524 JOURNAL OF CHEMICAL RESEARCH 2011
1H), 2.40 (s, 1H), 1.45–1.32 (m, 3H), 1.18 (s, 7H), 0.80 (t, J = 10.8
Hz, 3H); 13C NMR (75 MHz, CDCl3): δ ppm 133.0, 129.5, 129.1,
127.2, 70.0, 37.2, 36.6, 31.7, 29.3, 25.7, 22.6, 14.0.
selenides in PEG-400/H2O in the presence of sodium dithion-
ite. Compared to previous reported methodologies, the present
protocol features high regioselectivity and yield, reasonably
rapid reaction rate, simple workup, and use of the cheap and
odourless reagent. We believe that this procedure provides a
valuable addition to current methodologies.
1
1-Butoxy-3-(phenylselanyl)propan-2-ol (2h)4: Oil; H NMR (300
MHz, CDCl3): δ ppm 7.52–7.49 (m, 2H), 7.25–7.22 (m, 3H), 3.89 (s,
1H), 3.52–3.39 (m, 4H), 3.10–3.05 (m, 2H), 2.87 (s, 1H), 1.56–1.48
(m, 2H), 1.38–1.25 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H); 13C NMR
(75 MHz, CDCl3): δ ppm 132.4, 129.7, 129.1, 127.0, 73.3, 71.4, 69.2,
31.7, 31.6, 29.7, 19.3.
Experimental
trans-2-(Phenylselanyl)cyclohexanol (2i)13: Oil; 1H NMR (300
MHz, CDCl3): δ ppm 7.63–7.58 (m, 2H), 7.32–7.25 (m, 3H), 3.39–
3.25 (m, 1H), 3.06 (s, 1H), 2.94–2.87 (m, 1H), 2.20–2.13 (m, 2H),
1.74–1.59 (m, 2H), 1.43–1.26 (m, 4H); 13C NMR (75 MHz, CDCl3):
δ ppm 136.2, 128.9, 128.0, 126.7, 72.2, 53.2, 33.9, 33.1, 26.7, 24.5.
Chemicals and apparatus
All reagents were purchased and used without further purification.
NMR spectroscopy was performed on a Bruker-300 spectrometer
using CDCl3 as the solvent with tetramethylsilane (TMS) as an inter-
nal standard at room temperature. Ultrasonication was performed in a
SY-5200DH water bath of a laboratory ultrasonic cleaner (with a fre-
quency of 55 kHz and a constant output power of 150 W; Shanghai
Shengyuan ultrasonic instrument Co., Ltd.). The reaction flask was
located in the water bath of the ultrasonic cleaner, where the surface
of reactants is slightly lower than the level of the water. The reaction
temperature was controlled at 22–25 °C by addition or removal of
water from ultrasonic bath.
(R)-1-Chloro-3-(phenylselanyl)propan-2-ol (2j)13: [α]D −21.9 (c
25
2.41, CHCl3). HPLC analysis using a Chiracel OJ-H column [iPrOH/
hexane: 1/99; flow rate: 0.8 mL min−1; detector: 254 nm]. Retention
time: tR(R) 15.50 min, tR (S) 16.71 min.
(S)-1-Chloro-3-(phenylselanyl)propan-2-ol (2k)18: [α]D +22.4 (c
25
1.31, CHCl3). HPLC analysis using a Chiracel OJ-H column [iPrOH/
hexane: 1/99; flow rate: 0.8 mL min−1; detector: 254 nm]. Retention
time: ts(R) 15.21 min, ts (S) 16.49 min.
Synthesis of β-hydroxy selenides; general procedure
We are grateful for financial support from the Science
and Technology Department of Zhejiang Province (No.
2010C33061) and the Wenzhou Science & Technology Bureau
Program (No. S20100004).
A mixture of epoxides 1 (0.5 mmol) and 1,2-diphenyldiselenide
(0.2 mmol) (0.2 mmol), sodium dithionite (3 equiv., 0.6 mmol) and
K2CO3 (1.5 equiv., 0.3 mmol) was irradiated under ultrasound in PEG-
400/H2O (4 mL, volume ratio is 3:1) at room temperature (22–25 °C)
for the appropriate time indicated in Table 3. After completion of the
reaction as indicated by TLC, ethyl acetate (10 mL) was then added to
the mixture. The mixture was washed with brine. The organic layer
was separated and dried with sodium sulfate, filtered and concen-
trated. The residue was purified by silica gel chromatography using
ethyl acetate-hexane as eluent to afford the pure product of 2. The
physical and spectral data of compounds 2a–k are as follows.
1-Phenoxy-3-(phenylselanyl)propan-2-ol (2a)10: Oil, 1H NMR (300
MHz, CDCl3): δ ppm 7.52–7.19 (m, 7H), 6.94–6.83 (m, 3H), 4.11–
4.07 (m, 1H), 4.01–3.96 (m, 2H), 3.17 (dd, J = 12.9 and 6.9 Hz, 1H),
3.10 (dd, J = 12.9 and 6.0 Hz, 1H), 3.01 (s, 1H); 13C NMR (75 MHz,
CDCl3): δ ppm 158.2, 132.6, 129.3, 129.2, 129.0, 127.1, 121.0, 114.4,
70.4, 68.9, 31.5.
Received 13 July 2011; accepted 29 August 2011
Paper 1100792 doi: 10.3184/174751911X13149579868111
Published online: 30 September 2011
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1-Phenyl-2-(phenylselanyl)ethanol (2b)13: Oil, 1H NMR (300 MHz,
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3.30–3.23 (m, 1H), 3.19–3.09 (m, 1H), 2.92 (s, 1H); 13CNMR (75MHz,
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38.3.
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1-(Phenylselanyl)propan-2-ol (2c)13: Oil, 1H NMR (300 MHz,
CDCl3): δ ppm 7.43–7.41 (m, 2H), 7.15–7.13 (m, 3H), 3.81–3.75 (m,
1H), 2.99 (dd, J = 12.6 and 8.4 Hz, 1H), 2.80 (dd, J = 12.6 and 4.6 Hz,
1H), 2.60 (s, 1H), 1.35–1.16 (m, 3H); 13C NMR (75 MHz, CDCl3):
δ ppm 133.2, 129.3, 129.2, 127.5, 66.1, 38.5, 22.8.
1
1-(Phenylselanyl)dec-9-en-2-ol (2d)13: Oil, H NMR (300 MHz,
CDCl3): δ ppm 7.52–7.50 (m, 2H), 7.25–7.21 (m, 3H), 5.83–5.74 (m,
1H), 5.01–4.90 (m, 2H), 3.67–3.66 (m, 1H), 3.10 (dd, J = 12.6 and 9.0
Hz, 1H), 2.87 (dd, J = 12.6 and 4.2 Hz, 1H), 2.59 (s, 1H), 2.05–1.98
(m, 2H), 1.52–1.48 (m, 2H), 1.42–1.28 (m, 8H); 13C NMR (75 MHz,
CDCl3): δ ppm 139.0, 132.78, 129.5, 129.0, 127.0, 114.1, 69.9, 37.0,
36.5, 33.7, 29.3, 28.9, 28.7, 25.9.
1-(Allyloxy)-3-(phenylselanyl)propan-2-ol (2e)18: Oil, 1H NMR
(300 MHz, CDCl3): δ ppm 7.57–7.50 (m, 2H), 7.28–7.24 (m, 3H),
5.87–5.83 (m, 1H), 5.29–5.16 (m, 2H), 3.98–3.92 (m, 3H), 3.54–3.46
(m, 2H), 3.09–3.03 (m, 2H), 2.75 (s, 1H); 13C NMR (75 MHz, CDCl3):
δ ppm 134.1, 132.7, 129.6, 129.1, 127.1, 117.4, 72.7, 72.2, 69.4,
32.1.
2-Hydroxy-3-(phenylselanyl)propyl methacrylate (2f)18: Oil; 1H
NMR (300 MHz, CDCl3): δ ppm 7.45–7.17 (m, 5H), 6.02 (s, 1H),
5.49 (s, 1H), 4.20–4.10 (m, 2H), 3.95–3.89 (m, 1H), 3.02 (dd, J = 12.9
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and 5.1 Hz, 1H), 2.92 (dd, J = 12.9 and 7.6 Hz, 1H), 1.83 (s, 3H); 13
C
NMR (75 MHz, CDCl3): δ ppm 167.2, 135.6, 132.8, 129.1, 129.0,
127.2, 125.80, 68.5, 67.0, 32.0, 18.4.
1-(Phenylselanyl)octan-2-ol (2g)2: Oil; 1H NMR (300 MHz,
CDCl3): δ ppm 7.47–7.43 (m, 2H), 7.20–7.16 (m, 3H), 3.60–3.57 (m,
1H), 3.04 (dd, J = 12.6 and 3.6 Hz, 1H), 2.79 (dd, J = 12.6 and 8.4 Hz,
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