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K.V. Raghavendra Rao, Y. Vallee / Tetrahedron 72 (2016) 4442e4447
4445
Fig. 1. 1H NMR Spectra of fluoride 1e, sulfonium 3e and benzothiepinone 5e.
performed on Macherey-Nagel Silica Gel 60 M (0.04e0.063 mm)
using a forced flow of eluents. Concentration under reduced pres-
sure was performed by rotary evaporation at 40 ꢁC at appropriate
pressure and by exposing the product to high vacuum at room
temperature if necessary.
14.2 (CH3). HRMS-ESIþ (m/z): calcd for C19H31O4 [MþH]þ 323.2222,
found 323.2217. FTIR (neat) ṽ 2951, 2848, 1698, 1663, 1605, 1412,
1226, 1154, 717.
3.3.2. 1-(3-Iodo-4-methoxyphenyl)decan-1-one (4l). Colorless oil,
1H NMR spectra were recorded at 300, 400 or 500 MHz. 13C NMR
spectra were recorded at 75, 100 or 125 MHz. 19F spectra were
recorded at 376 MHz. Chemical shifts for 1H spectra are values from
228 mg, 59%. 1H NMR (400 MHz, CDCl3)
d
8.37 (d, J¼2.0 Hz, 1H,
ArH), 7.94 (dd, J¼8.5, 2.0, Hz, 1H, ArH), 6.83 (d, J¼8.5 Hz, 1H, ArH),
3.93 (s, 3H, OCH3), 2.87 (t, J¼7.4 Hz, 2H, CH2), 1.70 (quint, J¼7.4 Hz,
2H, CH2), 1.40e1.18 (m, 12H), 0.87 (t, J¼7.0 Hz, 3H, CH3). 13C NMR
tetramethylsilane in CDCl3
spectra are values from CDCl3 (
spectra are values from CCl3F (
(
d
0.00 ppm). Chemical shifts for 13C
77.16 ppm). Chemical shifts for 19
0.00 ppm). NMR spectra were
d
F
(100 MHz, CDCl3) d 198.0, 161.6, 140.0 (CH), 131.9, 130.3 (CH), 110.1
d
(CH), 86.0 (C-I), 56.7, 38.4, 32.0, 29.5, 29.4 (2), 24.5, 22.7, 14.2 (CH3).
HRMS-ESIþ (m/z): calcd for C17H26O2I [MþH]þ 389.0977, found
389.0987. FTIR (neat) ṽ 2943, 2920, 2847, 1675, 1585, 1463, 1263,
1252, 1218, 807.
recorded at room temperature at the frequency stated and run as
dilute solution in CDCl3. Chemical shifts are reported in ppm with
the solvent resonance as internal standard. Data are reported as
follows: s¼singlet, d¼doublet, t¼triplet, q¼quartet, quint¼quintet,
m¼multiplet, coupling constants (Hz) and integration. Assign-
ments of 13C spectra were made with the aid of DEPT experiments.
High resolution mass spectra (HRMS) were recorded on a TOF mass
spectrometer. Melting points were measured using a micromelting
point apparatus.
3.3.3. Cyclohexyl(3-iodo-4-methoxyphenyl)methanone (4m). Clear
oil, 65 mg, 19%. 1H NMR (400 MHz, CDCl3)
d
8.36 (d, J¼2.0 Hz, 1H,
ArH), 7.94 (dd, J¼8.5, 2.0, Hz, 1H, ArH), 6.84 (d, J¼8.5 Hz, 1H, ArH),
3.94 (s, 3H, OCH3), 3.16 (tt, J¼11.0, 3.0 Hz, 1H, CH), 1.88e1.80 (m,
4H), 1.52e1.26 (m, 6H). 13C NMR (100 MHz, CDCl3)
d 201.3, 161.6,
140.1 (CH), 131.1, 130.5 (CH), 110.2, 86.1 (C-I), 56.7 (CH), 45.4 (CH),
29.6 (CH2), 26.0 (CH2), 25.9 (CH2). HRMS-ESIþ (m/z): calcd for
C14H18O2I [MþH]þ 345.0351, found 345.0363. FTIR (neat) ṽ 2918,
2848, 1675, 1652, 1586, 1252, 1194, 1014, 798.
3.2. General procedure for FriedeleCrafts acylation reactions
and rearrangements
The acid fluoride (1 mmol) in dichloromethane (3.0 ml) was
treated with TMSOTf (1.2 mmol), followed by addition of an elec-
tron rich aromatic compounds (1 mmol). The reaction mixture was
stirred at room temperature and monitored by TLC. After comple-
tion of the reaction, DCM was evaporated and the product was
purified by silica gel column chromatography using pentane/ethyl
acetate mixtures as eluent.
3.3.4. Cyclopentyl(3-iodo-4-methoxyphenyl)methanone (4o). Clear
oil, 105 mg, 32%. 1H NMR (400 MHz, CDCl3)
d
8.39 (d, J¼2.0 Hz, 1H,
ArH), 7.95 (dd, J 8.6, 2.0, Hz, 1H, ArH), 6.84 (d, J¼8.6 Hz, 1H, ArH),
3.94 (s, 3H, OCH3), 3.61 (quint, J¼8.0 Hz, 1H, CH), 1.94e1.83 (m, 4H),
1.77e1.58 (m, 4H). 13C NMR (100 MHz, CDCl3)
d 200.3, 161.5, 140.3
(CH), 131.7, 130.7 (CH), 110.1 (CH), 86.0 (C-I), 56.7 (CH), 46.1 (CH),
30.1 (CH2), 26.4 (CH2). HRMS-ESIþ (m/z): calcd for C13H16O2I
[MþH]þ 331.0195, found: 331.0201. FTIR (neat) ṽ 2943, 2864, 1667,
1586, 1486, 1251, 1200, 1044, 807.
3.3. Results and spectroscopic data
3.3.5. 1,16-Di(thiophen-2-yl)hexadecane-1,16-dione
(4p). White
3.3.1. 1-(2,4,6-Trimethoxyphenyl)decan-1-one (4e). Colorless oil,
solid, mp 73.4e73.6 ꢁC, 313 mg, 75%. 1H NMR (400 MHz, CDCl3)
177 mg, 55%. 1H NMR (400 MHz, CDCl3)
d 6.09 (s, 2H, ArH), 3.80 (s,
d
7.70 (dd, J¼3.5, 1.0, Hz, 1H, ArH), 7.60 (dd, J¼4.5, 1.2, Hz, 1H, ArH),
3H, OCH3), 3.75 (s, 6H, OCH3), 2.70 (t, J¼7.6 Hz, 2H, CH2), 1.63 (quint,
7.11 (dd, J¼5.0, 4.0, Hz, 1H, ArH), 2.88 (t, J¼7.5 Hz, 2H, CH2), 1.74
J¼7.6 Hz, 2H, CH2), 1.36e1.19 (m, 12H), 0.87 (t, J¼7.0 Hz, 3H, CH3).
(quint, J¼7.4 Hz, 2H, CH2), 1.44e1.19 (m, 10H, CH2). 13C NMR
13C NMR (100 MHz, CDCl3)
d 205.0, 162.1, 158.1, 114.0, 90.7 (CH),
(100 MHz, CDCl3)
d 193.6, 144.7, 133.3 (CH), 131.7 (CH), 128.1 (CH),
55.8 (OCH3), 55.5 (OCH3), 45.1, 32.0, 29.6, 29.5, 29.4, 29.3, 24.0, 22.7,