(E )-1,1,1-Trifluoro-4-(phenylsulfinyl)but-3-ene-2,2-diol (2).
Yield 76%, white solid, mp 156–158 ЊC. Found C, 45.02; H,
3.53. Calc for C10H9F3O3S C, 45.11; H, 3.41%; νmax(Nujol)/cmϪ1
127.8, 127.6, 127.5, 115.4 (J 292.0), 115.2 (J 292.3), 115.0
(J 292.2), 114.9 (J 292.3), 66.2, 66.0, 65.5, 64.7, 49.3, 49.0, 48.9,
48.9, 48.7, 48.1, 47.9, 47.1, 47.0, 46.7, 46.6, 46.4, 44.9, 44.8,
44.7, 44.5.
1675 (C᎐C), 3180 (OH). Sulfoxide 2 exist in keto-form in
᎐
CDCl3. δH (400 MHz, CDCl3) 7.94 (2 H, m, Ph), 7.79 (1 H, d,
J 15.3, CH᎐), 7.76 (1 H, m, Ph), 7.67 (2 H, m, Ph), 7.34 (1 H, d,
Preparation of sulfonium salt 10
᎐
J 15.3, CH᎐). δ (100 MHz, CDCl ) 177.6 (J 37.8), 137.9, 135.7,
᎐
C
3
Compound 10 could not be purified for analysis, and slowly
decomposed at room temperature. It was stored in the freezer
until it was used. To a solution of vinyl sulfoxide 2 (0.1 mmol)
in CDCl3 (0.5 ml) in an NMR tube TFAA (0.2 mmol) was
added. The mixture was stirred for 1 min at room temperature
and NMR spectra were taken (CF3CO2H is a by-product that is
seen in the 1H and 13C NMR).
129.5, 127.8, 127.7, 127.6, 121.8 (J 289.9).
Preparation of Diels–Alder cycloadducts 4–9
To a solution of vinyl sulfoxide 2 (1 mmol) in CH2Cl2 (5 ml) the
corresponding diene (2 mmol) was added. The mixture was
stirred at room temperature (in the case of the reaction with
anthracene reactions were carried out at 40 ЊC with stirring).
Removal of the solvent under reduced pressure afforded
products, which were purified by column chromatography over
silica gel using hexane as eluent.
Phenyl[(trifluoroacetyl)oxy][(1E )-4,4,4-trifluoro-3-oxobut-1-
enyl]sulfonium trifluoroacetate (10). δH (400 MHz, CDCl3) 12.3
(2 H, s, CF COOH), 8.55 (1 H, d, J 14.4, CH᎐), 8.20 (2 H, m,
᎐
3
Ph), 7.93 (3 H, m, Ph), 7.81 (1 H, d, J 14.4, CH᎐). δ (100 MHz,
᎐
C
1-Cyclohexa-1,4-dien-1-yl-2,2,2-trifluoroethanone (5). Yield
CDCl3) 177.6 (J 37.8), 166.0 (J 27.2), 164.5 (J 40.2), 160.3
(J 42.3), 148.1, 139.5, 135.6, 130.7, 129.0, 128.4, 121.6 (J 289.9),
118.9 (J 290.1), 115.6 (J 287.3), 115.4 (J 288.0).
1
81%. The H and 13C NMR data of 5 were in agreement with
the literature.12
1-(4,5-Dimethylcyclohexa-1,4-dien-1-yl)-2,2,2-trifluoro-
ethanone (6). Yield 85%. The 1H and 13C NMR data of 6 were in
agreement with the literature.12
Reaction of sulfonium salt 10 with isoprene and cyclopentadiene
To a solution of vinyl sulfoxide 2 (1 mmol) in absolute CH2Cl2
(5 ml) TFAA (2 mmol) was added. The mixture was stirred at
room temperature 10 min. Then cyclopentadiene (3 mmol) or
isoprene (3 mmol) was added dropwise during 10 min at Ϫ10 ЊC
in the case of isoprene and Ϫ35 ЊC in the case of cyclopenta-
diene. The temperature of the reaction mixture was slowly
increased to 20 ЊC. Removal of the solvent under reduced
pressure afforded products, which were purified by column
chromatography over silica gel using hexane as eluent.
The reaction of 2 with isoprene gave a mixture of regio-
isomers 7a/7b (by NMR 5 : 1, crude; 4 : 1 after purification
by chromatography), yield 80%, colourless oil. The 1H and 13
C
NMR data of 7a/7b were in agreement with the literature.12
1-[1,8-Dimethyltetracyclo[6.6.2.0.2,7.09,14]hexadeca-
2,4,6,9,11,13,15-heptaen-15-yl]-2,2,2-trifluoroethan-1-one (8).
Yield 63%. The 1H and 13C NMR data of 8 were in agreement
with the literature.12
The reaction of 10 with isoprene gave a mixture of regio-
isomers 7a/7b (by NMR 1 : 1.5, crude; 1 : 1.3 after purification
by chromatography), yield 67%, colourless oil.
The reaction of 2 with cyclopentadiene gave a mixture of
stereoisomers 1-[3-endo-(phenylsulfinyl)bicyclo[2.2.1]hept-5-en-
2-exo-yl]-2,2,2-trifluoroethanones (9a/9b) and 1-[3-exo-(phen-
ylsulfinyl)bicyclo[2.2.1]hept-5-en-2-endo-yl]-2,2,2-trifluoro-
ethanone (9c/9d) (by NMR 7 : 9 : 37 : 47 after purification by
chromatography), yield 72%, colourless oil; Found for mixture
of isomers: C, 57.14; H, 4.01. Calc for C15H13F3O3S C, 57.32; H,
The reaction of 10 with cyclopentadiene gave a mix-
ture of stereoisomers 1-[3-endo-(phenylsulfinyl)bicyclo[2.2.1]-
hept-5-en-2-exo-yl]-2,2,2-trifluoroethanones (9a/9b) and 1-[3-
exo-(phenylsulfinyl)bicyclo[2.2.1]hept-5-en-2-endo-yl]-2,2,2-tri
fluoroethanone (9c/9d) (by NMR 19 : 19 : 31 : 31 after purifi-
cation by chromatography), after purification, yield 85%,
colourless oil; Found for mixture of isomers: C, 57.19; H, 4.06.
Calc for C15H13F3O3S C, 57.32; H, 4.17 %; νmax(Nujol)/cmϪ1
4.17 %; νmax(Nujol)/cmϪ1 1760–1770 (C᎐O).
᎐
(9a). δH (400 MHz, CDCl3) 7.68–7.46 (5 H, m, Ph), 6.41 (1 H,
dd, J 3.5, J 5.3, CH᎐), 6.33 (1 H, dd, J 3.0, J 5.3, CH᎐), 3.94
1760–1770 (C᎐O).
᎐
᎐
᎐
(1 H, dd, J 3.2, J 4.4, CH-SOPh), 3.53 (1 H, br s, CH), 3.27
(1 H, br s, CH), 3.08 (1 H, br d, J 4.4, CH-COCF3), 1.61 (1 H,
ddd, J 9.6, J 1.4, J 1.4, CH-7b), 1.49 (1 H, br d, J 9.6, CH-7a).
Acknowledgements
Financial support from the Russian Fundamental Investigation
1
1
(9b). δH (400 MHz, CDCl3) 7.68–7.46 (5 H, m, Ph), 6.57 (1 H,
Foundation (Grants
00–03–32760 and
00–03–32763) is
dd, J 3.0, J 5.6, CH᎐), 6.42 (1 H, dd, J 3.1, J 5.6, CH᎐), 3.69
᎐
᎐
gratefully acknowledged.
(1 H, dd, J 3.2, J 4.4, CH-SOPh), 3.39 (1 H, br s, CH), 3.38
(1 H, br d, J 4.4, CH-COCF3), 3.06 (1 H, br s, CH), 1.94 (1 H,
br d, J 9.2, CH-7a), 1.44 (1 H, ddd, J 9.2, 1.5, J 1.4, CH-7b).
References
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(9c). δH (400 MHz, CDCl3) 7.68–7.46 (5 H, m, Ph), 6.27 (1 H,
dd, J 3.5, J 5.6, CH᎐), 5.87 (1 H, dd, J 3.3, J 5.6, CH᎐), 3.61
᎐
᎐
(1 H, br s, CH), 3.33 (1 H, dd, J 4.5, J 3.4, CH-COCF3), 3.30
(1 H, br d, J 4.5, CH-SOPh), 3.23 (1 H, br s, CH), 2.01 (1 H, br
d, J 9.4, CH-7a), 1.65 (1 H, ddd, J 9.4, J 1.8, J 1.4, CH-7b).
(9d). δH (400 MHz, CDCl3) 7.68–7.46 (5 H, m, Ph), 6.40 (1 H,
dd, J 3.5, J 5.5, CH᎐), 5.88 (1 H, dd, J 3.3, J 5.5, CH᎐), 3.81
᎐
᎐
(1 H, dd, J 4.4, J 3.5, CH-COCF3), 3.45 (1 H, br s, CH), 3.43
(1 H, br s, CH), 3.15 (1 H, br d, J 4.4, CH-SOPh), 2.18 (1 H, br
d, J 9.6, CH-7a), 1.55 (1 H, ddd, J 9.6, J 2.0, J 1.4, CH-7b).
For mixture of isomers δC (100 MHz, CDCl3) 189.4 (J 34.8),
189.2 (J 34.7), 188.6 (J 34.8), 188.5 (J 34.6), 138.9, 138.7, 138.5,
138.1, 135.6, 135.5, 135.5, 135.1, 134.7, 134.4, 134.4, 134.2,
134.0, 133.9, 132.6, 132.5, 129.4, 129.3, 129.0, 128.9, 127.9,
J. Chem. Soc., Perkin Trans. 1, 2002, 2554–2560
2559