β-Phenylselenoethanol, an efficient reagent for the one-pot synthesis of aryl vinyl ethers

Article abstract of DOI:10.3184/030823408X360355

β-Phenylselenoethanol was treated with phenols under Mitsunobu conditions and subsequent oxidation-elimination with 30% hydrogen peroxide furnished aryl vinyl ethers with good yields (85-90%) in a one-pot, two-step transformation.

Full text of DOI:10.3184/030823408X360355

JOURNAL OF CHEMICAL RESEARCH 2008
OCTOBER, 595–597
RESEARCH PAPER 595
b-Phenylselenoethanol, an efficient reagent for the one-pot synthesis of
aryl vinyl ethers
Gui-Yun Fu*, La-Mei Yu, Xue-Chun Mao and Dan Wu
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022, P. R. China
b-Phenylselenoethanol was treated with phenols under Mitsunobu conditions and subsequent oxidation-
elimination with 30% hydrogen peroxide furnished aryl vinyl ethers with good yields (85–90%) in a one-pot, two-
step transformation.
Keywords: aryl vinyl ether, β-phenylselenoethanol, phenol, Mitsunobu reaction, oxidation–elimination
Aryl vinyl ethers with unsubstituted vinyl moiety, have
many synthetic applications1 and are employed as key
intermediates for the generation of new polymeric materials,2
as dienophiles for cycloaddition reactions such as [2 + 2],3
[2 + 4]4 and 1,3-dipolar cycloadditons,5 in cyclopropanations,6
in hydroformylations,7 and in natural product analogue
synthesis.8 Aryl vinyl ethers are usually prepared by the
dehydrohalogenation of aryl 2-haloethyl ethers,9–13 the
addition of phenols to acetylene14,15 or the copper(II)-promoted
coupling of arylboronic acids with phenols.16 Recently, the
use of vinyl acetate in an iridium-catalysed reaction with
phenols,17 and the transformations with copper(II) acetate
mediated coupling of 2,4,6-trivinylcyclotriboroxane as
a vinylboronic acid equivalent,18 and tributy(vinyl)tin19
with phenols have also been reported. However, most of
these methods involved difficulties such as harsh reactions,
laborious manipulation and low overall yields. In some cases
the reactions are unsuitable for sensitive substrates, vigorous
toxic compounds are used and some reagents are not readily
available. Therefore, exploring more efficient, experimentally
simple methodology is still interesting. Selenium-based
methods have been developed rapidly over the past few
years and are now a very important tool for introducing new
functional groups into organic substrates under extremely mild
conditions.20 For example, the phenylseleno group is readily
converted to a leaving group giving access to a carbon–carbon
double bond via oxidation followed by β-elimination.21
b-Hydroxyalkyl selenides can be converted to allylic alcohols,
olefins, bromohydrins and vinyl selenides and epoxide.22 They
can be used to prepare tetrahydrofuran derivatives23 and some
important nature products, such as sphingosine, pancratistatin,
schweinfurthin B, spirotryprostatin B and siastatin B.24
Additionally, the Mitsunobu reaction of alcohols has been
extensively used in organic synthesis for the preparation of
esters, alcohols, aryl ethers, amine, and thioethers.25 Based on
these, we designed a novel, convenient, and efficient one-pot,
two-step route for the preparation of aryl vinyl ethers from
β-phenylselenoethanol (Scheme 1). This was treated with
phenols under Mitsunobu conditions followed by oxidation-
elimination with 30% hydrogen peroxide (Scheme 2).
The present method has advantages such as mild reaction
condition, convenient manipulation and good yields.
In general, β-hydroxyalkyl phenyl selenides were prepared
by the ring-opening of epoxides with benzeneselenolate ions
in ethanol at ambient temperature.26 However, the required
β-phenylselenoethanol was only obtained in 50% yield
by the reaction of sodium borohydride with an ethylene
epoxide in our trial. Interestingly, 2-chloroethanol was
reacted with phenylselenium anion to give the corresponding
β-phenylselenoethanol (2) in excellent yield (Scheme 1).
With 2 in hand, the preparation of intermediate 2-phenyl-
selenoethyl aryl ethers 4, was investigated from 2 with
phenol (3a). Firstly, the etherification reaction was carried
out with dicyclohexylcarbodiimide (DCC), but the yield of
corresponding product 4a was about 60%, and a large excess
of both DCC and substrate 3a were required. In addition,
forcing conditions were required involving heating to reflux
temperature in a solution of THF and triethylamine. This
prompted the search for a mild coupling reaction that would
consistently produce high yields. The alkylation of phenols
with alcohols effected by the triphenylphosphine/diethyl
azodicarboxylate (TPP/DEAD) system is well-documented in
the literature.27 Treatment of β-phenylselenoethanol (2) with
phenol (3a) with both standard reagents (TPP and DEAD)
afforded the corresponding 2-phenylselenoethyl phenyl
ether (4a) in 85% yield. After a series of experiments, the
best result with 94% yield of 4a was obtained when the N,
N-diisopropylethylamine (DIPEA) was added to the above
OH
Cl
NaH, THF
OH
PhSeNa
PhSeSePh
PhSe
rt, 24 h
HMPA, rt
1
2
Scheme 1
R
(3)
OH
R
H2O2
THF
R
O
OH
OCH=CH2
PhSe
PhSe
Ph3P/DEAD
DIPEA/THF, rt
2
4
5
Scheme 2
* Correspondent. E-mail: fuguiyunjxsd@163.com

596 JOURNAL OF CHEMICAL RESEARCH 2008
showed that the starting selenide was completely converted into the
corresponding selenated intermediates 4 (5–6 h). The mixture was
cooled to 0°C, the 30% hydrogen peroxide (1.0 ml, 11.6 mmol) was
added and. stirred until the reaction was finished as determined by
TLC (2–2.5 h). Powered K2CO3 (0.53 g, 5 mol) was then added to the
reaction mixture and stirred at room temperature and the mixture was
extracted with ether (20 × 3 ml). The combined organic layers were
washed with saturated NaHCO3 solution, brine and twice with water
and then dried over magnesium sulfate. The solvent was removed in
vacuo and the residue was purified by column chromatography on
silica gel using chloroform/hexane (10:90) as eluent to give pure
products 5a–k.
Table 1 Yields of aryl vinyl ethers 5a–5k
Entry
Phenol
R
Product
Yield/%a
1
2
3a
3b
3c
3d
3e
3f
3g
3h
3i
H
3a
3b
3c
3d
3e
3f
3g
3h
3i
89
90
88
87
86
86
90
88
86
88
85
3-CH3
3
4-t-C4H9
4-C6H5
4-Cl
4
5
6
2-Br
7
4-NO2
8
4-CN
9
4-CO2CH3
4-NHCOCH3
1-naphthol
Phenylvinylether(5a):Colourlessoil(Lit.10 oil);1HNMR:δ=7.15–
7.02 (m, 5H), 6.58 (dd, J = 14.0, 6.0 Hz, 1H), 4.70 (dd, J = 14.0,
1.5 Hz, 1H), 4.34 (dd, J = 6.0, 1.5 Hz, 1H); 13C NMR: δ = 154.0,
144.4, 133.1, 120.5, 115.3, 95.3; IR (neat): ν = 3045, 1640, 1623,
1600, 1495, 1230, 1212, 1165, 1155, 1145, 956, 942 cm-1.
10
11
3j
3k
3j
3k
aIsolated yield based on b-phenyselenoethanol (2).
3-Methylphenylvinylether(5b):Colourlessoil(Lit.14 oil);1HNMR:
δ = 6.83–7.20 (m, 4H), 6.50 (dd, J = 14.2, 6.5 Hz, 1H), 4.32 (dd,
Mitsunobu reaction system. Subsequent oxidation–elimination
of 4a with 30% hydrogen peroxide afforded phenyl vinyl ether
(5a) in 90% yield. In fact, although selenated intermediate
4a can be isolated and purified by chromatography, we have
found it most convenient to carry out the oxidation of the
material in one-pot. Mild oxidation of the selenide 4a and
elimination of the selenoxide provided 5a in 89% yield.
After successfully completing the initial studies on the
preparation of 5a, extension of this method to the synthesis
of other analogues in good yields was investigated (Table 1).
As seen from the Table 1, phenolic substrates having either
an electron-withdrawing or an electron-donating substituent
on the aromatic ring resulted in no obvious effect on the
reaction yields.The phenylseleno moiety, introduced in the
starting material is eliminated as benzeneseleninic acid in
the oxidation step. Diphenyl diselenide can be recovered in
60% yield by the addition of hydrazine monohydrate to the
aqueous extract.
J = 14.2, 1.8 Hz, 1H), 4.04 (dd, J = 6.5, 1.8 Hz, 1H), 2.30 (s, 3H); 13
C
NMR: δ = 154.6, 140.4, 132.1, 123.7, 122.6, 119.5, 115.3, 95.6, 21.5;
IR (neat): ν = 3050, 1640, 1622, 1600, 1500, 1380, 1230, 1160, 1149,
960, 822 cm-1.
4-t-Butylphenyl vinyl ether (5c): Colourless oil (Lit.19 oil); 1H NMR:
δ = 6.80 (d, J = 8.2 Hz, 2H), 7.18 (d, J = 8.2 Hz, 2H), 6.51 (dd,
J = 14.0, 6.2 Hz, 1H), 4.28 (dd, J = 14.0, 1.6 Hz, 1H), 4.24 (dd,
J = 6.2, 1.6 Hz, 1H), 1.31 (s, 9H); 13C NMR: δ = 157.1, 145.5, 133.7,
120.0, 117.3, 95.8, 38.0, 28.5; IR (neat): ν = 3045, 2940, 1640, 1600,
1600, 1500, 1378, 1240, 1180, 1149, 825 cm-1.
4-Vinyloxybiphenyl (5d): White solid, 52–53°C. (Lit.19 52–53°C);
1H NMR: δ = 7.66–7.34 (m, 7 H), 7.12–7.06 (m, 2 H), 6.80 (dd,
J = 13.5, 6.0 Hz, 1 H), 4.72 (dd, J = 13.5, 1.5 Hz, 1 H), 4.47 (dd,
J = 6.0, 1.5 Hz, 1 H); 13C NMR: δ = 156.6, 148.2, 140.6, 136.3,
129.0, 128.5, 127.2, 126.8, 117.5, 95.5; IR (KBr): ν = 3050, 3021,
1636, 1595, 1509, 1476, 1240, 1136, 826, 755 cm-1.
4-Chlorophenyl vinyl ether (5e): Colourless oil (Lit.10 oil); 1H NMR:
δ = 7.43 (d, J = 8.4 Hz, 2H), 7.01 (d, J = 8.4 Hz, 2H), 6.63 (dd,
J = 13.7, 6.1 Hz, 1H), 4.80 (dd, J = 13.7, 1.8 Hz, 1H), 4.51 (dd,
J = 6.1, 1.8 Hz, 1H); 13C NMR: δ = 156.2, 148.1, 132.8, 119.1, 116.1,
95.8; IR (neat): ν = 3048, 1635, 1595, 1475, 1232, 1165, 1142, 1058,
1002, 955, 834 cm-1.
In summary, we have developed a novel and convenient
method for the preparation of aryl vinyl ethers in good yield in
a one-pot, two-step transformation employing the Mitsunobu
reaction of β-phenylselenoethanol with phenols followed by
oxidation-elimination.
2-Bromophenyl vinyl ether (5f): Colourless oil (Lit.18 oil); 1H NMR:
δ = 7.67–7.65 (m, 1H), 7.42–7.36 (m, 1H), 7.21–7.18 (m, 1H),
7.10–7.06 (m, 1H), 6.80 (dd, J = 6.3, 13.5 Hz, 1H), 4.68 (dd, J = 1.8,
13.5 Hz, 1H), 4.53 (dd, J = 1.8, 6.3 Hz, 1H); 13C NMR: δ = 153.5,
148.7, 133.7, 129.7, 125.3, 118.5, 113.6, 96.2; IR (neat): ν = 3043,
1640, 1595, 1472, 1232, 1164, 1142, 1063, 1005, 953, 765 cm-1.
4-Nitrophenyl vinyl ether (5g): Pale yellow oil (Lit.19 oil); 1H NMR:
δ = 8.25 (d, J = 8.9 Hz, 2H), 7.10 (d, J = 8.9 Hz, 2H), 6.68 (dd,
J = 13.6, 6.0 Hz, 1H), 5.01 (dd, J = 13.6, 1.9 Hz, 1H), 4.70 (dd,
J = 6.0, 1.9 Hz, 1H); 13C NMR: δ = 161.3, 145.5, 142.8, 125.7, 116.3,
99.1; IR (neat): ν = 3060, 1638, 1600, 1580, 1498, 1481, 1330, 1230,
1160, 1120, 1100, 945, 840 cm-1.
Experimental
1
Melting points were uncorrected. H NMR (400 MHz) and 13C
NMR (100 MHz) spectra were recorded on a Bruker Avance
(400 MHz) spectrometer, using CDCl3 as the solvent and TMS as
internal standard. FT-IR spectra were recorded on a Perkin-Elmer
SP One FT-IR spectrophotometer. All reagents were purchased from
commercial suppliers and used without further purification. THF was
distilled from sodium-benzophenone immediately prior to use.
4-Cyanophenyl vinyl ether (5h): Colourless oil (Lit.19 oil); 1H NMR:
δ = 7.70 (d, J = 8.6 Hz, 2H), 7.10 (d, J = 8.6 Hz, 2H), 6.66 (dd,
J = 13.7, 6.1 Hz, 1H), 4.98 (dd, J = 13.7, 2.0 Hz, 1H), 4.68 (dd,
J = 6.1, 2.0 Hz, 1H); 13C NMR: δ = 159.8, 145.8, 134.1, 118.6, 117.1,
106.1, 98.6; IR (neat): ν = 3050, 2200, 1635, 1595, 1492, 1300, 1235,
1160, 1125, 950, 824 cm-1.
Preparation of β-phenylselenoethanol (2):
Sodium hydride (0.14 g, 6.0 mmol) was added to a solution
of diphenyl disselenide (0.96 g, 3.0 mmol), in anhydrous THF
(30 ml), The suspension was refluxed for 2 h and then allowed to
cool to 40°C. HMPA (6 ml) was then added. 2-Chloroethanol (0.48 g,
6.0 mmol) was added to the resulting orange-coloured solution,
After 24 h the reaction was quenched with a 10% solution of NH4Cl
(10 ml). The reaction mixture was extracted with Et2O (3 × 30 ml)
and the combined organic layers were dried over anhydrous Na2SO4
and evaporated to give the crude product. This was purified by
column chromatography on a silica gel column using a mixture of
Et2O and light petroleum (4:6) as eluent to afford pure compound
Methyl 4-(vinyloxy)benzoate (5i): Colourless oil (Lit.19 oil);
1H NMR: δ = 8.00 (d, J = 8.3 Hz, 2H), 7.15 (d, J = 8.3 Hz, 2H), 6.88
(dd, J = 13.6, 6.0 Hz, 1H), 4.85 (dd, J = 13.6, 1.6 Hz, 1H), 4.55 (dd,
J = 6.0, 1.6 Hz, 1H), 3.84 (s, 3H); 13C NMR: δ = 166.5, 160.2, 146.6,
131.5, 124.5, 116.1, 97.3, 51.8; IR (neat): ν = 3050, 2985, 2940, 1710,
1635, 1596, 1498, 1425, 1300, 1272, 1235, 1156, 1132, 1100, 840 cm-1.
N-[4-(Vinyloxy)phenyl]acetamide (5j): White solid, m.p. 102–
1
103°C (Lit.19 103–103.5°C) H NMR: δ = 7.40–7.50 (m, 2H), 7.26
1
2 (1.13 g) as a pale yellow oil in 94%. H NMR: δ = 7.24–7.23 (m,
(br s, 1H), 6.95–7.05 (m, 2H), 6.63 (dd, J = 13.7, 6.1 Hz, 1H), 4.75
(dd, J = 13.7, 1.7 Hz, 1H), 4.55 (dd, J = 6.1, 1.7 Hz, 1H), 2.18 (s, 3H).
13C NMR: δ = 169.2, 153.2, 148.5, 133.4, 122.1, 117.3, 94.6, 24.1.
IR: ν = 3258, 3188, 3130, 3055, 1650, 1600, 1495, 1300, 1235, 1210,
1162, 1145, 940, 830 cm-1. Anal. Calcd for C10H11NO2: C, 67.78; H,
6.26; N, 7.90. Found: C, 67.87; H, 6.36; N, 7.96.
3 H), 7.06–7.04 (m, 2 H), 4.10–3.99 (m, 2 H), 3.18–3.12 (m, 2 H),
2.85 (br s, 1H). 13C NMR: δ = 135.1, 128.3, 128.2, 127.6, 65.1, 51.0.
IR (neat): ν = IR (neat): 3400, 3052, 2921, 1580, 1475, 1060, 941,
730, 688 cm-1.
1-Naphthyl vinyl ether (5k): White solid, 31–32°C (Lit.28 32°C);
1H NMR: δ = 7.00–7.50 (m, 7H), 6.71 (dd, J = 14.1, 6.0 Hz, 1H),
4.81 (dd, J = 14.1, 1.6 Hz, 1H), 4.45 (dd, J = 6.0, 1.6 Hz, 1H); 13C
NMR: δ = 152.7, 144.9, 133.9, 132.6, 128.9, 128.7, 128.3, 126.7,
125.9, 123.5, 115.8, 95.7; IR (KBr): ν = 3050, 1630, 1600, 1495,
1255, 1226, 1172, 1152, 1142, 942 cm-1.
Preparation of aryl vinyl ethers (5); general procedure
Phenols (3) (2.0 mmol) and DIPEA (1.0 ml, 6.0 mmol) in dry THF
(20 ml), DEAD (316 μl, 2.0 mmol) were added dropwise under
ice-cooling. To the stirred mixture of β-phenylselenoethanol (2)
(2.01 g, 1.0 mmol), TPP (525 mg, 2.0 mmol), under nitrogen. The
reaction mixture was stirred at room temperature until TLC analysis

JOURNAL OF CHEMICAL RESEARCH 2008 597
5
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Recovery of diphenyl diselenide
Hydrazine monohydrate (3.5 mmol, 0.16 ml) was added gradually
to the aqueous extract containing the benzeneseleninic acid from the
oxidation procedure. Stirring was continued until diphenyl diselenide
was formed, as indicated by the yellow colour. The mixture was then
concentrated in vacuo, poured into water (30 ml) and extracted with
Et2O (3 × 20 ml). The organic layer was dried over anhydrous sodium
sulfate and evaporated. Diphenyl diselenide was recovered as a pure
compound in 60% yield.
7
8
9
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We gratefully acknowledge financial support from the Natural
Science Foundation of Jiangxi Province (No. 0620021 and
No. 2007GZW0185).
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Received 15 July 2008; accepted 15 August 2008
Paper 08/0056 doi: 10.3184/030823408X360355
Published online: 10 October 2008
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