M. A. Carroll et al.
FULL PAPER
36.4 Hz, C=O), 143.2 (C1), 140.4 (C4Ј), 132.6, 130.3 (C2/C6), Phenyl(2Ј,4Ј,6Ј-trimethylphenylethynyl)iodonium
Trifluoroacetate
129.9, 129.4, 128.4, 120.4, 115.4 (q, J = 291.4 Hz, CF3), 100.7
(7k): Using (2,4,6-trimethylphenyl)acetylene, the product was ob-
(C7Ј), 43.0 (C8Ј), 26.8 (o-Me), 20.8 (p-Me) ppm. 13C NMR tained as a white crystalline solid (0.95 g, 2.06 mmol, 45%), m.p.
(100 MHz, [D6]DMSO): δ = 159.5 (q, J = 33.2 Hz, C=O), 143.4,
141.0, 133.1, 131.4, 130.1, 129.5, 127.7, 120.3, 116.8 (q, J =
297.6 Hz, CF3), 99.9 (C7Ј), 42.6 (C8Ј), 26.61 (o-Me), 21.0 (p-Me)
81–84 °C (dec., from CH2Cl2/diethyl ether/petroleum ether). 1H
NMR (400 MHz, CDCl3): δ = 8.16 (dd, J = 8.7, J = 1.8 Hz, 2 H,
H2/H6), 7.57 (t, J = 7.7 Hz, 1 H, H4), 7.46 (t, J = 8.7 Hz, 2 H,
ppm. 19F NMR (376 MHz, [D6]DMSO): δ = –73.6 ppm. IR (neat): H3/H5), 6.86 (s, 2 H, H3Ј/H5Ј), 2.31 (s, 6 H, o-Me), 2.27 (s, 3 H,
ν = 2160, 1662, 1489, 1444, 1417, 1382, 1302, 1180, 1132,
p-Me) ppm. 13C NMR (100 MHz, CDCl3): δ = 162.3 (q, J =
1026 cm–1. MS (ESI): m/z (%): 347 (100) [M – TFA]+, 220 (49). 35.5 Hz, C=O), 142.1, 140.7, 133.2, 131.9, 131.7, 127.9, 120.9,
˜
HRMS (ESI): calcd. for C17H16I 347.0297; found 347.0291 [M –
TFA]+. C19H16F3IO2 (460.23): calcd. C 49.58, H 3.50; found C
49.69, H 3.36.
117.2, 115.5 (q, J = 290.4 Hz, CF3), 103.3 (C7Ј), 50.1 (C8Ј), 21.3
(p-Me), 20.7 (o-Me) ppm. 13C NMR (100 MHz, [D6]DMSO): δ =
159.2 (q, J = 32.2 Hz, C=O), 141.9, 140.7, 135.1, 132.5, 132.3,
128.4, 121.2, 117.5, 101.0 (C7Ј), 49.8 (C8Ј), 21.5 (p-Me), 20.7 (o-
Me) ppm. 19F NMR (376 MHz, CDCl3): δ = –75.3 ppm. IR (neat):
Phenyl(3Ј-thienylethynyl)iodonium Trifluoroacetate (7h): Using 3-
ethynylthiophene, the product was obtained as a white crystalline
solid (2.09 g, 4.92 mmol, 76%), m.p. 94–96 °C (dec., from CH2Cl2/
ν = 2969, 2917, 2137, 1671, 1569, 1475, 1445, 1424, 1189,
˜
1
1125 cm–1. MS (ESI): m/z (%): 347 (100) [M – TFA]+. HRMS
(ESI): calcd. for C17H16I 347.0297; found 347.0291 [M – TFA]+.
C19H16F4IO2 (479.23): calcd. C 49.58, H 3.50; found C 49.71, H
3.38.
diethyl ether/petroleum ether). H NMR (300 MHz, [D6]DMSO):
δ = 8.32 (d, J = 7.5 Hz, 2 H, H2/H6), 8.09 (s, 1 H, H2Ј), 7.73–7.68
(m, 2 H), 7.59 (t, J = 7.5 Hz, 2 H, H3/H5), 7.25 (d, J = 4.5 Hz, 1
H, H5Ј) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 159.2 (q, J
= 32.6 Hz, C=O), 134.7, 134.5, 131.9, 131.8, 129.8, 127.7, 120.4,
118.9, 116.3 (q, J = 296.2 Hz, CF3), 97.3 (C6Ј), 40.4 (C7Ј) ppm.
Phenyl(2Ј,4Ј,5Ј-trimethylphenylethynyl)iodonium
Trifluoroacetate
(7l): Using (2,4,5-trimethylphenyl)acetylene, the product was ob-
19F NMR (376 MHz, [D ]DMSO): δ = –73.7 ppm. IR (neat): ν =
˜
6
tained as a white crystalline solid (1.24 g, 2.70 mmol, 54%), m.p.
3093, 2161, 1652, 1469, 1444, 1417, 1180, 1133 cm–1. MS (ESI):
m/z (%): 311 (100) [M – TFA]+. HRMS (ESI): calcd. for C12H8IS
310.9391; found 310.9384 [M – TFA]+. C14H8F3IO2S (424.17):
calcd. C 39.64, H 1.90; found C 39.77, H 1.69.
1
110–111 °C (dec., from CH2Cl2/diethyl ether/petroleum ether). H
NMR (300 MHz, [D6]DMSO): δ = 8.33 (d, J = 6.0 Hz, 2 H, H2/
H6), 7.70 (t, J = 7.5 Hz, 1 H, H4), 7.59 (t, J = 7.5 Hz, 2 H, H3/
H5), 7.21 (s, 1 H, H6Ј) 7.07 (s, 1 H, H3Ј), 2.22 (s, 2 H, p-Me), 2.19
(s, 3 H, o-Me), 2.13 (s, 3 H, m-Me) ppm. 13C NMR (100 MHz,
[D6]DMSO): δ = 159.1 (q, J = 32.6 Hz, C=O), 139.8, 138.8, 134.5,
134.2, 133.1, 131.9, 131.7, 131.0, 130.7, 120.7, 117.0, 116.4 (q, J =
297.1 Hz, CF3), 101.5 (C7Ј), 46.1 (C8Ј), 19.4 (p-Me), 19.3 (o-Me),
Phenyl(4Ј-n-pentylphenylethynyl)iodonium Trifluoroacetate (7i):
Using (4-n-pentylphenyl)acetylene, the product was obtained as a
white crystalline solid (2.01 g, 4.12 mmol, 82%), m.p. 79–81 °C
(dec., from CH2Cl2/diethyl ether/petroleum ether). 1H NMR
(300 MHz, CDCl3): δ = 8.18 (dd, J = 7.8, J = 1.2 Hz, 2 H, H2/
H6), 7.63 (t, J = 6.8 Hz, 1 H, H4), 7.52 (t, J = 7.2 Hz, 2 H, H3/
H5), 7.41 (d, J = 7.8 Hz, 2 H, H2Ј/H6Ј), 7.20 (d, J = 8.1 Hz, 2 H,
H3Ј/H5Ј), 2.64 (t, J = 8.1 Hz, 2 H, H9Ј), 1.61 (m, 2 H), 1.32 (m, 4
H), 0.90 (t, J = 6.9 Hz, 3 H, H13Ј) ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.3 (q, J = 35.5 Hz, C=O), 146.2, 133.3, 132.7,
131.7, 131.5, 128.6, 120.3, 117.4, 115.5 (q, J = 292.4 Hz, CF3),
104.3 (C7Ј), 43.8 (C8Ј), 35.8, 31.2, 30.6, 22.3, 13.8 ppm. 13C NMR
(100 MHz, [D6]DMSO): δ = 159.6 (q, J = 33.2 Hz, C=O), 146.3,
134.9, 133.0, 132.3, 132.2, 129.4, 120.9, 117.7, 116.8 (q, J =
296.6 Hz, CF3), 102.5 (C7Ј), 44.1 (C8Ј), 35.6, 31.3, 30.8, 22.4,
14.3 ppm. 19F NMR (376 MHz, CDCl3): δ = –74.9 ppm. IR (neat):
18.5 (m-Me) ppm. 19F NMR (376 MHz, [D6]DMSO):
δ =
–73.63 ppm. IR (neat): ν = 2916, 2160, 1666, 1567, 1495, 1474,
˜
1443, 1421, 1184, 1126, 1070, 1008 cm–1. MS (ESI): m/z (%): 347
(100) [M – TFA]+. HRMS (ESI): calcd. for C17H16I 347.0297;
found 347.0294 [M – TFA]+. C19H16F3IO2 (460.23): calcd. C 49.58,
H 3.50; found C 49.75, H 3.40.
Phenyl(4Ј-methoxyphenylethynyl)iodonium Trifluoroacetate (7m):
Using (4-methoxyphenyl)acetylene, the product was obtained as a
pale yellow/white crystalline solid (0.70 g, 1.56 mmol, 61%), m.p.
89–91 °C (dec., from CH2Cl2/diethyl ether/petroleum ether). 1H
NMR (400 MHz, CDCl3): δ = 8.13 (d, J = 8.2 Hz, 2 H, H2/H6),
7.57 (t, J = 7.3 Hz, 1 H, H4), 7.46 (t, J = 8.0 Hz, 2 H, H3/H5),
7.41 (d, J = 8.7 Hz, 2 H, H2Ј/H6Ј), 6.85 (d, J = 8.7 Hz, 2 H, H3Ј/
H5Ј), 3.80 (s, 3 H, OMe) ppm. 13C NMR (100 MHz, CDCl3): δ =
161.6, 134.7, 133.2, 131.9, 131.7 (C4), 120.5, 114.3, 112.0, 105.1,
55.4 (OMe), 42.9 (C8Ј) ppm. 19F NMR (376 MHz, CDCl3): δ =
ν = 2953, 2926, 2855, 2165, 1666, 1505, 1475, 1443, 1419, 1183,
˜
1130, 1013 cm–1. MS (ESI): m/z (%): 375 (100) [M – TFA]+. HRMS
(ESI): calcd. for C19H20I 375.0610; found 375.0582 [M – TFA]+.
C21H20F3IO2 (488.29): calcd. C 51.66, H 4.13; found C 51.53, H
3.97.
–75.3 ppm. IR (neat): ν = 2141, 1648, 1600, 1507, 1442, 1420, 1296,
˜
1250, 1138, 1030 cm–1. MS (ESI): m/z (%): 335 (100) [M – TFA]+.
HRMS (ESI): calcd. for C15H12IO 334.9933; found 334.9929 [M –
TFA]+.
Phenyl(4Ј-bromophenylethynyl)iodonium
Trifluoroacetate
(7j):
Using (4-bromophenyl)acetylene, the product was obtained as a
white crystalline solid (1.65 g, 3.32 mmol, 66%), m.p. 101–103 °C
(dec., from CH2Cl2/diethyl ether/petroleum ether). 1H NMR
(400 MHz, [D6]DMSO): δ = 8.32 (dd, J = 8.5, J = 1.2 Hz, 2 H,
H2/H6), 7.70 (t, J = 7.3 Hz, 1 H, H4), 7.64 (d, J = 8.7 Hz, 2 H,
H2Ј/H6Ј), 7.58 (t, J = 7.8 Hz, 2 H, H3/H5), 7.45 (d, J = 8.7 Hz, 2
H, H3Ј/H5Ј) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 135.1
(C2Ј/C6Ј), 134.9 (C3Ј/C5Ј), 132.7 (C2/C6), 132.7 (C4), 132.4 (C3/
Subsequent repetition of this reaction yielded only the α-trifluo-
roacetato ketone, 9.
Phenyl(2Ј-methoxyphenylethynyl)iodonium Trifluoroacetate (7n):
Using (4-methoxyphenyl)acetylene, the product was obtained as a
pale yellow crystalline solid (1.07 g, 2.40 mmol, 48%), m.p. 62–
C5), 125.3 (C4Ј), 120.7 (C1Ј), 119.6 (C1), 101.0 (C7Ј), 46.0 (C8Ј) 65 °C (dec., from CH2Cl2/diethyl ether/petroleum ether). 1H NMR
ppm. 19F NMR (376 MHz, [D6]DMSO): δ = –73.4 ppm. IR (neat): (400 MHz, CDCl3): δ = 8.17 (d, J = 8.2 Hz, 2 H, H2/H6), 7.57 (t,
ν = 2165, 1662, 1473, 1423, 1186, 1136, 1069, 1011 cm–1. MS (ESI): J = 7.3 Hz, 1 H, H4), 7.47 (t, J = 8.2 Hz, 2 H, H3/H5), 7.40–7.36
˜
m/z (%): 385 (94) [81Br][M – TFA]+, 383 (100) [79Br][M – TFA]+.
HRMS (ESI): calcd. for C14H979BrI 382.8932; found 382.8929 [M –
TFA]+. C16H9BrF3IO2 (497.05): calcd. C 38.66, H 1.83; found C
38.57, H 1.79.
(m, 2 H, H4Ј/H6Ј), 6.92 (t, J = 7.8 Hz, 1 H, H5Ј), 6.89 (d, J =
8.7 Hz, 1 H, H3Ј), 3.85 (s, 3 H, OMe) ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.4 (q, J = 36.4 Hz, C=O), 161.7 (C2Ј), 134.5 (C6Ј),
133.2 (C2/C6), 132.4 (C4Ј), 131.9 (C3/C5), 131.7 (C4), 120.7 (C1Ј),
2342
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Eur. J. Org. Chem. 2013, 2334–2345