ACCEPTED MANUSCRIPT
8
Tetrahedron
411.0449.
6H), 6.84 (d, 1H, J = 5.4 Hz), 6.93 (s, 2H), 7.00 (d, 2H, J = 7.8
Hz), 7.40 (d, 2H, J = 7.8 Hz), 7.48 (d, 1H, J = 5.4 Hz) ppm. 13C
NMR (75 MHz, CDCl3) δ 217.7, 20.9, 21.2, 27.1, 96.9, 125.8,
126.4, 128.3, 129.6, 129.7, 134.3, 139.2, 141.2, 142.3, 143.1,
147.2 ppm. HRMS (DART) Calcd for C14H16IS [M – OTs]+
343.0017, found 343.0026.
4.3.5.
(5-Benzoyl-2,4-dimethoxyphenyl)(mesity)iodonium(III)
o
tosylate (1e-OTs).23a Off-white solid, mp 163−166 C. IR (KBr)
cm-1: 3020, 2929, 2947, 1661, 1588, 1556, 1460, 1384, 1315,
1
1287, 1249, 1216, 1192, 1133, 1044, 1015. H NMR (400 MHz,
CD3OD) δ 2.24 (s, 3H), 2.25 (s, 3H), 2.53 (s, 6H), 3.72 (s, 3H),
3.98 (s, 3H), 6.62 (s, 1H), 6.90 (s, 2H), 6.95 (d, 2H, J = 8.3 Hz),
7.25 (s, 1H), 7.36 (t, 2H, J = 7.8 Hz), 7.42 (d, 2H, J = 8.3 Hz),
7.52 (t, 1H, J = 7.4 Hz), 7.60 (d, 2H, J = 7.3 Hz) ppm. 13C NMR
(100 MHz, CD3OD) δ 20.9, 21.2, 26.8, 56.3, 57.3, 90.8, 96.8,
120.6, 124.0, 125.7, 128.2, 128.3, 129.5, 129.9, 133.1, 135.3,
137.3, 139.1, 142.3, 142.7, 143.5, 160.4, 162.7, 193.0 ppm.
4.3.11. Dimesityliodonium(III) tosylate (1k-OTs). White solid, mp
138−142 oC. IR (KBr) cm-1: 3022, 2976, 1454, 1191, 1132, 1045.
1H NMR (300 MHz, CD3OD) δ 2.33 (s, 6H), 2.35 (s, 3H), 2.51 (s,
12H), 7.17–7.22 (m, 6H), 7.66 (d, 2H, J = 7.8 Hz) ppm. 13C NMR
(75 MHz, CD3OD) δ 20.8, 21.3, 26.1, 119.1, 126.9, 129.7, 131.7,
141.5, 143.6, 143.6, 145.2 ppm. HRMS (DART) Calcd for
C18H22I [M – OTs]+ 365.0766, found 365.0780.
4.3.6. [3-Carboxymethyl-4-methoxyphenyl](mesityl)iodonium(III)
o
tosylate (1f-OTs). Pale red solid, mp 168−170 C. IR (KBr) cm-1:
4.3.12. (2-Iodo-4-methoxyphenyl)(mesityl)iodonium(III) tosylate
o
3025, 2946, 1733, 1490, 1457, 1300, 1285, 1257, 1191, 1133,
1036, 1013. H NMR (400 MHz, CD3OD) δ 2.32 (s, 3H), 2.36 (s,
(1l-OTs). Pale red solid, mp 156−159 C. IR (KBr) cm-1: 3023,
1
1
2977, 2943, 1568, 1457, 1290, 1192, 1132, 1044, 1015. H NMR
3H), 2.67 (s, 6H), 3.62 (s, 2H), 3.86 (s, 3H), 7.07 (d, 2H, J = 8.3
Hz), 7.16–7.25 (m, 4H), 7.68 (d, 2H, J = 7.2 Hz), 7.82 (d, 2H, J =
8.8 Hz) ppm. 13C NMR (100 MHz, CD3OD) δ 21.0, 21.3, 27.0,
56.6, 102.3, 115.1, 122.8, 126.9, 129.5, 129.8, 131.1, 136.8, 138.2,
141.6, 143.3, 143.6, 145.4, 162.2, 174.3 ppm. HRMS (DART)
Calcd for C18H20IO3 [M – OTs]+ 411.0452, found 411.0455.
(400 MHz, CD3OD) δ 2.36 (s, 6H), 2.65 (s, 6H), 3.82 (s, 3H),
7.00 (dd, 1H, J = 8.8, 2.4 Hz), 7.17–7.27 (m, 4H), 7.59–7.72 (m,
4H) ppm. 13C NMR (100 MHz, CD3OD) δ 21.0, 21.3, 27.3, 56.7,
104.3, 113.7, 118.5, 126.9, 127.9, 129.8, 131.6, 139.0, 141.6,
143.5, 143.6, 145.8, 164.1 ppm. HRMS (DART) Calcd for
C16H17I2O [M – OTs]+ 478.9363, found 478.9364.
4.3.7. Mesityl[4-(2-propenyloxy)phenyl]iodonium(III) tosylate
(1g-OTs). White solid, mp 181−182 oC. IR (KBr) cm-1: 3024,
2986, 2939, 2921, 1578, 1483, 1456, 1426, 1397, 1296, 1248,
Iodonium salts 1m-n having a triflate counterion could be
prepared based on the abovementioned procedure, followed by
treatment of the in situ formed corresponding tosylate iodonium
salts with aqueous sodium triflate (10 equiv.) at room temperature.
1
1192, 1173, 1132, 1044, 1014. H NMR (400 MHz, CD3OD) δ
2.30 (s, 3H), 2.34 (s, 3H), 2.59 (s, 6H), 5.29 (dd, 1H, J = 10.4, 1.2
Hz), 5.36 (dd, 1H, J = 17.2, 1.6 Hz), 5.96 (ddd, 1H, J = 17.2, 10.8,
5.6 Hz), 6.84 (d, 2H, J = 7.2 Hz), 6.99 (s, 2H), 7.04 (d, 2H, J = 8.4
Hz), 7.54–7.63 (m, 4H) ppm. 13C NMR (100 MHz, CD3OD) δ
21.0, 21.3, 27.0,70.2, 102.8, 118.3, 119.6, 122.9, 126.9, 129.8,
131.2, 133.8, 137.5, 141.6, 143.2, 143.5, 145.5, 163.1 ppm.
HRMS (DART) Calcd for C18H20IO [M – OTs]+ 379.0553, found
379.0553.
4.3.13.
(3,5-Dimethyl-1H-pyrazol-4-yl)(mesityl)iodonium(III)
o
triflate (1m-OTf).2d White solid, mp 185−187 C. IR (KBr) cm-1:
3192, 3178, 3108, 3033, 2972, 2873, 1570, 1457, 1403, 1285,
1245, 1223, 1163, 1131, 1067, 1029. 1H NMR (400 MHz,
CD3OD) δ 2.30–2.38 (m, 9H), 2.63 (s, 6H), 7.19 (s, 2H) ppm. 13C
NMR (100 MHz, CD3OD) δ 20.9, 21.3, 26.6, 81.0, 121.8 (q, JCF
317 Hz), 121.3, 126.9, 129.8, 131.3, 142.9, 145.3 ppm.
=
4.3.8.
(2,4-Dimethoxy-5-formylphenyl)(mesityl)iodonium(III)
4.3.14.
Mesityl[5-(methoxycarbonyl)-1-methyl-1H-pyrrol-3-
tosylate (1h-OTs). Yellowish solid, mp 162−165 oC. IR (KBr) cm-
1: 2923, 1685, 1586, 1562, 1456, 1435, 1395, 1315, 1283, 1250,
1217, 1190, 1148, 1132, 1043, 1014. 1H NMR (400 MHz,
CDCl3) δ 2.31(s, 3H), 2.33 (s, 3H), 2.58 (s, 6H), 3.98 (s, 3H), 4.05
(s, 3H), 6.57 (s, 1H), 6.98−7.05 (m, 4H), 7.49 (d, 1H, J = 7.8 Hz),
7.62 (s, 1H), 10.15 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ
20.9, 21.1, 26.6, 56.7, 57.7, 92.8, 96.9, 120.6 (x 2), 125.6, 128.2,
129.8, 134.5, 139.0, 142.2, 142.6, 143.4, 162.8, 166.4, 186.2 ppm.
HRMS (DART) Calcd for C18H20IO [M – OTs]+ 379.0553, found
379.0553.
yl]iodonium(III) triflate (1n-OTf). Brownish solid, mp 158−160
oC. IR (KBr) cm-1: 3115, 2952, 1716, 1519, 1437, 1383, 1328,
1
1275, 1247, 1203, 1161, 1113 1053, 1031. H NMR (400 MHz,
DMSO-d6) δ 2.27 (s, 3H), 2.63 (s, 6H), 3.75 (s, 3H), 3.88 (s, 3H),
7.17 (s, 2H), 7.37 (d, 1H, J = 1.9 Hz), 7.93 (d, 1H, J = 1.9 Hz)
ppm. 13C NMR (100 MHz, DMSO-d6) δ 20.4, 26.3, 37.1, 51.6,
81.5, 120.7 (q, JCF = 321 Hz), 121.6, 124.2, 124.6, 129.5, 135.9,
140.8, 142.7, 159.5 ppm. HRMS (DART) Calcd for C16H19INO2
[M – OTs]+ 384.0455, found 384.0457.
4.4. Synthetic procedure for mesityl iodonium(III) salts using
MesI(OAc)2 (Scheme 6)
4.3.9. (2,4-Dimethoxy-3-pyridinyl)(mesity)iodonium(III) tosylate
(1i-OTs). White solid, mp 184−186 oC. IR (KBr) cm-1: 3016,
2979, 2952, 2923, 1567, 1496, 1460, 1410, 1375, 1319, 1274,
To a stirred solution of thiophene (42 mg, 0.50 mmol) in 2,2,2-
trifluoroethanol (2.5 mL) and dichloromethane (0.25 mL),
MesI(OAc)2 (182 mg, 0.50 mmol) was added in one portion at
room temperature. The organic acid (p-TsOH·H2O, 95 mg, 0.50
mmol, 1 equiv.; trifluoroacetic acid, 114 mg, 1.0 mmol, 2 equiv.)
was then added, and the resulting solution was stirred for 3 h.
After the addition of methanol (~2 mL), the solvents were
removed under reduced pressure. The residue was then treated
with diethyl ether, with stirring for precipitation of the
iodonium(III)salt, 1o-OTs or 1o-OCOCF3. The precipitate was
filtered and dried in vacuo to give pure iodonium(III) salt in
powder form.
1
1192, 1132, 1082, 1045, 1015. H NMR (400 MHz, CD3OD) δ
2.32 (s, 3H), 2.36 (s, 3H), 2.66 (s, 6H), 3.95 (s, 3H), 4.00 (s, 3H),
6.45 (d, 1H, J = 7.9 Hz), 7.13−7.25 (m, 4H), 7.66 (d, 2H, J = 8.1
Hz), 8.26 (d, 1H, J = 8.8 Hz) ppm. 13C NMR (100 MHz,
CD3OD) δ 21.0, 21.3, 54.9, 55.7, 85.3, 106.7, 122.0, 126.9, 129.8,
131.0, 141.6, 143.5, 143.6, 145.3, 149.7, 162.1, 167.9 ppm.
HRMS (DART) Calcd for C16H19INO2 [M – OTs]+ 384.0455,
found 384.0451.
4.3.10. Mesityl(3-methyl-2-thienyl)iodonium(III) tosylate (1j-OTs).
White powder, mp 145 oC. IR (KBr) cm-1: 3637, 3466, 3061, 2953,
1
1923, 1600, 1450, 1377, 1300, 1215, 1132, 1043. H NMR (300
4.4.1. Mesityl(2-thienyl)iodonium(III) tosylate (1o-OTs).45
MHz, CDCl3) δ 2.27 (s, 3H), 2.30 (s, 3H), 2.47 (s, 3H), 2.67 (s,