N. Chumachenko, P. Sampson / Tetrahedron 62 (2006) 4540–4548
4547
2-(4-Methylphenylsulfonyl)propan-1-ol (12d) (assigned
from the mixture with 11d): 1H NMR (CDCl3) d 1.24
(d, JZ6.4 Hz, 3H, O–CHCH3, coincides with 11d), 2.45 (s,
3H, CH3-Ar, coincides with 11d), 3.21–3.37 (masked by
11d) (m, 1H, SO2–CHCH3), 3.73 (dd, JZ12.1, 5.0 Hz, 1H,
CHCHAHBOH), 3.98 (dd, JZ12.1, 6.2 Hz, 1H, CHCHA-
HBOH), 7.39 (app. d, JZ8.5 Hz, 2H, Ar, coincides with
11d), 7.76 (app. d, JZ8.3 Hz, 2H, Ar); 13C NMR (CDCl3) d
11.4, 18.9, 61.3, 61.8, 128.9, 130.0, 134.1, 139.7.
and was then subjected to column chromatography (silica,
EtOAc/hexanes 1.5:1) to afford the title compound 7a as a
colorless oil (1.95 g, 12.0 mmol, 30%). 1H NMR (CDCl3) d
3.22 (t, JZ6.0 Hz, 1H, OH), 3.26–3.31 (m, 2H, H2), 4.02–
4.10 (m, 2H, H1), 5.68 (br d, JZ10.0 Hz, 1H, H6b), 5.77 (br
d, JZ16.9 Hz, 1H, H6a), 6.47 (dd, JZ14.9, 0.6 Hz, 1H, H3),
6.48 (dddd, JZ16.9, 10.9, 10.0, 0.6 Hz, 1H, H5), 7.21 (br
dd, JZ15.0, 10.8 Hz, 1H, H4); 13C NMR (CDCl3) d 56.4,
57.4, 129.0 (two signals coincide), 132.5, 144.3.
4.4. Synthesis of 1,3-butadienyl sulfone derivatives
4.4.3. 1-((E)-Buta-1,3-diene-1-sulfonyl)propan-2-ol (7b).
The title compound 7b was prepared from propylene oxide
(8.4 mL, 120 mmol, 3 equiv) according to the procedure
described above for 7a, as a colorless oil (2.14 g,
4.4.1. Zinc (Z)-buta-1,3-diene-1-sulfinate dihydrate (15).
2,5-Dihydrothiophene-1,1-dioxide (butadiene sulfone, 4)
(4.73 g, 40.0 mmol, 1.00 equiv) was dissolved in anhydrous
THF (120 mL) under argon, and cooled in a dry ice/acetone
bath. n-BuLi (2.5 M in hexanes, 16.00 mL, 40.0 mmol,
1.00 equiv) was added dropwise over 25 min, maintaining
the reaction temperature below K68 8C. Initially a yellow
solution was observed and then a cream precipitate formed.
The addition of n-BuLi was stopped after a bright red
coloration had developed in the reaction mixture. The
reaction mixture was allowed to warm up to K50 8C, and
then water (30 mL) and hydroquinone (ca. 0.05 g) were
added. The precipitate immediately dissolved, and the red
coloration disappeared. The organic solvents were removed
in vacuo, resulting in a light yellow aqueous solution (ca.
30 mL) of lithium (Z)-buta-1,3-diene-1-sulfinate. The
solution was cooled in ice, and a solution of ZnCl2
(2.705 g, 19.85 mmol) in water (5 mL) was added dropwise
with stirring. The reaction mixture was left in an ice bath for
20 min, and then the resulting white precipitate was filtered,
washed with ice-cold water (20 mL) followed by dichloro-
methane (20 mL) and dried in vacuo. The title compound 15
was obtained as a cream solid (4.80 g, 14.3 mmol, 72%), mp
128–130 8C. 1H NMR (400 MHz, DMSO-d6) d 3.43 (s, 4H,
H2O), 5.26 (br d, JZ10.0 Hz, 2H, HcisHtransC]CH), 5.34
(br d, JZ16.8 Hz, 2H, HcisHtransC]CH), 6.02 (br d, JZ
10.0 Hz, 2H, ]CH–SO2), 6.26 (dd, JZ11.2, 10.4 Hz, 2H,
CH]CH–SO2), 6.94 (dddd, JZ16.8, 11.2, 10.1, 1.0 Hz,
2H, CH2]CH); 13C NMR (DMSO-d6) d 121.8, 131.2,
131.6, 146.6. Anal. Calcd for C8H14O6S2Zn: C, 28.62; H,
4.20; S, 19.10; Zn, 19.48. Found: C, 28.04; H, 4.33; S,
18.61; Zn, 19.01.
1
12.1 mmol, 30%). H NMR (CDCl3) d 1.31 (d, JZ6.4 Hz,
3H, CH3), 3.09 (dd, JZ14.4, 2.8 Hz, 1H, H2), 3.17 (dd, JZ
14.5, 8.7 Hz, 1H, H2), 3.21 (d, JZ2.8 Hz, 1H, OH), 4.39
(app. dqt JZ9.0, 6.3, 2.8 Hz, 1H, H1), 5.69 (br d, JZ
10.0 Hz, 1H, H6b), 5.77 (br d, JZ16.7 Hz, 1H, H6a), 6.43 (br
d, JZ15.0 Hz, 1H, H3), 6.47 (dddd, JZ16.9, 10.8, 10.0,
0.5 Hz, 1H, H5), 7.22 (br dd, JZ15.0, 10.9 Hz, 1H, H4); 13
C
NMR (CDCl3) d 22.9, 62.4, 62.7, 128.7, 129.4, 132.4, 144.8.
Acknowledgements
We thank Kent State University for financial support and
Yehor Novikov for valuable discussions.
Supplementary data
Supplementary data associated with this article can be
043. Synthetic procedures, 1H and 13C NMR data for
compounds 9b–d, 11b,c, 11d (synthesis from 8d), 6a,b, 16,
17, 18a, cis-18b, trans-18b and 19; partial 1H and 13C NMR
1
data for compounds 12b,c, 13b,c; copies of H and 13C
NMR spectra of compounds 9b, 15, 6a,b, 7a,b, 17, a
mixture of 16/17 (1/1.35), 18a, cis-18b, trans-18b and 19.
References and notes
4.4.2. 1-((E)-Buta-1,3-diene-1-sulfonyl)ethanol (7a). The
light yellow aqueous solution (ca. 30 mL) of Li (Z)-buta-
1,3-diene-1-sulfinate (40.0 mmol) obtained in experiment
Section 4.4.1 was added dropwise with stirring and cooling
in ice to the glass pressure vessel containing ZnCl2 (2.67–
2.84 g, 19.6–20.8 mmol, 0.49–0.52 equiv) in water
(60 mL). A white precipitate of zinc (Z)-buta-1,3-diene-1-
sulfinate was formed. Ethylene oxide (6 mL, 120 mmol,
3 equiv) was added, and the solution was heated with
stirring for 3 h at 70–75 8C. The resulting reaction mixture
was cooled to rt and filtered. The precipitate was washed
with water (3!20 mL) and the combined aqueous filtrate
was extracted with dichloromethane (4!100 mL). The
combined dichloromethane extracts (ca. 400 mL) were
treated with 2,6-di-tert-butyl-4-methylphenol (0.200 g,
0.908 mmol), dried (MgSO4), filtered, concentrated to a
volume of ca. 150 mL and treated with DMAP (0.500 g,
4.09 mmol). The resulting solution was kept at rt for 36 h,
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