl)amino)phenyl)
sulfonyl)acetate (4). Isolated as a side-product of target compound
3mb that was prepared according to the general procedure A from
3-(dimethylamino)phenylboronic acid and methyl 2-bromoacetate;
yield 24% (29.4 mg). Ruby red oil. Rf = 0.21 (EtOAc/hexanes 2:3).
1H NMR (500 MHz, CDCl3): 7.39 (dt, J = 8.4, 7.8 Hz, 1H), 7.26
(ddd, J = 7.8, 1.8, 0.9 Hz, 1H), 7.16 (dd, J = 2.8, 1.8 Hz, 1H), 6.90
(ddd, J = 8.4, 2.8, 0.9 Hz, 1H), 4.12 (s, 2H), 4.09 (s, 2H), 3.73 (s,
3H), 3.71 (s, 3H), 3.10 (s, 3H). 13C1H NMR (126 MHz, CDCl3):
170.6, 163.0, 149.4, 139.7, 130.2, 117.4, 116.5, 111.3, 61.0, 54.0,
53.2, 52.3, 39.7. HRMS (ESI) m/z: [M + H]+ Calcd for
C13H18NO6S 316.0849; Found 316.0824. IR (neat, cm⁻1): 2953,
1737 (C=O), 1597, 1496, 1434, 1368, 1311 (SO2), 1278, 1203,
1146 (SO2), 1094.
Methyl 2-((4-nitrophenyl)sulfonyl)acetate (3ob).33 Prepared
according to the general procedure A from (4-nitrophenyl)boronic
acid and methyl 2-bromoacetate; yield 72% (72.1 mg). Yellowish
solid. Rf = 0.44 (EtOAc/hexanes 2:3). 1H NMR (500 MHz,
CDCl3): 8.478.39 (m, 2H), 8.218.13 (m, 2H), 4.20 (s, 2H), 3.73
(s, 2H). 13C1H NMR (126 MHz, CDCl3): 162.6, 151.3, 144.1,
130.4, 124.5, 60.5, 53.5.
Methyl
2-((4-iodophenyl)sulfonyl)acetate
(3jb).
Prepared
according to the general procedure A from (4-iodophenyl)boronic
acid and methyl 2-bromoacetate; yield 79% (103 mg). White
amorphous
solid.
Rf = 0.52
(EtOAc/hexanes
2:3).
1H NMR (500 MHz, CDCl3): 7.95 (d, J = 8.5 Hz, 2H), 7.65 (d,
J = 8.5 Hz, 2H), 4.11 (s, 2H), 3.72 (s, 3H). 13C1H NMR
(126 MHz, CDCl3): 162.8, 138.7, 138.4, 130.0, 102.8, 60.8, 53.3.
HRMS (ESI) m/z: [M + H]+ Calcd for C9H10IO4S 340.9339; Found
340.9353. IR (neat, cm⁻1): 2941, 1735 (C=O), 1564, 1430, 1380,
1318 (SO2), 1271, 1146 (SO2), 1126, 1079.
Methyl 2-((4-methoxyphenyl)sulfonyl)acetate (3kb). Prepared
according
to
the
general
procedure
A
from
(4-methoxyphenyl)boronic acid and methyl 2-bromoacetate; yield
79% (74.0 mg). Yellowish oil. Rf = 0.35 (EtOAc/hexanes 2:3).
1H NMR (500 MHz, CDCl3): 7.897.82 (m, 2H), 7.056.99 (m,
2H), 4.09 (s, 2H), 3.88 (s, 3H), 3.70 (s, 3H). 13C1H NMR
(126 MHz, CDCl3): 164.4, 163.2, 130.9, 130.2, 114.5, 61.2, 55.9,
53.2. HRMS (ESI) m/z: [M + H]+ Calcd for C10H13O5S 245.0478;
Found 245.0475. IR (neat, cm⁻1): 2950, 1739 (C=O), 1593, 1497,
1437, 1324 (SO2), 1299, 1258, 1141 (SO2), 1084.
Methyl
Prepared according to the general procedure
(4-(trifluoromethyl)phenyl)boronic acid and
2-((4-(trifluoromethyl)phenyl)sulfonyl)acetate
(3pb).
from
methyl
A
Methyl 2-((4-(methylthio)phenyl)sulfonyl)acetate (3lb). Prepared
2-bromoacetate; yield 88% (95.5 mg). White solid. Rf = 0.61
(EtOAc/hexanes 2:3). 1H NMR (500 MHz, CDCl3): 8.10 (d,
J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 4.17 (s, 2H), 3.73 (s, 3H).
13C1H NMR (126 MHz, CDCl3): 162.7, 142.2, 136.1 (q,
J = 33 Hz), 129.5, 126.5 (q, J = 4 Hz), 123.2 (q, J = 272 Hz), 60.6,
53.4. HRMS (ESI) m/z: [M + H]+ Calcd for C10H10F3O4S
283.0246; Found 283.0266. IR (neat, cm⁻1): 2980, 2935, 1742
according
to
the
general
procedure
A
from
(4-(methylthio)phenyl)boronic acid and methyl 2-bromoacetate;
yield 82% (82.1 mg). Yellowish oil. Rf = 0.41 (EtOAc/hexanes
2:3). 1H NMR (500 MHz, CDCl3): 7.877.74 (m, 2H), 7.397.29
(m, 2H), 4.10 (s, 2H), 3.71 (s, 3H), 2.52 (s, 3H). 13C1H NMR
(126 MHz, CDCl3): 163.1, 148.4, 134.2, 128.9, 125.3, 61.0, 53.2,
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