Reactions of 2-Chloro-4,4-ethylenedioxy-3-phenylsulfonyl-cyclopent-2-en-1- one with some hydride reducing agents and carbon-centered nucleophiles

Article abstract of DOI:10.1134/S107042800709014X

2-Chloro-4,4-ethylenedioxy-3-phenylsulfonylcyclopent-2-en-1-one reacts with NaBH₄ and LiAlH₄ to give, depending on the conditions, 4,4-ethylenedioxy-2-chloro-3-phenylsulfonylcyclopent-2-en-1-ol and 4,4-ethylenedioxy-3-phenylsulfonylc

Full text of DOI:10.1134/S107042800709014X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 9, pp. 1342–1346. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © N.A. Ivanova, F.G. Usmanova, M.S. Miftakhov, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 9,
pp. 1346–1350.
Reactions of 2-Chloro-4,4-ethylenedioxy-3-phenylsulfonyl-
cyclopent-2-en-1-one with Some Hydride Reducing Agents
and Carbon-Centered Nucleophiles
N. A. Ivanova, F. G. Usmanova, and M. S. Miftakhov
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: bioreg@anrb.ru
Received August 8, 2006
Abstract—2-Chloro-4,4-ethylenedioxy-3-phenylsulfonylcyclopent-2-en-1-one reacts with NaBH4 and LiAlH4
to give, depending on the conditions, 4,4-ethylenedioxy-2-chloro-3-phenylsulfonylcyclopent-2-en-1-ol and
4,4-ethylenedioxy-3-phenylsulfonylcyclopent-2-en-1-ol, as well as 4,4-ethylenedioxy-3-phenylsulfonylcyclo-
pentan-1-ol. Reactions of the title compound with diethyl malonate under basic conditions occurs at the double-
bonded carbon atoms to form a couple of the addition–elimination products at C2 and C3.
DOI: 10.1134/S107042800709014X
We previously described the synthesis and reduc-
tive transformations of highly functionalized cyclopen-
tene building block I [1] which was designed for the
development of new approaches to prostaglandins [2],
carbanucleosides [3], and their analogs. In the present
work we continued study on the hydride reduction and
vinylic nucleophilic substitution reaction of sulfonyl-
cyclopentenone acetal I with the goal of estimating its
reactivity and obtaining more important precursors of
the above compounds.
Increase of the amount of hydride reagent to
1.5 equiv and prolongation of the reaction to 1 h with
a view to obtain alcohol V led to formation of a mix-
ture of acetals II and IV at a ratio of 1:3; the product
mixture can be readily separated by column chroma-
tography on silica gel. Like hydroxy acetal II, com-
pound IV is readily converted into the corresponding
hydroxy enone V on treatment with dilute aqueous
solutions of mineral acids.
Further raising the amount of the reducing agent
(2 equiv of NaBH4) and reaction time or performing
the reduction with LiAlH4 at room temperature re-
sulted in the formation of complete reduction product,
alcohol VI. Unlike compound V, the acetal protecting
group in alcohol VI is stable, and it remains unchanged
upon acid treatment of the reaction mixture. Presum-
ably, conformational or other variations in the mole-
cule eliminate assistance by the hydroxy group. Cyclo-
pentanol VI can also be synthesized by hydride
reduction of unsaturated alcohol II.
Experiments with accessible reducing agents
(NaBH4 and LiAlH4) showed that, depending on the
conditions, the reduction may involve the carbonyl
group, double C=C bond, and/or vinylic chlorine atom
on C2. Using the system NaBH4–CeCl3 [4] or 1 mol of
NaBH4 in EtOH–THF at 0°C, followed by treatment
under mild conditions, we succeeded in effecting
chemoselective reduction of the ketone group in I and
obtaining hydroxy acetal II (Scheme 1) [1]. The ethyl-
ene acetal protecting group in II is anomalously sen-
sitive to hydrolysis, so that partial formation of hy-
droxy ketone III was observed even when the reaction
mixture was treated with water. Such a behavior of
structurally related ketone acetals having no sulfonyl
group was discussed by us previously: we presumed
intramolecular assistance to hydrolysis by the free
hydroxy group in II [5, 6].
We also examined the behavior of unsaturated keto
sulfone I in reactions with carbon-centered nucleo-
philes. We found that in the reaction with diethylmalo-
nate in the presence of potassium hydroxide substitu-
tion is possible at both vinylic carbon atoms. It should
be emphasized that the phenylsulfonyl group was re-
placed more readily than the chlorine atom, and com-
1342

REACTIONS OF 2-CHLORO-4,4-ETHYLENEDIOXY-3-PHENYLSULFONYLCYCLOPENT-...
1343
Scheme 1.
O
O
O
a or b
c
SO2Ph
SO2Ph
HO
Cl
HO
Cl
III, 70%
II, 90%
O
O
O
O
O
c
d
SO2Ph
SO2Ph
SO2Ph
II
+
O
Cl
HO
HO
IV
V, 70%
I
II :IV = 1:3, 86%
O
O
e or f
a
SO2Ph
II
HO
VI, 70% (e), 50% (f)
a: NaBH4 (1.0 equiv), EtOH–THF (1:1), 0°C, 20 min, +Me2CO; b: NaBH4 (4.0 equiv), CeCl3·7H2O (4 equiv), MeOH, –30°C, 1 h,
+Me2CO; c: H+/H2O; d: NaBH4 (1.5 equiv), EtOH–THF (1:1), 0°C, 1 h, +Me2CO; e: NaBH4 (2.0 equiv), EtOH–THF (1:1), 20°C,
4 h, +H+/H2O; f: LiAlH4 (2.0 equiv), Et2O–THF (1:1), 20°C, 4 h, +H+/H2O.
develop procedures for the preparation of synthetic
blocks II–VI that are interesting as intermediates in the
convergent synthesis of prostanoids and other cyclo-
pentanoids.
pounds VII and VIII were formed at a ratio of 3:2.
Obviously, this is the result of stronger electron-with-
drawing effect of the oxo group on the β-carbon atom
in the conjugated enone system. The reaction of I with
copper reagent obtained from prop-2-yn-1-ylmagnesi-
um bromide and CuI was less selective; apart from
the corresponding replacement products IX and X, we
isolated 1,2-adduct XI (Scheme 2).
EXPERIMENTAL
The IR spectra were recorded on UR-20 and
Specord M-80 spectrometers from samples prepared as
1
thin films or dispersed in mineral oil. The H and 13C
Thus the results of our study allowed us to refine
some aspects of the reactivity of vinylic sulfone I and
NMR spectra were measured on a Bruker AM-300
Scheme 2.
O
O
O
O
CH2(COOEt)2
KOH, THF
CH(COOEt)2
SO2Ph
+
O
Cl
O
CH(COOEt)2
VIII, 36%
VII, 57%
I
O
O
O
O
O
O
CH
≡
CCH2MgBr
CuI, THF, Et2O
SO2Ph
SO2Ph
+
+
HC
CH
CH
O
Cl
O
Cl
HO
IX, 25%
X, 18%
XI, 10%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

IVANOVA et al.
1344
instrument at 300.13 and 75.47 MHz, respectively,
using chloroform-d as solvent and reference (CHCl3,
δ 7.27 ppm; CDCl3, δC 77.00 ppm). The progress of re-
actions was monitored by TLC on Silufol plates using
petroleum ether–ethyl acetate as eluent; spots were
visualized by treatment with a p-methoxybenzalde-
hyde-based reagent or an alkaline solition of potassium
permanganate [7].
13C NMR spectrum, δC, ppm: 45.22 (C5), 78.59 (C4),
129.10 (Co), 130.39 (Cm), 133.92 (Cp), 134.82 (Ci),
148.02 (C2), 176.95 (C3), 195.92 (C1). Found, %:
C 48.32; H 3.17; Cl 12.85; S 11.58. C11H9ClO4S. Cal-
culated, %: C 48.45; H 3.33; Cl 13.00; S 11.76.
4,4-Ethylenedioxy-3-phenylsulfonylcyclopent-2-
en-1-ol (IV). A solution of 0.2 g (0.64 mmol) of keto
sulfone I in 10 ml of a 1:1 ethanol–tetrahydrofuran
mixture was cooled to 0°C, 0.036 g (0.96 mmol) of
sodium tetrahydridoborate was added, and the mixture
was stirred for 1 h and was then treated as described
above in a. By column chromatography on silica gel
using petroleum ether–ethyl acetate (7:3) as eluent we
isolated 0.04 g (22%) of compound II and 0.11 g
(64%) of alcohol IV as a yellow oily substance, Rf 0.36
(petroleum ether–ethyl acetate, 7:3; three successive
elutions). IR spectrum, ν, cm–1: 1340 (SO2), 1590
Reaction of compound I with NaBH4. A solution
of 0.2 g (0.64 mmol) of keto sulfone I in 10 ml of
a 1:1 ethanol–tetrahydrofuran mixture was cooled to
0°C, 0.024 g (0.64 mmol) of sodium tetrahydrido-
borate was added, and the mixture was stirred for
20 min and treated as follows (methods a and b)
a. The mixture was diluted with 10 ml of acetone,
the solvent was distilled under reduced pressure, and
the residue was subjected to flash chromatography on
silica gel using petroleum ether–ethyl acetate (7:3) as
eluent to isolate 0.18 g (90%) of alcohol II.
b. The mixture was treated with 5 ml of 5% hy-
drochloric acid, the solvent was distilled off under
reduced pressure, the residue was diluted with 10 ml of
a saturated solution of sodium chloride, and the mix-
ture was extracted with chloroform (3×10 ml). The
extracts were combined, washed with water, dried over
MgSO4, and concentrated under reduced pressure. The
residue was subjected to column chromatography on
silica gel using petroleum ether–ethyl acetate (7:3) as
eluent to isolate 0.14 g (70%) of hydroxy ketone III.
1
(C–Carom), 3390 (OH). H NMR spectrum, δ, ppm:
2.20 d.d (1H, 5-HA, J = 6.3, 15.4 Hz), 2.72 d.d (1H,
5-HB, J = 6.3, 15.4 Hz), 3.91–4.32 m (5H, CH2O, OH),
4.60 m (1H, 1-H), 6.17 m (1H, 3-H) 7.01–7.23 m (5H,
H
arom). 13C NMR spectrum, δC, ppm: 46.59 (C5), 65.78
(CH2O), 66.32 (CH2O), 71.15 (C1), 114.74 (C4), 125.26
(Co), 127.37 (Cm), 128.67 (Cp), 135.46 (Ci), 142.01
(C2), 158.45 (C3). Found, %: C 55.42; H 5.15; S 11.49.
C13H14O5S. Calculated, %: C 55.31; H 5.00; S 11.36.
4-Hydroxy-2-phenylsulfonylcyclopent-2-en-1-
one (V). A solution of 0.2 g (0.64 mmol) of keto
sulfone I in 10 ml of a 1:1 ethanol–tetrahydrofuran
mixture was cooled to 0°C, 0.036 g (0.96 mmol) of
sodium tetrahydridoborate was added, and the mixture
was stirred for 1 h and was then treated as described
above in b. Column chromatography on silica gel
(eluent petroleum ether–ethyl acetate, 7:3) gave 0.13 g
(70%) of compound V as a colorless oily substance,
Rf 0.26 (petroleum ether–ethyl acetate, 1:1). IR spec-
trum, ν, cm–1: 1344 (SO2), 1696 (C=C), 1712 (C=O),
2-Chloro-4,4-ethylenedioxy-3-phenylsulfonyl-
cyclopent-2-en-1-ol (II). Colorless oily substance,
Rf 0.38 (petroleum ether–ethyl acetate, 7:3; three suc-
cessive elutions). IR spectrum, ν, cm–1: 1342 (SO2),
1
1615 (C–Carom), 3400 (OH). H NMR spectrum, δ,
ppm: 2.11 d.d (1H, 5-HA, J = 4.0, 16.0 Hz), 2.60 d.d
(1H, 5-HB, J = 4.0, 16.0 Hz), 3.70–3.90 m (4H, CH2O),
13
4.60 br.s (1H, 4-H), 7.10–7.3 m (5H, Harom). C NMR
1
spectrum, δC, ppm: 45.22 (C5), 66.13 and 65.76
(CH2O), 70.96 (C1), 115.20 (C4), 146.88 (C2), 130.14
(C3), 128.01 (Co), 129.09 (Cm), 129.95 (Cp), 132.19
(Ci). Found, %: C 49.34; H 4.23; Cl 11.28; S 9.33.
C13H13ClO5S. Calculated, %: C 49.29; H 4.14;
Cl 11.19; S 9.56.
3400 (OH). H NMR spectrum, δ, ppm: 3.0 br.s (1H,
OH), 3.15 m (2H, 5-H), 4.32 m (1H, 4-H), 6.11 m (1H,
3-N), 7.70 m (2H, o-H), 7.77 m (1H, p-H), 7.88 m (2H,
m-H). 13C NMR spectrum, δC, ppm: 30.73 (C5), 65.35
(C4), 128.91 (Co), 133.1 (Cm), 134.23 (Cp), 136.32 (Ci),
138.32 (C2), 163.92 (C3), 197.25 (C1). Found, %:
C 55.32; H 4.05; S 13.41. C11H10O4S. Calculated, %:
C 55.45; H 4.23; S 13.46.
3-Chloro-4-hydroxy-2-phenylsulfonylcyclopent-
2-en-1-one (III). Colorless crystals, mp 111–113°C,
Rf 0.34 (petroleum ether–ethyl acetate, 7:3; three suc-
cessive elutions). IR spectrum, ν, cm–1: 1344 (SO2),
4,4-Ethylenedioxy-3-phenylsulfonylcyclopentan-
1-ol (VI). a. A solution of 0.50 g (1.56 mmol) of
sulfone I in 10 ml of anhydrous tetrahydrofuran was
added dropwise at 0°C to a suspension of 0.12 g
(3.12 mmol) of LiAlH4 in 10 ml of anhydrous diethyl
1
1584 (C–Carom), 1733 (C=O), 3400 (OH). H NMR
spectrum, δ, ppm: 2.23 m (2H, 5-H), 4.39 m (1H, 4-H),
7.50 m (2H, o-H), 7.57 m (1H, p-H), 7.96 (2H, m-H).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

REACTIONS OF 2-CHLORO-4,4-ETHYLENEDIOXY-3-PHENYLSULFONYLCYCLOPENT-...
1345
mp 46–48°C, Rf 0.33 (petroleum ether–ethyl acetate,
7:3; three successive elutions). IR spectrum, ν, cm–1:
1024 (CH2), 1148 (O–C–O), 1584 (C=C), 1738 (C=O,
ether. The mixture was stirred for 4 h at room tem-
perature, 5 ml of 5% hydrochloric acid was added, and
the mixture was concentrated under reduced pressure.
The residue was diluted with 10 ml of water, and the
product was extracted into chloroform (3×10 ml). The
extracts were combined, washed with water, and dried
over MgSO4, the solvent was distilled off under
reduced pressure, and the residue was subjected to
column chromatography on silica gel using petroleum
ether–ethyl acetate (7:3) as eluent to isolate 0.25 g
(50%) of a ~1:1 mixture of diastereoisomeric alcohols
VI as a colorless oily substance, Rf 0.15 (benzene–
ethyl acetate, 7:3; two successive elutions).
1
ester), 1756 (C=O, ketone). H NMR spectrum, δ,
ppm: 1.24 t (6H, CH3, J = 7.1 Hz), 2.69 s (2H, 4-H),
4.02 m and 4.10 m (4H, OCH2CH2O), 4.22 q (4H,
OCH2CH3, J = 7.1 Hz), 4.41 s (1H, 1-CH). 13C NMR
spectrum, δC, ppm: 13.80 (CH3), 45.40 (C4), 49.34
(1-CH), 62.33 and 65.94 (CH2O), 109.44 (C5), 136.35
(C2), 154.47 (C1), 164.95 (OC=O), 194.50 (C3). Found,
%: C 50.67; H 5.01; Cl 10.84. C14H17ClO7. Calculated,
%: C 50.54; H 5.15; Cl 10.65.
Diethyl 2-(3,3-ethylenedioxy-5-oxo-2-phenylsul-
fonylcyclopent-1-en-1-yl)malonate (VIII). Colorless
crystals, mp 95–97°C, Rf 0.21 (petroleum ether–ethyl
acetate, 7:3; three successive elutions). IR spectrum, ν,
cm–1: 1048 (O–C–O), 1240 (SO2), 1372 (SO2), 1590
b. A solution of 0.2 g (0.64 mmol) of sulfone I in
10 ml of a 1:1 ethanol–tetrahydrofuran mixture was
cooled to 0°C, 0.048 g (1.28 mmol) of sodium tetra-
hydridoborate was added, and the mixture was stirred
for 4 h and was then treated as described in b for
compound II. The product was isolated by column
chromatography on silica gel using petroleum ether–
ethyl acetate (7:3) as eluent. Yield 0.13 g (70%). IR
spectrum, ν, cm–1: 1306 (SO2), 1450 (C–Carom), 3508
1
(C–Carom), 1738 (C=O). H NMR spectrum, δ, ppm:
1.21 t (3H, CH3, J = 7.0 Hz), 2.75 s (2H, 4-H), 3.99 m
(2H, OCH2), 4.14 q (4H, OCH2, J = 6.9 Hz), 4.24 m
(2H, OCH2), 5.38 s (1H, CH) 7.56 q (2H, m-H, J = 7.4,
7.8 Hz), 7.67 t (1H, p-H, J = 7.2, 7.4 Hz), 7.97 d (2H,
o-H, J = 7.9 Hz). 13C NMR spectrum, δC, ppm: 13.91
(CH3), 48.39 (C4), 62.40 (OCH2CH3), 66.44 (CH2O),
111.24 (C2), 128.05 (Co), 129.27 (Cm), 134.43 (Cp),
140.51 (Ci), 145.42 (C1), 158.91 (C2), 164.99 (OC=O),
198.01 (C5). Found, %: C 54.62; H 5.08; S 7.23.
C20H22O9S. Calculated, %: C 54.79; H 5.06; S 7.31.
1
(OH). H NMR spectrum, δ, ppm: 1.92–2.51 m (4H,
2-H, 5-H), 2.88 br.s (1H, OH), 3.53–3.90 m (5H,
CH2O, 3-H), 4.15 q (0.5H, 1-H, J = 6.2 Hz), 4.33 br.s
(0.5H, 1-H, J = 6.2 Hz), 7.51–7.88 m (5H, Harom).
13C NMR spectrum, δC, ppm: 35.54 and 36.38 (C2),
43.77 and 45.86 (C5), 64.20 and 65.27 (CH2O), 64.55
and 65.13 (CH2O), 67.95 and 68.03 (C3), 68.36 and
68.82 (C1), 114.12 and 115.10 (C4), 128.44 and 128.59
(Co), 128.80 (Cm), 133.33 and 133.44 (Cp), 139.10 and
139.30 (Ci). Found, %: C 54.80; H 5.54; S 11.35.
C13H16O5S. Calculated, %: C 54.91; H 5.67; S 11.28.
Reaction of sulfone I with prop-2-yn-1-ylmagne-
sium bromide. Copper(I) iodide, 0.18 g (0.95 mmol),
was added under argon to 0.56 ml (1.43 mmol) of
a 2.58 M solution of prop-2-yn-1-ylmagnesium bro-
mide in anhydrous tetrahydrofuran, cooled to 0°C, and
the mixture was stirred for 20 min. The mixture was
cooled to –50°C, a solution of 0.3 g (0.95 mmol) of
sulfone I in 4 ml of anhydrous THF was added drop-
wise over a period of 10 min, and the mixture was
stirred for 1 h at 0°C and for 12 h at room temperature.
It was then cooled to 0°C, treated with 2 ml of a satu-
rated solution of ammonium chloride, and extracted
with ethyl acetate (3×15 ml). The extracts were com-
bined, washed with a saturated solution of sodium
chloride, dried over magnesium sulfate, and concen-
trated under reduced pressure. The residue was sub-
jected to chromatography on silica gel using petroleum
ether–ethyl acetate (8:2) as eluent to isolate 0.09 g
(30%) of initial sulfone I, 0.04 g (25%) of chloro
ketone IX, 0.04 g (18%) of keto sulfone X, and 0.03 g
(10%) of alcohol XI.
Reaction of sulfone I with diethyl malonate.
Potassium hydroxide, 0.20 g (3.52 mmol), and diethyl
malonate, 0.51 g (3.18 mmol), were added at room
temperature to a solution of 0.20 g (0.64 mmol) of
sulfone I in 8 ml of THF. The mixture was stirred for
20 min, diluted with 25 ml of ethyl acetate and 5 ml of
10% hydrochloric acid, and extracted with ethyl ace-
tate (2×15 ml). The extracts were combined, washed
with 10% hydrochloric acid to pH 7 and a saturated
solution of sodium chloride, and dried over MgSO4,
the solvent was distilled off under reduced pressure,
and the residue was subjected to column chromatog-
raphy on silica gel using petroleum ether–ethyl acetate
(8:2) as eluent to isolate 0.08 g (57%) of enone VII
and 0.05 g (36%) of sulfone VIII.
Diethyl 2-(2-chloro-5,5-ethylendioxy-3-oxocyclo-
pent-1-en-1-yl)malonate (VII). Yellow crystals,
2-Chloro-4,4-ethylenedioxy-3-(prop-2-yn-1-yl)-
cyclopent-2-en-1-one (IX). Yellow crystals, mp 90–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007

IVANOVA et al.
1346
1
93°C, Rf 0.26 (petroleum ether–ethyl acetate, 7:3;
three successive elutions). 1H NMR spectrum, δ, ppm:
2.05 t (1H, ≡CH, J = 3.1 Hz), 2.23 d (1H, 5-HA, J =
13.9 Hz), 2.50 d (1H, 5-HB, J = 13.9 Hz), 3.50 d (1H,
1′-HA, J = 12.5 Hz), 3.56 d (1H, 1′-HB, J = 12.5 Hz),
4.05–4.28 m and 4.28–4.48 m (4H, CH2O). 13C NMR
spectrum, δC, ppm: 28.09 (C1′), 46.98 (C5), 57.14 and
58.54 (CH2O), 64.51 (C3′), 77.50 (C2′), 108.57 (C4),
135.05 (C2), 158.79 (C3), 191.70 (C1). Found, %:
C 56.61; H 4.35; Cl 16.58. C10H9ClO3. Calculated, %:
C 56.49; H 4.27; Cl 16.67.
7:3; three successive elutions). H NMR spectrum, δ,
ppm: 1.93 d (1H, 1′-HA, J = 26.7 Hz), 2.25 d.d (1H,
1′-HB, J = 2.6, 26.7 Hz), 2.00 s (1H, ≡CH), 2.56 d
(1H, 5-HA, J = 2.6 Hz), 2.65 d.d (1H, 5-HB, J = 2.6,
25.6 Hz), 2.60 br.s (1H, OH), 4.13–4.36 m (4H, CH2O),
7.52–7.62 m (3H), 8.00 d (2H). 13C NMR spectrum,
δC, ppm: 28.80 (C1′), 49.91 (C5), 65.99 and 66.05
(CH2O), 76.59 (≡CH), 77.84 (C2′), 79.14 (C1), 114.06
(C4), 127.86 (Co), 128.76 (Cm), 133.70 (Cp), 138.90
(Ci), 140.78 (C3), 152.94 (C2). Found, %: C 54.23;
H 4.42; Cl 10.04; S 9.11. C16H15ClO5S. Calculated, %:
C 54.16; H 4.26; Cl 9.99; S 9.04.
4,4-Ethylenedioxy-3-phenylsulfonyl-2-(prop-2-
yn-1-yl)cyclopent-2-en-1-one (X). Brown oily sub-
stance, Rf 0.33 (petroleum ether–ethyl acetate, 7:3;
three successive elutions). IR spectrum, ν, cm–1: 1033,
1145, 1342 (SO2), 1610 (C–Carom), 1725 (C=O), 2124
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14.0 Hz), 2.62 d.d (1H, 1′-HB, J = 2.7, 14.0 Hz), 2.47 d
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H 4.58; S 10.46. C16H14ClO4S. Calculated, %: C 60.37;
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the title Tonkosloinaya khromatografiya, Moscow: Mir,
1981, vol. 1, p. 616.
2-Chloro-4,4-ethylenedioxy-3-phenylsulfonyl-1-
(prop-2-yn-1-yl)cyclopent-2-en-1-ol (XI). Yellow
oily substance, Rf 0.13 (petroleum ether–ethyl acetate,
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