The Journal of Organic Chemistry
Article
CDCl ): δ = −66.05, −145.6. HRMS (FAB, double focusing): m/z [M
22.4 Hz, 2H), 3.67 (s, 3H), 6.70 (d, J = 14.4 Hz, 1H), 7.50 (t, J = 8 Hz,
2H), 7.64 (t, J = 8 Hz, 1H), 7.96 (d, J = 8 Hz, 2H). C{ H} NMR
3
+
13
1
−
BF ] calcd for C H FI 305.0197, found 305.0202.
4
12 15
(
E)-2-Fluoro-1-dodecen-1-yl(phenyl)iodonium Tetrafluoroborate
(100 MHz, CDCl ): δ = 24.4, 25.3, 28.2, 28.39, 28.43, 28.47, 31.5 (d, J
3
6b
(
2c). The product was obtained as white solids. Mp: 65−67 °C.
= 24.0 Hz), 33.5, 51.1, 78.6 (d, J = 47.2 Hz), 112.1, 131.9, 132.3,
1
19
Yield: 190 mg (80%). H NMR (400 MHz, CDCl ): δ = 0.88 (t, J = 7
134.3, 174.0, 175.4 (d, J = 277.2 Hz). F NMR (376 MHz, CDCl ): δ
3
3
+
Hz, 3H), 1.18−1.32 (m, 14H), 1.52 (t, J = 7 Hz, 2H), 2.80 (dt, J = 7,
= −65.1, −146.1. HRMS (FAB, double focusing): m/z [M _ -BF ]
calcd for C H FIO 419.0878, found 419.0882.
4
2
2.4 Hz, 2H), 6.70 (d, J = 14.8 Hz, 1H), 7.49 (t, J = 8 Hz, 2H), 7.63 (t,
18
25
2
13
1
J = 8 Hz, 1H), 7.97 (d, J = 8 Hz, 2H). C{ H} NMR (100 MHz,
(E)-2-Fluoro-10-tosyloxy-1-decen-1-yl(phenyl)iodonium Tetra-
CDCl ): δ = 13.8, 22.4, 25.5, 28.5, 29.0, 29.1 (two peaks overlapped),
fluoroborate (2j). The product was obtained as white solids. Mp:
3
1
2
1
9.2, 31.6, 31.8 (d, J = 24.0 Hz), 78.5 (d, J = 47.3 Hz), 112.0, 132.0,
83−84 °C. Yield: 241 mg (78%). H NMR (400 MHz, CDCl ): δ =
3
32.3, 134.5, 175.7 (d, J = 285.0 Hz). 19F NMR (376 MHz, CDCl ): δ
1.15−1.30 (m, 8H), 1.48−1.53 (m, 2H), 1.58−1.65 (m, 2H), 2.45 (s,
3H), 2.79 (dt, J = 7.6, 22.0 Hz, 2H), 4.01 (t, J = 6.4 Hz, 2H), 6.72 (d, J
= 14.0 Hz, 1H), 7.35 (t, J = 8 Hz, 2H), 7.48 (t, J = 8 Hz, 2H), 7.63 (t, J
3
=
−65.0, −145.8.
E)-2-Fluoro-5-methyl-1-hexen-1-yl(phenyl)iodonium Tetrafluor-
oborate (2d). The product was obtained as white solids. Mp: 83−86
(
1
3
1
= 8 Hz, 1H), 7.78 (d, J = 8 Hz, 2H), 7.97 (d, J = 8 Hz, 2H). C{ H}
1
°
C. Yield: 150 mg (74%). H NMR (400 MHz, CDCl ): δ = 0.87 (d, J
NMR (100 MHz, DMSO-d ): δ = 20.9, 24.5, 25.0, 27.9 (two peaks
3
6
=
7 Hz, 6H), 1.38 (q, J = 7 Hz, 2H), 1.51−1.62 (m, 1H), 2.78 (dt, J =
overlapped), 28.0, 28.2, 31.3 (d, J = 24.0 Hz), 70.4, 78.3 (d, J = 47.2
8
, 22.0 Hz, 2H), 6.71 (d, J = 14.4 Hz, 1H), 7.48 (t, J = 8 Hz, 2H), 7.63
Hz), 111.7, 127.1, 129.5, 131.8, 132.0, 132.2, 134.2, 144.5, 175.3 (d, J
t, J = 8 Hz, 1H), 7.97 (d, J = 8 Hz, 2H). 13C{ H} NMR (100 MHz,
1
19
(
= 284.1 Hz). F NMR (376 MHz, CDCl ): δ = −65.3, −145.9.
3
+
CDCl ): δ = 21.8, 27.3, 30.0 (d, J = 23.2 Hz), 34.3, 78.2 (d, J = 48.0
HRMS (FAB, double focusing): m/z [M − BF ] calcd for
C H FIO S 531.0861, found 531.0866.
3
4
19
Hz), 111.9, 132.1, 132.5, 134.5, 176.0 (d, J = 284.2 Hz). F NMR
376 MHz, CDCl ): δ = −64.9, −145.7. HRMS (FAB, double
23
29
3
(
(E)-2-Fluoro-10-phthalimido-1-decen-1-yl(phenyl)iodonium Tet-
3
+
focusing): m/z [M − BF ] calcd for C H FI 319.0353, found
rafluoroborate (2k). The product was obtained as white solids. Mp:
4
13 17
1
3
19.0359.
E)-3-Cyclohexyl-2-fluoro-1-propen-1-yl(phenyl)iodonium Tetra-
fluoroborate (2e). The product was obtained as white solids. Mp:
81−83 °C. Yield: 255 mg (86%). H NMR (400 MHz, CD OD): δ =
3
(
1.23−1.35 (m, 8H), 1.46−1.54 (m, 2H), 1.62−1.68 (m, 2H), 2.84 (dt,
J = 7.2, 22.0 Hz, 2H), 3.65 (t, J = 7 Hz, 2H), 7.03 (d, J = 15.6 Hz, 1H),
7.59 (t, J = 8 Hz, 2H), 7.72−7.84 (m, 5H), 8.10 (d, J = 8 Hz, 2H).
1
1
0
25−126 °C. Yield: 179 mg (83%). H NMR (400 MHz, CDCl ): δ =
3
13
1
.89−0.98 (m, 2H), 1.09−1.30 (m, 3H), 1.63−1.65 (m, 6H), 2.69 (dd,
C{ H} NMR (100 MHz, CD OD): δ = 26.6, 27.4, 29.2, 29.4, 29.6,
3
J = 7, 23.0 Hz, 2H), 6.74 (d, J = 14.4 Hz, 1H), 7.49 (t, J = 8 Hz, 2H),
29.9, 32.5 (d, J = 23.4 Hz), 38.5, 81.7 (d, J = 43.6 Hz), 115.0, 123.8,
.63 (t, J = 8 Hz, 1H), 7.97 (d, J = 8 Hz, 2H). 13C{ H} NMR (100
1
19
7
132.7, 133.0, 133.5, 135.2, 135.9, 169.4, 175.8 (d, J = 281.2 Hz). F
MHz, CDCl ): δ = 26.0 (two peaks overlapped), 32.3, 35.5, 38.7 (d, J
NMR (376 MHz, CD OD): δ = −65.5, −145.8. HRMS (FAB, double
3
3
+
=
22.4 Hz), 85.0 (d, J = 40.3 Hz), 116.4, 132.1, 132.4, 135.2, 172.4 (d,
focusing): m/z [M − BF ] calcd for C H FINO 506.0987, found
4
24 26
2
19
J = 277.9 Hz). F NMR (376 MHz, CDCl ): δ = −62.4, −146.0.
HRMS (FAB, double focusing): m/z [M-BF ] calcd for C H FI
506.0992.
3
+
4
15 19
Synthesis of β-Fluorovinyliodonium Salts 2 Using Iodoben-
zene and m-CPBA. In a Teflon tube were placed PhI (0.153 g, 0.75
mmol), Py·HF (0.286 g, 10 mmol), m-CPBA (0.172 g, 0.75 mmol),
and CH Cl (2 mL). The mixture was stirred at room temperature for
3
45.0510, found 345.0517.
E)-4-Fluoro-3-hexen-3-yl(phenyl)iodonium Tetrafluoroborate
2f). The product was obtained as brownish oil. Yield: 118 mg
(
(
2
2
1
(
60%). H NMR (400 MHz, CDCl ): δ = 1.13 (t, J = 7 Hz, 3H), 1.22
3 h, and then alkyne 1 (0.5 mmol) was added at this temperature.
3
(
t, J = 7 Hz, 3H), 2.70−2.75 (m, 2H), 2.94 (dq, J = 7.4, 22.2 Hz, 2H),
After the mixture was cooled to −78 °C, BF ·Et O (0.25 mL, 2.0
3
2
7
.52 (t, J = 8 Hz, 2H), 7.67 (t, J = 8 Hz, 1H), 7.94 (d, J = 8 Hz, 2H).
mmol) was added and the mixture stirred for 10 min. The reaction
mixture was warmed to room temperature and stirred for 20 min. The
reaction mixture was poured into water (15 mL) and extracted with
CH Cl (10 mL × 3). The combined organic layer was washed with an
1
3
1
C{ H} NMR (100 MHz, CDCl ): δ = 10.4, 13.3, 25.6, 27.1 (d, J =
3
2
2
5.6 Hz), 106.4 (d, J = 41.0 Hz), 109, 132.3, 132.7, 134.8, 169.5 (d, J =
79.5 Hz). 19F NMR (376 MHz, CDCl ): δ = −80.8, −146.4. HRMS
3
2
2
+
(
FAB, double focusing): m/z [M − BF ] calcd for C H FI
aqueous solution (15 mL) of NaBF (0.548 g, 5.0 mmol) and dried
4
12 15
4
3
05.0197, found 305.0205.
E)-7-Fluoro-6-dodecen-6-yl(phenyl)iodonium Tetrafluoroborate
2g). The product was obtained as brownish solids. Mp: 68−69 °C.
over anhydrous Na SO . After evaporation of the solvent, the residue
2
4
(
was submitted to column chromatography on silica gel (5 g). Organic
compounds containing m-chlorobenzoic acid were first eluted with
hexane/EtOAc (9:1), and β-fluorovinyliodonium salts 2 were eluted
with EtOAc. The same procedure was conducted for the reactions with
4-iodotoluene and 1-chloro-4-iodobenzene (Scheme 4). In the
reaction using 1-chloro-4-iodobenzene, the mixture of 1-chloro-4-
(
1
Yield: 186 mg (78%). H NMR (400 MHz, CD OD): δ = 0.87 (t, J =
3
7
4
2
1
1
3
1
Hz, 3H), 0.90−0.96 (m, 3H), 1.21−1.33 (m, 4H), 1.33−1.45 (m,
H), 1.51 (t, J = 7 Hz, 2H), 1.60−1.65 (m, 2H), 2.68−2.74 (m, 2H),
.94 (dt, J = 7.6, 22.4 Hz, 2H), 7.61 (t, J = 8 Hz), 7.77 (t, J = 8 Hz,
H), 8.11 (d, J = 8 Hz, 2H). 13C{ H} NMR (100 MHz, CDCl ): δ =
1
3
iodobenzene, Py·HF, m-CPBA, and CH Cl2 was stirred at room
2
3.5 (two peaks overlapped), 21.7, 21.9, 25.7, 27.7, 30.0, 30.7, 31.9,
temperature for 6 h.
3.4 (d, J = 25.5 Hz), 105.0 (d, J = 40.2 Hz), 109.7, 132.2, 132.7,
(E)-2-Fluoro-1-dodecen-1-yl(4-methylphenyl)iodonium Tetra-
34.6, 169.2 (d, J = 277.9 Hz). 19F NMR (376 MHz, CDCl ): δ =
5b
fluoroborate (3a). The product was obtained as white solids. Mp:
3
+
1
−
77.1, −147.1. HRMS (FAB, double focusing): m/z [M − BF ] calcd
73−74 °C. Yield: 181 mg (74%). H NMR (400 MHz, CDCl
3
): δ =
4
for C H FI: 389.1136, found 389.1142.
0.89 (t, J = 7 Hz, 3H), 1.20−1.33 (m, 14H), 1.50−1.65 (m, 2H), 2.43
(s, 3H), 2.79 (dt, J = 7.2, 22.0 Hz, 2H), 6.66 (d, J = 14.4 Hz, 1H), 7.29
(d, J = 8.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H). 13C{ H} NMR (100
18
27
(
E)-2-Fluoro-4-phenyl-1-buten-1-yl(phenyl)iodonium Tetrafluor-
1
oborate (2h). The product was obtained as white solids. Mp: 111−
1
1
14 °C. Yield: 161 mg (73%). H NMR (400 MHz, CDCl ): δ = 2.96
MHz, CDCl ): δ = 13.8, 21.0, 22.4, 25.5, 28.6, 29.06, 29.13, 29.3, 31.6,
3
3
(
1
1
t, J = 7 Hz, 2H), 3.16 (dt, J = 7, 21.6 Hz, 2H), 6.54 (d, J = 14.4 Hz,
31.8 (d, J = 24.7 Hz), 78.7 (d, J = 47.2 Hz), 108.3, 132.7, 134.6, 143.4,
175.4 (d, J = 284.1 Hz). 19F NMR (376 MHz, CDCl ): δ = −65.4,
H), 7.22−7.38 (m, 7H), 7.48 (d, J = 8 Hz, 2H), 7.56 (t, J = 8 Hz,
3
H). 13C{ H} NMR (100 MHz, CDCl ): δ = 31.2, 33.3 (d, J = 24.7
1
−146.3.
3
Hz), 84.9 (d, J = 39.5 Hz), 115.5, 126.9, 128.8, 128.9, 131.9, 132.2,
1
(E)-4-Chlorophenyl(2-fluoro-1-dodecen-1-yl)iodonium Tetra-
35.0, 139.6, 171.4 (d, J = 277.2 Hz). 19F NMR (376 MHz, CDCl ): δ
fluoroborate (3b). The product was obtained as yellowish solids.
3
+
1
−
67.1, −146.4. HRMS (FAB, double focusing): m/z [M − BF ] calcd
Mp: 96−99 °C. Yield: 174 mg (68%). H NMR (400 MHz, CDCl
3
): δ
4
for C H FI 353.0197, found 353.0202.
= 0.89 (t, J = 7 Hz, 3H), 1.18−1.30 (m, 14H), 1.48−1.60 (m, 2H),
2.79 (dt, J = 7.6, 22.0 Hz, 2H), 6.70 (d, J = 14.0 Hz, 1H), 7.44 (d, J =
8.8 Hz, 2H), 7.89 (d, J = 8.8 Hz, 2H). 13C{ H} NMR (100 MHz,
16
15
(E)-2-Fluoro-10-methoxycarbonyl-1-decen-1-yl(phenyl)iodonium
1
Tetrafluoroborate (2i). The product was obtained as a yellow oil.
Yield: 187 mg (74%). H NMR (400 MHz, CDCl ): δ = 1.23−1.32
(
1
CDCl ): δ = 14.0, 22.5, 25.6, 28.7, 29.2, 29.3, 29.4, 31.7, 31.9 (d, J =
3
3
m, 8H), 1.51−1.62 (m, 4H), 2.30 (t, J = 7.5 Hz, 2H), 2.80 (dt, J = 7.5,
24.0 Hz), 78.9 (d, J = 48.0 Hz), 108.9, 132.0, 136.1, 139.3, 176.2 (d, J
E
J. Org. Chem. XXXX, XXX, XXX−XXX