Synthesis of dicyclopropanes from 4,7,7-Trimethyl-3-oxabicyclo[4.1.0]hept- 4-en-2-one

Article abstract of DOI:10.1134/S1070428007060061

New optically active dicyclopropanes were synthesized on the basis of transformation products of 4,7,7-trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one using dichlorocarbene or sulfoxonium ylide in the key cyclopropanation stages.

Full text of DOI:10.1134/S1070428007060061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 6, pp. 834–838. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © V.G. Kasradze, I.I. Gilyazetdinova, O.S. Kukovinets, E.V. Salimova, I.V. Naleukhin, R.A. Zainullin, A.N. Lobov, L.V. Spirikhin,
F.Z. Galin, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 6, pp. 838–842.
Synthesis of Dicyclopropanes from 4,7,7-Trimethyl-3-oxa-
bicyclo[4.1.0]hept-4-en-2-one
V. G. Kasradze, I. I. Gilyazetdinova, O. S. Kukovinets, E. V. Salimova, I. V. Naleukhin,
R. A. Zainullin, A. N. Lobov, L. V. Spirikhin, and F. Z. Galin
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: galin@anrb.ru
Received July 19, 2006
Abstract—New optically active dicyclopropanes were synthesized on the basis of transformation products of
4,7,7-trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one using dichlorocarbene or sulfoxonium ylide in the key
cyclopropanation stages.
DOI: 10.1134/S1070428007060061
Cyclopropane ring is a structural fragment of many
biologically active compounds, including highly ef-
ficient insecticides and incest growth and development
regulators. In the recent years, strong physiological
activity has been revealed in the series of conjugated
polycyclopropane derivatives, and interest in these
compounds has increased considerably [1]. Almost all
known syntheses of such polycyclopropanes are based
on a combination of olefination and Simmons–Smith
cyclopropanation.
hept-4-en-2-one (I) which is readily available via suc-
cessive transformations of (+)-3-carene [3].
It was reported previously that cyclopropanation of
unsaturated lactone I with dichlorocarbene generated
from PhHgCCl3 [4] or by the Makosza reaction under
temperature-controlled conditions (CHCl3/NaOH/
Et3BzlN+Cl–, 30°C) [5] leads to the formation in both
cases of 5,5-dichloro-4,8,8-trimethyl-3-oxatricyclo-
[5.1.0.04,6]octan-2-one (II) in a good yield. However,
the yield of the corresponding dibromo derivative III
in the cyclopropanation of I with dibromocarbene
generated under analogous conditions (CHBr3/NaOH/
Et3BzlN+Cl–, 30°C) did not exceed 55% [5]. We have
found that the reaction performed above 30°C is ac-
companied by formation of a considerable amount (up
The goal of the present study was to develop syn-
thetic routes to new polycyclopropanes on the basis of
2,2-dimethylcyclopropanecarboxylic acid derivatives
which exhibit strong biological activity [2]. As starting
material we used 4,7,7-trimethyl-3-oxabicyclo[4.1.0]-
Scheme 1.
X
Me
Me
X
CHX3/NaOH, Bu4N+ Br–
CH2Cl2, MeOH
O
O
O
OMe
+
Me
O
O
Me
Me
O
Me
Me
Me
Me
I
II, III
IV
CHCl3/K2CO3/Bu4N+ Br–/CCl3COONa
or CHBr3/K2CO3/Bu4N+ Br–
I
II, III
83–85%
II, X = Cl; III, X = Br.
834

SYNTHESIS OF DICYCLOPROPANES
835
Scheme 2.
(1) SOCl2
(2) m-PhOC6H4CH2OH
pyridine
O
O
O
O
NaOH, MeOH–H2O (1:1) or
NaOH, MeOH–H2O (30:1)
Me
OR
Me
OR
II
Cl
Cl
Me
Me
Me
VII
Me
V, VI
O
O
O
O
Silica gel
Me
OR
Me
OR
VI, VII
+
Cl
Cl
Me
Me
Me
Me
(1R)-cis-VI, (1R)-cis-VII
(1S)-trans-VI, (1S)-trans-VII
V, R = H; VI, R = Me; VII, R = m-PhOC6H4CH2.
esters VI and VII. In both cases, we isolated mixtures
of syn and anti diastereoisomers, the syn isomer pre-
vailing, which is typical of cyclopropanation of cis-
vinylcyclopropanes having an electron-deficient double
bond [7]. The syn-to-anti ratio was 3:2 for compounds
VIII and IX and 4:1 for X and XI. Diastereoisomeric
esters VIII and IX were isolated as individual sub-
stances by column chromatography on silica gel.
to 65%) of methyl 3,3-dimethyl-6-oxohept-4-enoate
(IV) [6] in addition to compound II or III (Scheme 1).
When dihalocarbene is generated by the action of
K2CO3 on CHX3, the corresponding dicyclopropane II
or III is formed as the only product in a high yield.
Alkaline hydrolysis of the lactone ring in II in
aqueous methanol, depending on the solvent ratio,
gives 3-(2-chloro-3-oxobut-1-en-1-yl)-2,2-dimethyl-
cyclopropane-1-carboxylic acid (V) or its methyl ester
VI that are precursors of conjugated dicyclopropanes.
The hydrolysis of lactone II is accompanied by partial
epimerization at the C1 center to afford a mixture of
(1R)- and (1S)-isomers VI and VII at a ratio of 4:1
(Scheme 2); the isomers can be separated by column
chromatography on silica gel [5].
Thus, from the transformation products of (+)-3-
carene we obtained optically active dicyclopropane-
carboxylic acid esters VIII–XI that can be regarded as
analogs of highly efficient pyrethroids and fungicides;
the products also attract interest as intermediate com-
pounds in the synthesis of polycyclopropanes.
EXPERIMENTAL
Cyclopropanation of the Z-configured double bond
was performed with the (1R)-cis isomers of acid V
esters, methyl ester VI and m-phenoxybenzyl ester
VII. Dicyclopropanes VIII–XI were synthesized by
the action of dichlorocarbene or sulfoxonium ylide on
1
The H and 13C NMR spectra were recorded on
a Bruker AM-300 spectrometer at 300 and 75.46 MHz,
respectively, from solutions in CDCl3; the chemical
shifts were measured relative to tetramethylsilane. The
Scheme 3.
Cl
O
Cl
Cl
O
Cl
O
O
CHCl3/K2CO3/Bu4N+ Br–
CCl3COONa, SiO2
Me
OR
Me
OR
+
Cl
Cl
Me
Me
Me
Me
syn-VIII, syn-IX
syn:anti = 3:2 anti-VIII, anti-IX
(1R)-cis-VI
(1R)-cis-VII
O
O
Me3S+(O)I–, NaH/DMSO
Me
OR
Cl
Me
Me
X, XI syn:anti = 4:1
VIII, X, R = Me; IX, XI, R = 3-PhOC6H4CH2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007

KASRADZE et al.
836
IR spectra were obtained in the frequency range from
400 to 4000 cm–1 on a Specord M-80 spectrometer
from samples prepared as thin films. The optical
rotations were measured from solutions in CHCl3 on
a Perkin–Elmer 241 MS instrument. GLC analysis was
performed on a Chrom-5 chromatograph [1200×3-mm
column, stationary phase 5% of SE-30 on Chromaton
N-AW-DMSC (0.16–0.20 mm), oven temperature 50–
300°C, carrier gas helium].
isolate 0.19 g (25%) of compound II and 0.39 g (65%)
of IV or 0.2 g (19%) of III and 0.4 g (67%) of IV. The
products were identical to those described in [5, 6].
Methyl 3-[(1Z)-2-chloro-3-oxobut-1-en-1-yl]-2,2-
dimethylcyclopropane-1-carboxylate (VI). A mixture
of 1 g (4.25 mmol) of compound II, 0.6 g of KOH,
0.6 ml of water, and 40 ml of MeOH was stirred for
6 h. The mixture was diluted with ethyl acetate, the
organic phase was washed in succession with water
and a saturated solution of NaCl, and dried over
Na2SO4, and the solvent was distilled off. The residue
(0.85 g) was subjected to column chromatography on
silica gel using petroleum ether–ethyl acetate (19:1) to
isolate 0.56 g (57%) of (1R)-cis isomer and 0.14 g
5,5-Dichloro-4,8,8-trimethyl-3-oxatricyclo-
[5.1.0.04, 6]octan-2-one (II). Compound I, 2 g
(13.15 mmol), was dissolved in 50 ml of anhydrous
chloroform, 0.315 g (0.98 mmol) of Bu4N+ Br–, 6 g
(43.47 mmol) of K2CO3, 6.25 g (33.7 mmol) of
CCl3CO2Na, and 0.1 ml of MeOH were added, and the
mixture was heated for 4 h under reflux with stirring.
The mixture was diluted with ethyl acetate, washed
with water, and dried over Na2SO4, the solvent was
distilled off, and the residue was subjected to chroma-
tography on silica gel using petroleum ether–ethyl
acetate (9:1) as eluent to isolate 1.66 g (83%) of com-
pound II as a colorless crystalline substance which was
identical to that described in [5].
(14%) of (1S)-trans isomer of VI, which were identical
20
to those described in [5]. (1S)-trans Isomer: [α]
=
589
13
+71.9° (c = 0.17). C NMR spectrum, δC, ppm: 20.15
and 26.19 (2-CH3), 27.07 (C2), 29.58 (C1), 31.15
(CH3CO), 36.47 (C3), 51.93 (CH3O), 133.78 (CCl),
138.48 (C=CCl), 171.25 (COO), 191.02 (C=O).
m-Phenoxybenzyl 3-[(1Z)-2-chloro-3-oxobut-1-
en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate
(VII). A mixture of 1.9 g (8.55 mmol) of compound II,
1.42 g (25.45 mmol) of KOH, 47 ml of H2O, and 50 ml
of MeOH was stirred for 6 h at 30–40°C. The mixture
was poured into 9 ml of water and thoroughly washed
with diethyl ether (2×30 ml), the aqueous phase was
separated, acidified to pH 2 with dilute sulfuric acid,
and extracted with diethyl ether (3×30 ml), the ex-
tracts were combined, washed with a saturated solution
of NaCl, and dried over Na2SO4, and the solvent was
distilled off. Yield of acid V 1.6 g (91%). IR spectrum,
ν, cm–1: 590 (C–Cl), 1630 (C=C), 1690 (C=O), 1720
(CO2H), 2400–3400 (OH). Acid V, 0.3 g (1.3 mmol),
was dissolved in 15 ml of anhydrous benzene, 0.2 ml
of thionyl chloride was added dropwise under stirring,
and the mixture was stirred at 70–80°C until gaseous
products no longer evolved. The solvent was distilled
off to leave 0.28 g of the corresponding acid chloride.
IR spectrum, ν, cm–1: 590 (C–Cl), 1630 (C=C), 1690
(C=O), 1780 (COCl).
5,5-Dibromo-4,8,8-trimethyl-3-oxatricyclo-
[5.1.0.04,6]octan-2-one (III). Compound I, 2 g
(13.15 mmol), was dissolved in 6 ml of anhydrous
bromoform, 0.3 g (0.93 mmol) of Bu4N+ Br–, 5.4 g
(39.13 mmol) of K2CO3, and 0.1 ml of MeOH were
added, and the mixture was heated for 4 h under reflux
with stirring. The mixture was diluted with ethyl
acetate, washed with water, and dried over Na2SO4, the
solvent was distilled off, excess bromoform was
removed under reduced pressure, and the residue was
subjected to chromatography on silica gel using
petroleum ether–ethyl acetate (9:1) as eluent to isolate
1.7 g (85%) of compound III as a colorless crystalline
substance which was identical to that described in [5].
Methyl 3,3-dimethyl-6-oxohept-4-enoate (IV).
Compound I, 0.5 g (3.2 mmol), was dissolved in 6 ml
of anhydrous methylene chloride, 0.03 g (0.098 mmol)
of Bu4N+ Br–, 0.1 ml of MeOH, 3 ml of CHCl3 or
CHBr3, and 0.52 g (13.1 mmol) of freshly calcined
NaOH were added, and the mixture was heated for 6 h
under reflux with stirring. The mixture was diluted
with ethyl acetate, washed in succession with 3%
hydrochloric acid and a saturated solution of NaCl, and
dried over Na2SO4. The mixture was filtered, the sol-
vent was distilled off from the filtrate, and the residue
(0.58 g) was subjected to chromatography on silica gel
using petroleum ether–ethyl acetate (19:1) as eluent to
A mixture of 0.614 g (3.07 mmol) of m-phenoxy-
benzyl alcohol, 5 ml of CH2Cl2, and 0.358 g
(4.53 mmol) of pyridine was cooled to 10°C, 0.76 g
(4 mmol) of acid V chloride was added, and the
mixture was stirred for 4 h. Methylene chloride, 40 ml,
and water, 10 ml, were added to the mixture at room
temperature, the mixture was stirred for 30 min, the
aqueous phase was separated, and the organic phase
was washed in succession with 10% hydrochloric acid,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007

SYNTHESIS OF DICYCLOPROPANES
837
water, a solution of NaHCO3, and a solution of NaCl
and dried over Na2SO4. The solvent was distilled off,
and the residue was subjected to column chromatog-
raphy on silica gel using petroleum ether–ethyl acetate
(19:1) as eluent to isolate 0.66 g (52%) of (1R)-cis and
1-H, J = 8.5 Hz), 2.54 s (3H, CH3CO), 3.23 d (1H,
1′-H, J = 8.5 Hz), 3.73 s (3H, OCH3). 13C NMR spec-
trum, δC, ppm: 14.95 (2-CH3), 25.57 (C2), 27.65
(2-CH3), 28.12 (CH3CO), 28.58 (C1), 28.78 (C3), 32.56
(C1′), 51.74 (OCH3), 59.60 (C2′), 65.58 (CCl2), 171.41
(COO), 195.83 (C=O).
0.165 g (13%) of (1S)-trans isomers of VII.
20
589
1
(1R)-cis-VII. [α] = –5.92° (c = 0.09). IR spec-
anti-VIII. H NMR spectrum, δ, ppm: 1.15 t (1H,
trum, ν, cm–1: 590 (C–Cl), 1590 (C–Carom), 1620
3-H, J3,1 = J3,1′ = 8.6 Hz), 1.28 s (3H, 2-CH3), 1.71 d
(1H, 1-H, J = 8.6 Hz), 2.53 s (3H, CH3CO), 3.32 d
(1H, 1′-H, J = 8.6 Hz), 3.68 s (3H, OCH3). 13C NMR
spectrum, δC, ppm: 15.39 (2-CH3), 25.47 (C2), 27.95
(C1), 28.08 (C3), 28.27 (2-CH3), 28.56 (CH3CO), 32.95
(C1′), 51.59 (OCH3), 60.05 (C2′), 65.85 (CCl2), 171.13
(COO), 195.86 (C=O).
1
(C=C), 1690 (C=O), 1735 (COO). H NMR spectrum,
δ, ppm: 1.33 s (3H, 2-CH3), 1.35 s (3H, 2-CH3), 2.15 d
(1H, 1-H, J = 8.5 Hz), 2.35 d.d (1H, 3-H, J = 8.5,
9.4 Hz), 2.42 s (3H, CH3CO), 5.12 s (2H, CH2), 6.92–
7.41 m (9H, Harom), 7.44 d (1H, CH=, J = 9.4 Hz).
13C NMR spectrum, δC, ppm: 15.04, 25.88 (2-CH3);
28.31 (C1); 29.92 (C2); 32.87 (CH3CO); 34.05 (C3);
65.88 (CH2); 118.13, 118.36, 118.94, 119.23, 122.58,
123.42, 129.67, 129.83, 129.97 (Carom); 134.68 (CCl);
137.96 (C=CCl); 138.24 (CCH2); 156.75, 157.47
m-Phenoxybenzyl (1R)-cis-3-(2-acetyl-2,3,3-tri-
chlorocyclopropyl)-2,2-dimethylcyclopropane-1-
carboxylate (IX). Compound (1R)-cis-VII, 0.2 g
(0.484 mmol), was dissolved in 20 ml of anhydrous
chloroform, 0.126 g (0.4 mmol) of Bu4N+Br–, 0.89 g
(6.5 mmol) of K2CO3, 0.95 g (5 mmol) of CCl3CO2Na,
and 0.1 ml of MeOH were added, and the mixture was
heated for 8 h under reflux with stirring. The mixture
was diluted with ethyl acetate, washed with water, and
dried over Na2SO4. The solvent was distilled off, and
the residue was subjected to column chromatography
on silica gel using petroleum ether–ethyl acetate
(19:1) as eluent to isolate 0.08 g (33%) of syn-IX and
0.05 g (21%) of anti-IX. IR spectrum, ν, cm–1: 560,
590 (C–Cl); 1600 (C–Carom); 1720 (C=O); 1735 (COO).
(C–O–C); 169.99 (COO); 190.89 (C=O).
20
589
(1S)-trans-VII. [α] = +7.204° (c = 0.04). IR spec-
trum, ν, cm–1: 590 (C–Cl); 1600 (C–Carom); 1625
1
(C=C); 1690 (C=O); 1735 (COO). H NMR spectrum,
δ, ppm: 1.23 s (3H, 2-CH3), 1.35 s (3H, 2-CH3), 1.92 d
(1H, 1-H, J = 5 Hz), 2.40 s (3H, CH3CO), 2.55 d.d
(1H, 3-H, J = 5, 10 Hz), 5.13 s (2H, CH2), 6.64 d (1H,
CH=, J = 10 Hz), 6.92–7.42 m (9H, Harom). 13C NMR
spectrum, δC, ppm: 20.26, 25.67 (2-CH3); 26.52 (C2);
31.05 (C1); 31.44 (CH3CO); 36.44 (C3); 66.06 (CH2);
118.19, 118.39, 118.77, 118.96, 122.64, 123.40,
129.71, 129.83, 130.05 (Carom); 134.22 (CCl); 137.73
(C=CCl); 138.24 (CCH2); 156.84, 157.47 (C–O–C);
170.21 (COO); 191.67 (C=O).
20
589
1
syn-IX. [α] = –10.3° (c = 0.086). H NMR spec-
trum, δ, ppm: 1.21 t (1H, 3-H, J3,1 = J3,1′ = 8.5 Hz),
1.23 s (3H, 2-CH3), 1.25 s (3H, 2-CH3), 1.80 d (1H,
1-H, J = 8.5 Hz), 2.52 s (3H, CH3CO), 3.26 d (1H,
1′-H, J = 8.5 Hz), 5.15 s (2H, CH2), 6.91–7.40 m (9H,
Harom). 13C NMR spectrum, δC, ppm: 14.36 (2-CH3);
26.26 (C2); 28.49 (2-CH3); 29.85 (CH3CO); 29.91
(C1); 30.35 (C3); 33.32 (C1′); 60.61 (C2′); 64.87 (CCl2);
66.27 (CH2); 118.53, 118.73, 119.39, 119.48, 123.05,
123.90, 130.19, 130.28, 130.52 (Carom); 138.54
(CCH2); 157.29, 157.95 (COC); 170.46 (COO);
195.50 (C=O).
Methyl (1R)-cis-3-(2-acetyl-2,3,3-trichlorocyclo-
propyl)-2,2-dimethylcyclopropane-1-carboxylate
(VIII). Compound VI, 0.5 g (2.2 mmol), was dis-
solved in 13 ml of anhydrous chloroform, 0.189 g
(0.59 mmol) of Bu4N+ Br–, 2.4 g (17.4 mmol) of
K2CO3, 4.25 g (22.9 mmol) of CCl3CO2Na, and 0.1 ml
of MeOH were added, and the mixture was heated for
8 h under reflux with stirring. The mixture was diluted
with ethyl acetate, washed with water, and dried over
Na2SO4, the solvent was distilled off, and the residue
(0.4 g) was subjected to column chromatography on
silica gel using petroleum ether as eluent to isolate
0.24 g (35%) of syn-VIII and 0.16 g (23%) of anti-
VIII. IR spectrum, ν, cm–1: 560, 590 (C–Cl); 1600
(C–Carom); 1720 (C=O); 1735 (COO).
1
anti-IX. H NMR spectrum, δ, ppm: 1.17 t (1H,
3-H, J3,1 = J3,1′ = 8.6 Hz), 1.26 s (3H, 2-CH3), 1.29 s
(3H, 2-CH3), 1.76 d (1H, 1-H, J = 8.6 Hz), 2.39 s (3H,
CH3CO), 3.42 d (1H, 1′-H, J = 8.6 Hz), 5.17 s (2H,
CH2), 6.83–7.22 m (9H, Harom). 13C NMR spectrum,
δC, ppm: 17.89 (2-CH3); 24.52 (C2); 27.44 (2-CH3);
28.87 (CH3CO); 29.03 (C1); 29.54 (C3); 32.85 (C1′);
52.74 (C2′); 60.24 (CCl2); 65.38 (CH2); 118.28, 118.91,
119.25, 119.53, 122.69, 122.72, 129.69, 129.75, 129.79
20
589
1
syn-VIII. [α] = +1.4° (c = 0.1). H NMR spec-
trum, δ, ppm: 1.18 t (1H, 3-H, J3,1 = J3,1′ = 8.5 Hz),
1.22 s (3H, 2-CH3), 1.27 s (3H, 2-CH3), 1.76 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007

KASRADZE et al.
838
(Carom); 137.97 (CCH2); 156.86, 157.41 (COC); 170.58
(COO); 195.57 (C=O).
mixture was cooled to 10°C, and a solution of 0.375 g
(0.909 mmol) of (1R)-cis-VII in 0.7 ml of dimethyl
sulfoxide was quickly added. The mixture was stirred
for 5 min at 10°C and for 2 h at room temperature,
poured into 1.5 ml of ice water, and extracted with
diethyl ether. The extracts were combined, washed
with water and a saturated solution of NaCl, dried over
Na2SO4, and evaporated to isolate 0.26 g (67%) of
a mixture of syn and anti isomers of XI at a ratio of
4:1. IR spectrum, ν, cm–1: 580 (C–Cl), 1600 (C–Carom),
1720 (C=O), 1735 (COO).
Methyl (1R)-cis-3-(2-acetyl-2-chlorocyclopro-
pyl)-2,2-dimethylcyclopropane-1-carboxylate (X).
Dimethyl sulfoxide, 1.5 ml, was slowly added under
argon to a mixture of 0.29 g (1.32 mmol) of finely
powdered trimethylsulfoxonium iodide and 0.032 g
(2.6 mmol) of sodium hydride, and the mixture was
stirred for 20 min at room temperature. The mixture
was cooled to 10°C, a solution of 0.285 g (1.24 mmol)
of (1R)-cis-VI in 0.7 ml of dimethyl sulfoxide was
quickly added, and the mixture was stirred for 5 min at
10°C and for 2 h at room temperature, poured into
1.5 ml of ice water, and extracted with three portions
of diethyl ether. The extracts were combined, washed
with water and a saturated solution of NaCl, dried over
Na2SO4, and evaporated. The residue was subjected to
column chromatography on silica gel using petroleum
ether as eluent to isolate 0.17 g (57%) of a mixture of
syn and anti isomers of compound X at a ratio of 4:1.
IR spectrum, ν, cm–1: 590 (C–Cl), 1715 (C=O), 1735
(COO).
1
syn-XI. H NMR spectrum, δ, ppm: 1.06 t (1H,
2
3-H, J = 8.7 Hz), 1.17 d.d (1H, 3′-Ha, J = 5.3, J3′,1′
=
8.1 Hz), 1.23 s (6H, 2-CH3), 1.71 d (1H, 1-H, J =
8.7 Hz), 1.98 d.d (1H, 3′-Hb, 2J = 5.3, J3′,1′ = 10.1 Hz),
2.27 d.d.d (1H, 1′-H, J1′,3′ = 10.1, J1′,2′ = 8.1, J1′,3
=
8.7 Hz), 2.39 s (3H, CH3CO), 5.06 s (2H, CH2), 6.69–
7.39 m (9H, Harom).
1
anti-XI. H NMR spectrum, δ, ppm: 1.05 t (1H,
2
3-H, J = 8.4 Hz), 1.16 d.d (1H, 3′-Hb, J = 5.1, J3′,1′
=
8.1 Hz), 1.30 s (6H, 2-CH3), 1.74 d (1H, 1-H, J =
8.4 Hz), 1.85 d.d.d (1H, 1′-H, J1′,3′ = 9.9, 8.1, J1′,3
=
syn-X. 1H NMR spectrum, δ, ppm: 1.05 t (1H, 3-H,
8.4 Hz), 2.08 d.d (1H, 3′-Ha, J = 5.1, J3′,1′ = 9.9 Hz),
2.43 s (3H, CH3CO), 5.09 s (2H, CH2), 6.69–7.39 m
(9H, Harom).
2
2
J = 8.7 Hz), 1.17 d.d (1H, 3′-Ha, J = 5.3, J3′, 1′
=
8.2 Hz), 1.22 s (6H, 2-CH3), 1.64 d (1H, 1-H, J =
2
8.7 Hz), 2.0 d.d (1H, 3′-Hb, J = 5.3, J3′,1′ = 10.0 Hz),
REFERENCES
2.27 d.d.d (1H, 1′-H, J3′,1′ = 10.0, 8.2, J1′,3 = 8.7 Hz),
2.42 s (3H, CH3CO), 3.67 s (3H, OCH3). 13C NMR
spectrum, δC, ppm: 14.53 (2-CH3), 25.62 (C2), 26.63
(2-CH3), 26.83 (CH2), 27.62 (C1), 28.22 (C3), 28.72
(CH3CO), 33.51 (C1′), 51.88 (CH3O), 52.44 (C2′),
171.66 (COO), 204.08 (C=O).
1. Barret, A.G.M., Doubleday, W.W., Hamprecht, D., Kas-
dorf, K., Tustin, G.J., White, A.J.P., and Williams, D.J.,
Chem. Commun., 1997, no. 18, p. 1693.
2. Krasutskii, P.A., Baula, O.P., Fokin, A.A., Yurchen-
ko, A.G., and Promonenkov, V.K., Itogi Nauki Tekh., Org.
Khim., 1989, no. 9, p. 3.
3. Galin, F.Z., Kukovinets, O.S., Shereshovets, V.V., Safi-
ullin, R.L., Kukovinets, A.G., Kabal’nova, N.N., Kasrad-
ze, V.G., Zaripov, R.N., Kargapol’tseva, T.A., Kashi-
na, Yu.A., and Tolstikov, G.A., Russ. J. Org. Chem., 1996,
vol. 32, p. 1429.
4. Fokin, A.A., Baula, O.P., Yurchenko, A.G., Krasuts-
kii, P.A., and Promonenkov, V.K., Zh. Org. Khim., 1990,
vol. 26, p. 1363.
anti-X. 1H NMR spectrum, δ, ppm: 1.02 t (1H, 3-H,
2
J = 8.5 Hz), 1.16 d.d (1H, 3′-Hb, J = 5.2, J3′, 1′
=
8.2 Hz), 1.30 s (6H, 2-CH3), 1.68 d (1H, 1-H, J =
8.5 Hz), 1.89 d.d.d (1H, 1′-H, J3′,1′ = 9.9, 8.2, 8.5 Hz),
2
2.09 d.d (1H, 3′-Ha, J = 5.2, J3′,1′ = 9.9 Hz), 2.37 s
(3H, CH3CO), 3.64 s (3H, OCH3). 13C NMR spectrum,
δC, ppm: 14.93 (2-CH3), 25.63 (C2), 25.82 (CH2),
27.37 (2-CH3), 27.46 (C1), 28.16 (C3), 29.60 (CH3CO),
33.33 (C1′), 51.33 (C2′), 51.68 (CH3O), 171.34 (COO),
205.13 (C=O).
5. Fokin, A.A., Butova, E.D., Kolomitsin, I.V., Gagae-
va, E.A., Gogoman, I.V., Kornilov, A.M., Sorochin-
skii, A.E., Yurchenko, A.G., and Krasutskii, P.A., Zh. Org.
Khim., 1994, vol. 30, p. 669.
m-Phenoxybenzyl (1R)-cis-3-(2-acetyl-2-chloro-
cyclopropyl)-2,2-dimethylcyclopropane-1-carbox-
ylate (XI). Dimethyl sulfoxide, 1.5 ml, was slowly
added under argon to a mixture of 0.64 g (2.9 mmol)
of finely powdered trimethylsulfoxonium iodide and
0.035 g (2.95 mmol) of sodium hydride, and the mix-
ture was stirred for 20 min at room temperature. The
6. Fokin, A.A., Baula, O.P., Krasutskii, P.A., and Yurchen-
ko, A.G., Ukr. Khim. Zh., 1992, vol. 58, p. 1127.
7. Cebula, R.E.Y., Hanna, M.R., Theberge, C.R., Ver-
bicky, C.A., and Zercher, C.K., Tetrahedron Lett., 1996,
vol. 37, p. 8341.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 6 2007