Cyclopropane intermediates in the synthesis of chiral alcohols with methyl-branched carbon skeleton. Application in the synthesis of insect pheromones

Article abstract of DOI:10.1134/S1070428014070033

Several chiral building blocks, (2R)-2-methylundec-10-en-1-ol, (3R)-3-methylheptan-1-ol, and (4R)-4-methyloctan-1-ol, have been synthesized using cyclopropane intermediate products. It has been shown that the obtained chiral alcohols can be used in the sy

Full text of DOI:10.1134/S1070428014070033

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 7, pp. 934–942. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.N. Kovalenko, I.V. Mineeva, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 7, pp. 954–962.
Cyclopropane Intermediates in the Synthesis of Chiral Alcohols
with Methyl-Branched Carbon Skeleton. Application
in the Synthesis of Insect Pheromones
V. N. Kovalenko and I. V. Mineeva
Belarusian State University, pr. Nezavisimosti 4, Minsk, 220030 Belarus
e-mail: i.mineyeva@yandex.ru
Received January 29, 2014
Abstract—Several chiral building blocks, (2R)-2-methylundec-10-en-1-ol, (3R)-3-methylheptan-1-ol, and
(4R)-4-methyloctan-1-ol, have been synthesized using cyclopropane intermediate products. It has been shown
that the obtained chiral alcohols can be used in the synthesis of insect pheromones.
DOI: 10.1134/S1070428014070033
Methyl-branched optically active compounds are
difficultly accessible but important intermediates in the
synthesis of complex organic molecules. For this
purpose, synthetic building blocks and optically active
monoterpenoids (citronellal, pulegone, camphor,
menthol, isomenthol, isolimonene, etc.) are used most
frequently [1]. However, synthetic methyl-branched
intermediate products are accessible in small amounts
and are expensive, whereas the use of terpene com-
pounds involves multistep transformations since
methyl substituents therein are attached to the ring or
are remote from the terminal parts of their molecules.
In some cases, the use of natural compounds is limited
by the optical purity of starting materials, multistep
and complicated transformations, the use of expensive
reagents and enzymes, and availability of only one
optical enantiomer [1–3].
A particular place is occupied by syntheses utilizing
ring opening of hydroxycyclopropane derivatives
[22–32]. Enantiopure methyl-branched compounds
were synthesized by cyclopropanation of chiral amino
and hydroxy acid esters, followed by cyclopropyl–allyl
isomerization of the three-membered ring and dia-
stereoselective reduction of the double bond in the
resulting unsaturated compound [33–37].
Cyclopropane derivatives having no activated sub-
stituent in the ring can also undergo ring opening by
the action of transition metal-based reagents [38] and
strong electrophiles, e.g., lead(IV) [39], thallium(III)
[40], and mercury(II) salts [41]. These reactions are
generally characterized by high regio- and stereoselec-
tivity, and the most interesting substrates are cyclo-
propylcarbinols which are readily accessible as optical-
ly active substances [42–48].
Apart from standard methylation procedures, cyclo-
propane derivatives are widely used to generate chiral
centers bearing a methyl group. The synthesis of
optically active cyclopropyl ketones as intermediate
products was reported in numerous publications
[4–10]. Methyl-branched compounds can be obtained
from vinylcyclopropanes and divinylcyclopropanes
[11–18]. In this respect, asymmetric [3+2]-cycload-
dition reactions [19] and tandem transformations
including cyclorpopanation and Cope rearrangement
attract considerable interest [20, 21]. Such reactions
ensure preparation of optically active substituted cy-
clopentenes and 1,4-cycloheptadienes without isolation
of intermediate vinyl- and divinylcyclopropane
derivatives.
Thus, numerous examples of the use of cyclo-
propanes in stereoselective syntheses of methyl-
branched natural compounds indicate their high syn-
thetic potential. However, it is not always possible to
obtain appropriate cyclopropane derivatives with a suf-
ficiently high enantiomeric excess. Moreover, opening
of the three-membered ring can be accompanied by
reduction of the optical purity when the substrate con-
tains a tertiary chiral center. Some procedures require
difficultly accessible and toxic reagents. Therefore,
development of new efficient methods for the syn-
thesis of compounds possessing a methyl-branched
carbon skeleton via transformations of cyclopropanes
and cyclopropanols without loss of optical purity is
an important problem of organic synthesis.
934

CYCLOPROPANE INTERMEDIATES IN THE SYNTHESIS OF CHIRAL ALCOHOLS
935
Scheme 1.
Me
O
Me
Me
COOMe
MeONa, MeOH
LiAlH4, THF
MeO
MeO
MeO
OMe
OH
Cl
Cl
(1S,3R)-I
OMe
(R)-II
OMe
(R)-III
Me
(1) MsCl, Et3N, Et2O
(2) Bu4NBr, Me2CO
MeO
Br
OMe
(R)-IV
Me
Me
COOMe
MeO
Br
54%
Cl
Cl
OMe
(S)-IV
(1R,3S)-I
We previously demonstrated the possibility for the
sulfonate to obtain difunctional building block (R)-IV.
Following an analogous scheme, from stereoisomeric
ester (1R,3S)-I we synthesized bromide (S)-IV [51]
(Scheme 1).
Coupling of (R)-IV with Grignard reagent afforded
acetal V possessing a chiral center on C2 (Scheme 2).
It is known that removal of acetal protection can be
accompanied by partial racemization of α-branched
aldehyde [52]. However, no racemization was ob-
served when compound V was hydrolyzed with aque-
ous acetic acid in the presence of a catalytic amount of
HCl. Key alcohol VI was obtained by careful reduc-
tion of the reaction mixture obtained after removal of
the acetal protection from V. The enantiomeric excess
transformation of readily accessible methyl 2,2-di-
chlorocyclopropanecarboxylate (1S,3R)-(I) into chiral
ortho ester (R)-II by the action of sodium methoxide
via nucleophilic replacement of both chlorine atoms
[49] and subsequent opening of the three-membered
ring [50] (Scheme 1). It is known that ortho esters are
readily hydrolyzed in acidic medium and are stable in
basic medium and that they react with strong nucleo-
philes. By reduction of (R)-II with lithium tetrahy-
dridoaluminate in boiling tetrahydrofuran we obtained
compound (R)-III possessing hydroxy and protected
aldehyde groups. The hydroxy group in (R)-III was
replaced by bromine through intermediate methane-
Scheme 2.
Me
Me
( )7
Li2CuCl4
N-methylpyrrolidin-2-one
(1) AcOH, H2O, HCl
(2) LiAlH4, Et2O
MeO
HO
(R)-IV
+ CH2=CH(CH2)5MgBr
( )7
CH2
CH2
OMe
V
VI
Me
Me
Me
[54]
Me
Br
( )3
( )3 ( )7
CH2
VII
Me
Me
(1) MsCl, Et3N, Et2O
(2) Bu4NBr, Me2CO
(1) Mg, THF
(2) (S)-IV, Li2CuCl4, NMP
MeO
( )7
VIII
( )3 ( )7
CH2
CH2
OMe
IX
(1) MsCl, Et3N, Et2O
(2) Bu4NBr, Me2CO
(3) PrMgBr, Li2CuCl4, NMP, THF
Me
Me
(1) AcOH, H2O, HCl
(2) LiAlH4, Et2O
HO
IX
VII
( )3 ( )7
CH2
X
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

KOVALENKO, MINEEVA
936
Scheme 3.
(1) MgBr2, CHCl3, Et2O (70%)
(2) 4-MeC6H4SO2Na, DMF (90%)
(3) Bu3SnH, AIBN, PhH (67%)
(1) MsCl, Et3N, Et2O (98%)
(2) HCl, H2O2, MeOH (70%)
OEt OH
O
OMs
O
CH2
SnBu3
EtO
MeO
MeO
O
XIV
XV
XIII
O
BzlOCH2CHO, (S)-BINOL
Ti(OPr-i)4, MePh
NaBH4, NiCl2·6H2O
H3BO3, THF–H2O
O
O
85%
94%
BzlO
BzlO
Me
Me
XII, ee 97%
XI, de 91%
(ee) of alcohol VI was no less than 99%, as followed
2 equiv of bromide VIII, which afforded acetal IX.
Compound VIII was synthesized from alcohol VI
according to the procedure described previously for
bromide (R)-IV. Acetal IX was converted into chiral
alcohol X (ee 99%) and then into the corresponding
bromide, and reaction of the latter with propylmagne-
sium bromide gave target compound VII in an overall
yield of 13% in 15 steps starting from methyl ester
(1R,3S)-I.
1
from the analysis of the H NMR spectra of the
corresponding Mosher ester [53]. The overall yield of
VI starting from (1S,3R)-I was 43%.
Compound VI is a convenient building block for
the synthesis of (10R,14R)-10,14-dimethyloctadec-1-
ene (VII) [54], a component of the apple leafminer
Lyonetia prunifoliella pheromone [55–57]. Only a few
syntheses of VII and its stereoisomers have been
reported [54, 57–59].
Optically active lactone XI also turned out to be
a convenient intermediate product for the preparation
of methyl-branched building blocks for insect phero-
The key step in the synthesis of VII was coupling
of (S)-IV with the Grignard compound prepared from
Scheme 4.
OH
OH
Me
O
Me
OH
EtMgBr, Ti(OPr-i)4, THF
KOH, MeOH
XI
OBzl
Me
OBzl
XVI
XVII
VII
(1) H2, Pd/C, MeOH
(2) PhI(OAc)2, MeOH
(3) NaBH4, MeOH
Me
Me
[62]
Me
Me
Me
( )3
( )3
( )11
XX
Me
OH
CH2
XIX
Me
Me
Me
N2H4 · H2O, NaOH
triethylene glycol
( )3
( )3 ( )5
XXI
Me
OH
Me
OBzl
( )3
Me
Me
XVIII
[71]
[72]
Me
Me
( )3
( )9
XXIII
Me
(1) MsCl, Et3N, Et2O
(2) LiAlH4, THF
(3) H2, Pd/C, MeOH
Me
Me
OH
Me
( )3
XXII
( )3
( )3
XXIV
( )21
Me
[74]
Me
OH
( )3
O
XXV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

CYCLOPROPANE INTERMEDIATES IN THE SYNTHESIS OF CHIRAL ALCOHOLS
937
mones. Compound XI was synthesized according to
the previously developed scheme which included dia-
stereoselective reduction of chiral lactone XII. Lactone
XII was obtained by Heck allylation of stannane XIII
[34, 36] which is available on a gram scale through
cyclopropanol intermediates XIV and XV [60, 61]
(Scheme 3). The overall yield of compound XII in
7 steps was 23%.
panes, cyclopropanols, and products of their trans-
formations and demonstrated broad potential of their
use in the preparation of various biologically active
compounds, primarily pest insect pheromones. In
particular, we have synthesized (10R,14R)-10,14-di-
methyloctadec-1-ene, a pheromone component of the
apple leafminer moth Lyonetia prunifoliella. Formal
schemes for the synthesis of pheromones of the peach
leafminer moth Lyonetia clerkella L., false hemlock
looper Nepytia freemani, and rhinoceros beetles of the
genus Oryctes and a component of the cuticular secre-
tion of the ant Diacamma sp. have been proposed.
Compound XI was smoothly subjected to cyclo-
propanation [30] (Scheme 4) to obtain hydroxyalkyl
cyclopropanol XVI which was converted into ethyl
ketone XVII. The Wolff–Kishner reduction of XVII
gave alcohol XVIII, and a series of simple transforma-
tions of the latter (removal of the benzyl protection,
oxidative cleavage of intermediate diol, and reduction
of the resulting aldehyde) afforded known chiral
alcohol XIX [62–69] with methyl-branched carbon
skeleton. Compound XIX was used previously to build
up a side-chain fragment of heptadepsipeptide HUN-
7293 [66] and to synthesize (14R)-methyloctadec-1-
ene (XX), sex pheromone of the peach leafminer moth
Lyonetia clerkella L. [62]. Alcohol XIX may also be
useful for the synthesis of other pheromones contain-
ing a similar structural fragment, e.g., of apple leaf-
miner pheromone VII and 5,9-dimethylpentadecane
stereoisomers (coffee leafminer moth Perileucoptera
coffeella pheromone XXI) [70]. The overall yield of
XIX starting from lactone XI (6 steps) was 34%, and
its ee value was estimated at 97% with the aid of
Mosher’s acid [53]. The overall yield of chiral building
block XIX was 8% in 13 steps starting from XIV.
Successive methanesulfonylation of XVIII, reduc-
tion of the resulting methanesulfonate, and removal of
the benzyl protection afforded known alcohol XXII
[71–73] which was also used in the synthesis of insect
pheromones (Scheme 3). For example, compound
XXII was converted into 3,13-dimethylheptadecane
stereoisomers XXIII (components of the false hemlock
looper Nepytia freemani sex pheromone [71]),
(R)-5-methylheptacosane XXIV (characteristic com-
ponent of the cuticular hydrocarbons of queen of the
ant, Diacamma sp. [72]), and (R)-4-methyloctanoic
acid (XXV, pheromone component of rhinoceros
beetles of the genus Oryctes that are dangerous wood
pests [74]). The overall yield of XXII was 39%
starting from lactone XI (6 steps) and 9% starting from
cyclopropanol XIV (13 steps).
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded from
solutions in chloroform-d on a Bruker AC 400 instru-
ment at 400 and 100 MHz, respectively. The IR spectra
were recorded from solutions in carbon tetrachloride
on a Bruker Vertex 70 spectrometer. The optical rota-
tions were measured at room temperature on an SM-3
polarimeter (scale division 0.05°). The products were
isolated by chromatography on silica gel (70–
230 mesh). Gas chromatographic/mass spectrometric
analyses were carried out on a Hewlett Packard
HP 5890 chromatograph coupled with an HP 5972
mass-selective detector (HP Innovax capillary column,
50 m×0.2 mm; carrier gas helium; electron impact,
70 eV). The elemental compositions were determined
by the semimicro method. All solvents were dried
according to standard procedures and distilled just
before use.
Methyl (3R)-4,4,4-trimethoxy-3-methylbutano-
ate (R)-(II). A solution of 90.0 mmol of sodium
methoxide in 45 mL of anhydrous methanol was added
dropwise under stirring to a solution of 7.50 g
(41.0 mmol) of ester (1S,3R)-I [50] in 30 mL of
anhydrous methanol on cooling with an ice bath. The
cooling bath was removed, and the mixture was heated
to 40°C and kept for 2 h at that temperature. The
mixture was cooled to 0°C, diluted with 200 mL of
water, and extracted with methylene chloride (5×
50 mL). The extracts were combined, washed with
brine, and dried over Na2SO4, the solvent was removed
under reduced pressure, and the residue was distilled in
a vacuum. Yield 6.93 g (82%), bp 48–50°C (1 mm),
[α]D = +9.2° (c = 7.5, Et2O). IR spectrum: ν 1741 cm–1.
1H NMR spectrum, δ, ppm: 0.96 d (3H, CH3CH, J =
6.8 Hz), 2.13 d.d (1H, CHCH2, J = 15.4, 9.5 Hz),
2.45–2.54 m (1H, CH3CH), 2.63 d.d (1H, CHCH2, J =
15.4, 4.1 Hz), 3.29 s (9H, 4-OCH3), 3.65 s (3H,
In summary, we have described simple and conve-
nient schemes for the synthesis of several optically
active alcohols as methyl-branched chiral building
blocks on the basis of halogen-substituted cyclopro-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

KOVALENKO, MINEEVA
938
CO2CH3). 13C NMR spectrum, δC, ppm: 14.2, 35.5,
36.4, 50.4 (3C), 51.4, 114.6, 173.8. Found, %: C 52.49;
H 8.82. C9H18O5. Calculated, %: C 52.41; H 8.80.
Methyl (3S)-4,4,4-trimethoxy-3-methyl-butano-
ate (S)-(II) was synthesized in a similar way from
ester (1R,3S)-I. Yield 82%, [α]D = –9.2° (c = 7.5,
Et2O). The spectral parameters of (S)-II were identical
to those of (R)-II.
evaporated under reduced pressure. The residue was
dissolved in 80 mL of acetone, 24.6 g (76.9 mmol) of
tetrabutylammonium bromide and 0.7 mL (5.1 mmol)
of triethylamine were added, and the mixture was
heated for 2 h at 50–55°C. The mixture was cooled and
evaporated under reduced pressure, the residue was
treated with 200 mL of water, and the product was
extracted into diethyl ether (4×50 mL). The combined
extracts were washed with water and brine, dried over
Na2SO4, and evaporated under reduced pressure, and
the residue was purified by chromatography using
petroleum ether–diethyl ether (20:1) as eluent. Yield
8.77 g (81%), [α]D = –14.5° (c = 5.0, Et2O). IR spec-
trum, ν, cm–1: 2935, 2831. 1H NMR spectrum, δ, ppm:
0.92 d (3H, CH3CH, J = 6.8 Hz), 1.63–1.71 m (1H,
CH3CH), 1.94–2.12 m (2H, CHCH2), 3.35 s and 3.36 s
(3H each, CH3O), 3.39–3.58 m (2H, CH2Br), 4.06 d
[1H, CH(OCH3)2, J = 6.0 Hz]. 13C NMR spectrum, δC,
ppm: 14.1, 32.1, 34.5, 34.9, 54.0, 54.5, 108.4. Found,
%: C 39.90; H 7.19. C7H15BrO2. Calculated, %:
C 39.83; H 7.16.
(3R)-4,4-Dimethoxy-3-methylbutan-1-ol
(R)-(III). Lithium tetrahydridoaluminate, 7.40 g
(195.0 mmol), was added in portions under stirring to
a solution of 20.00 g (97.0 mmol) of ester (R)-II in
100 mL of THF, and the mixture was heated for 8 h
under reflux in an argon atmosphere. The mixture was
cooled and treated in succession with 7 mL of water,
7 mL of 15% aqueous sodium hydroxide, and 20 mL
of water, 100 mL of methylene chloride was then
added, and the mixture was filtered. The filtrate was
dried over Na2SO4 and evaporated under reduced pres-
sure, and the residue was subjected to chromatography
using petroleum ether–diethyl ether (2:1) as eluent.
Yield 11.95 g (83%), [α]D = +5.5° (c = 3.2, Et2O). IR
(2S)-4-Bromo-1,1-dimethoxy-2-methylbutane
(S)-IV was synthesized in a similar way from (S)-III.
Yield 79%, [α]D = +14.0° (c = 5.0, Et2O). The spectral
parameters of the product coincided with those
of (R)-IV.
1
spectrum: ν 3487 cm–1. H NMR spectrum, δ, ppm:
0.94 d (3H, CH3CH, J = 6.9 Hz), 1.41–1.49 m and
1.70–1.78 m (1H each, CHCH2), 1.89–1.99 m (1H,
CH3CH), 2.07 br.s (1H, OH), 3.36 s and 3.39 s (3H
each, OCH3), 3.59–3.75 m (2H, CH2OH), 4.08 d [1H,
CH(OCH3)2, J = 6.0 Hz]. 13C NMR spectrum, δC, ppm:
15.4, 33.4, 35.0, 53.8, 54.9, 61.0, 109.0. Found, %:
C 56.75; H 10.85. C7H16O3. Calculated, %: C 56.73;
H 10.88.
(10R)-11,11-Dimethoxy-10-methylundec-1-ene
(V). The Grignard reagent prepared from 4.43 g
(25.0 mmol) of 7-bromohept-1-ene and 0.91 g
(37.5 mmol) of magnesium in 30 mL of THF [59] was
added under stirring at room temperature to a solution
of 2.25 g (10.7 mmol) of bromide (R)-IV, 8.92 g
(90.0 mmol) of N-methylpyrrolidin-2-one (NMP),
40 mg (0.94 mmol) of LiCl, and 63 mg (0.47 mmol) of
CuCl2 in 20 mL of THF. The mixture was stirred for
1 h at room temperature, treated with 40 mL of a satu-
rated aqueous solution of ammonium chloride, and the
aqueous phase was extracted with petroleum ether
(3×20 mL). The combined extracts were washed with
a saturated aqueous solution of NaHCO3 and dried
over Na2SO4, the solvent was distilled off under
reduced pressure, and the residue was subjected to
chromatography using petroleum ether–ethyl acetatate
(30:1) as eluent. Yield 2.30 g (94%), [α]D = +13.1°
(3S)-4,4-Dimethoxy-3-methylbutan-1-ol (S)-(III)
was synthesized in a similar way from ester (S)-II.
Yield 83%, [α]D = –5.5° (c = 3.0, Et2O). The spectral
parameters of the product were identical to those of
(R)-III.
(2R)-4-Bromo-1,1-dimethoxy-2-methylbutane
(R)-(IV). A solution of 7.59 g (51.3 mmol) of alcohol
(R)-III and 16.0 mL (115.0 mmol) of triethylamine in
50 mL of anhydrous diethyl ether was cooled to 0°C,
a solution of 6.0 mL (77.5 mmol) of methanesulfonyl
chloride in 25 mL of diethyl ether was added, and the
mixture was stirred for 1 h at 0°C. The mixture was
then treated with a saturated aqueous solution of
sodium hydrogen carbonate (100 mL), the organic
layer was separated, the aqueous layer was extracted
with ethyl acetate (3×30 mL), the extracts were com-
bined with the organic phase, dried over Na2SO4, and
evaporated under reduced pressure, the residue was
dissolved in 50 mL of benzene, and the solution was
1
(c = 1.8, hexane). IR spectrum: ν 3081 cm–1. H NMR
spectrum, δ, ppm: 0.88 d (3H, CH3CH, J = 6.8 Hz),
1.02–1.51 m [12H, (CH2)6CH2CH=], 1.66–1.76 m
(1H, CH3CH), 2.00–2.06 m (2H, CH2CH=CH2), 3.34 s
(6H, CH3O), 4.01 d [1H, CH(OCH3)2, J = 6.5 Hz],
4.90–5.00 m (2H, CH=CH2), 5.81 d.d.t (1H, CH=CH2,
J = 17.0, 10.2, 6.7 Hz). 13C NMR spectrum, δC, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

CYCLOPROPANE INTERMEDIATES IN THE SYNTHESIS OF CHIRAL ALCOHOLS
939
14.3, 26.9, 28.9, 29.1, 29.4, 29.8, 31.6, 33.8, 35.6,
53.8, 54.0, 108.9, 114.1, 139.2. Found, %: C 73.55;
H 12.35. C14H28O2. Calculated, %: C 73.63; H 12.36.
(10R,14S)-15,15-Dimethoxy-10,14-dimethylpen-
tadec-1-ene (IX). A solution of 0.89 g (3.60 mmol) of
bromide VIII in 4.5 mL of THF was added dropwise
under argon to 0.18 g (7.40 mmol) of magnesium. The
mixture was stirred for 1 h at 45°C and cooled to room
temperature, and the resulting solution of Grignard
reagent was added dropwise under stirring in an argon
atmosphere to a solution of 0.38 g (1.80 mmol) of
bromide (S)-IV, 1.45 g (14.6 mmol) of NMP, 4.2 mg
(0.10 mmol) of LiCl, and 6.7 mg (0.05 mmol) of CuCl2
in 5 mL of THF. The mixture was stirred for 1 h at
room temperature, treated with 10 mL of a saturated
aqueous solution of ammonium chloride, and extracted
with petroleum ether (3×10 mL). The combined
extracts were washed with a saturated solution of
NaHCO3 and dried over Na2SO4, the solvent was
removed under reduced pressure, and the product was
isolated by chromatography using petroleum ether–
ethyl acetate (30:1) as eluent. Yield 0.46 g [85%,
calculated on (S)-IV], [α]D = –10.3° (c = 1.9, hexane).
IR spectrum: ν 3079 cm–1. 1H NMR spectrum, δ, ppm:
0.83 d (3H, CH3CH, J = 6.5 Hz), 0.88 d [3H,
CH3CHCH(OCH3)2, J = 6.8 Hz], 1.02–1.48 m [19H,
(CH2)6CH2CH=, CH(CH2)3CH, CHCH3], 1.66–1.76 m
[1H, CH3CHCH(OCH3)2], 2.00–2.06 m (2H,
CH2CH=CH2), 3.34 s (6H, CH3O), 4.01 d [1H,
CH(OCH3)2, J = 6.5 Hz], 4.90–5.00 m (2H, CH=CH2),
5.81 d.d.t (1H, CH=CH2, J = 17.0, 10.2, 6.7 Hz).
13C NMR spectrum, δC, ppm: 14.3, 19.6, 24.3, 27.1,
28.9, 29.1, 29.5, 29.9, 31.9, 32.7, 33.8, 35.6, 37.1,
37.2, 53.8, 54.0, 109.0, 114.1, 139.2. Found, %:
C 76.54; H 12.85. C19H38O2. Calculated, %: C 76.45;
H 12.83.
(2R)-2-Methylundec-10-en-1-ol (VI). A mixture of
11.49 g (50.4 mmol) of acetal V, 100 mL of acetic
acid, 100 mL of water, and 1.0 mL of 5% aqueous HCl
was stirred for 5 h at room temperature under argon.
The mixture was diluted with 150 mL of water,
neutralized with solid NaHCO3, and extracted with
diethyl ether (4×80 mL). The combined extracts were
washed with brine and dried over Na2SO4, the solvent
was removed under reduced pressure, the residue was
dissolved in 50 mL of diethyl ether, and the solution
was added dropwise under stirring to a suspension of
1.00 g (26.3 mmol) of LiAlH4 in 50 mL of anhydrous
diethyl ether on cooling to –20°C. The mixture was
allowed to warm up to 0°C and treated with 100 mL of
10% aqueous H2SO4. The organic phase was separated,
the aqueous phase was extracted with diethyl ether
(3 ×50 mL), the extracts were combined with the
organic phase and washed in succession with water
and saturated aqueous solutions of NaHCO3 and NaCl,
the solvent was distilled off under reduced pressure,
and the residue was subjected to chromatography using
petroleum ether–ethyl acetate (40:1) as eluent. Yield
7.79 g (84%), [α]D = +8.4° (c = 4.6, CHCl3). IR spec-
trum, ν, cm–1: 3508, 3078. 1H NMR spectrum, δ, ppm:
0.90 d (3H, CH3CH, J = 6.8 Hz), 1.05–1.64 m [14H,
(CH2)6CH2CH=, CH3CH, OH], 2.00–2.06 m (2H,
CH2CH=CH2), 3.41 d.d (1H, CH2OH, J = 10.4,
6.5 Hz), 3.50 d.d (1H, CH2, J = 10.4, 5.7 Hz), 4.91–
5.01 m (2H, CH=CH2), 5.81 d.d.t (1H, CH=CH2, J =
17.0, 10.2, 6.7 Hz). 13C NMR spectrum, δC, ppm: 16.5,
26.9, 28.9, 29.1, 29.4, 29.8, 33.1, 33.8, 35.7, 68.3,
114.1, 139.2. Found, %: C 78.22; H 13.09. C12H24O.
Calculated, %: C 78.20; H 13.12.
(2S,6R)-2,6-Dimethylpentadec-14-en-1-ol (X)
was synthesized from acetal IX according to the
procedure described above for alcohol VI. Yield 82%.
The spectral parameters of the product coincided with
those reported in [56].
(10R)-11-Bromo-10-methylundec-1-ene (VIII)
was synthesized from alcohol VI according to the
procedure described above for compound (R)-IV.
The product was isolated by chromatography using
petroleum ether as eluent. Yield 93%. IR spectrum:
(10R,14R)-10,14-Dimethyloctadec-1-ene (VII).
Following the procedure described above for the
synthesis of (R)-IV, mesylation of 0.28 g (1.10 mmol)
of alcohol X, followed by replacement of the sulfonate
group by bromine, gave the corresponding bromide
which was dissolved (without additional purification)
in 3 mL of THF, 2.20 g (22.2 mmol) of NMP, 19 mg
(0.45 mmol) of LiCl, and 30 mg (0.22 mmol) of CuCl2
were added, and 5.0 mL (5.0 mmol) of a 1.0 M solu-
tion of propylmagnesium bromide in THF was added
dropwise under stirring in an argon atmosphere. The
mixture was stirred for 1 h at room temperature and
treated with 10 mL of a saturated aqueous solution of
1
ν 3078 cm–1. H NMR spectrum, δ, ppm: 1.00 d (3H,
C H 3 C H , J = 6 . 7 H z ) , 1 . 1 7 – 1 . 5 1 m [ 1 2 H,
(CH2)6CH2CH=], 1.75–1.82 m (1H, CH3CH), 2.00–
2.06 m (2H, CH2CH=CH2), 3.32 d.d (1H, CH2Br, J =
9.7, 6.4 Hz), 3.40 d.d (1H, CH2Br, J = 9.7, 5.0 Hz),
4.91–5.01 m (2H, CH=CH2), 5.81 d.d.t (1H, CH=CH2,
J = 17.0, 10.2, 6.7 Hz). 13C NMR spectrum, δC, ppm:
18.7, 26.8, 28.9, 29.1, 29.4, 29.6, 33.8, 34.8, 35.2,
41.6, 114.1, 139.2. Found, %: C 58.36; H 9.35.
C12H23Br. Calculated, %: C 58.30; H 9.38.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014

KOVALENKO, MINEEVA
940
ammonium chloride, and the aqueous phase was ex-
tracted with petroleum ether (3×10 mL). The com-
bined extracts were washed with a saturated aqueous
solution of NaHCO3 and dried over Na2SO4, the
solvent was removed under reduced pressure, and the
residue was subjected to chromatography using petro-
leum ether as eluent. Yield 0.28 g (91%). The spectral
parameters of the product coincided with those given
in [54, 56, 59]. According to the GLC data, compound
VII contained >98% of the main substance. Mass
spectrum: m/z 280 (Irel 0.4%) [M]+.
chromatography using petroleum ether–ethyl acetate
(25:1) as eluent. Yield 0.36 g (90%), [α]D = –4.2° (c =
1.8, CHCl3). IR spectrum, ν, cm–1: 3430, 1712, 1196,
1093. 1H NMR spectrum, δ, ppm: 0.91 d (3H, CHCH3,
J = 6.7 Hz), 0.95 t (3H, CH2CH3, J = 7.5 Hz), 1.58–
1.74 m (3H, CHCH3, CHCH2CHOH), 1.89 br.s (1H,
OH), 1.90–2.06 m (2H, CH3CH2CO), 2.27–2.46 m
(2H, COCH2CH), 3.41 d.d (1H, CH2OBzl, J = 10.0,
4.4 Hz), 3.47 d.d (1H, CH2OBzl, J = 10.0, 6.4 Hz),
4.09–4.15 m (1H, CHOH), 4.57 br.s and 4.59 br.s (1H
each, CH2Ph), 7.27–7.38 m (5H, Ph). 13C NMR spec-
trum, δC, ppm: 7.5, 22.1, 25.1, 26.0, 35.9, 40.6, 50.2,
69.6, 73.2, 73.7, 127.5, 126.6, 127.7, 128.3, 128.5,
138.5, 211.3. Found, %: C 72.72; H 9.13. C16H24O3.
Calculated, %: C 72.69; H 9.15.
1-[(2S,4S)-5-Benzyloxy-3-hydroxy-2-methylpen-
tyl]cyclopropanol (XVI). A solution of 45.0 mmol of
ethylmagnesium bromide in 45 mL of THF was added
under stirring over a period of 4.5 h to a solution
of 2.34 g (10.0 mmol) of lactone XI and 2.8 mL
(10.0 mmol) of Ti(OPr-i)4 in 10 mL of THF, and the
mixture was stirred for 12 h. The solvent was removed
under reduced pressure, and 50 mL of methylene
chloride and 6 mL of a saturated aqueous solution of
ammonium chloride were added to the residue under
efficient cooling. The mixture was filtered, the precip-
itate was washed with methylene chloride (3×20 mL),
and the organic phase was separated, washed with
a saturated aqueous solution of NaHCO3 (50 mL), and
dried over Na2SO4. The solvent was removed under
reduced pressure, and the product was isolated by
chromatography using petroleum ether–ethyl acetate
(10:1) as eluent. Yield 2.14 g (81%), [α]D = –3.2° (c =
1.2, CHCl3). IR spectrum, ν, cm-1: 3392, 1076, 1028.
1H NMR spectrum, δ, ppm: 0.98 d (3H, CH3CH, J =
6.7 Hz), 0.33–0.43 m and 0.68–0.78 m (2H each, CH2
in cyclopropane), 0.95–1.09 m and 1.24–1.36 m
(1H each, CCH2CHCH3), 1.60–1.69 m (1H, CH3CH),
1.73–1.82 m and 2.10–2.17 m (1H each, CH2CHOH),
3.29–3.34 m and 3.43–3.47 m (1H each, CH2OBzl),
3.91–3.98 m (1H, CHOH), 4.54 br.s (2H, CH2Ph),
7.27–7.38 m (5H, Ph). 13C NMR spectrum, δC, ppm:
12.9, 14.5, 20.7, 27.0, 39.2, 45.9, 53.5, 68.8, 73.30,
75.3, 127.7 (2C), 128.4 (2C), 137.9. Found, %: C 72.73;
H 9.13. C16H24O3. Calculated, %: C 72.69; H 9.15.
(2S,4R)-1-Benzyloxy-4-methyloctan-2-ol (XVIII).
Powdered potassium hydroxide, 0.30 g (5.4 mmol),
was added to a solution of 0.24 g (0.9 mmol) of ketone
XVII and 0.2 mL of hydrazine hydrate in 4.5 mL of
triethylene glycol. The mixture was carefully heated in
a stream of argon to 180°C over a period of 1 h and
then to 210°C, cooled to room temperature, and diluted
with 20 mL of water, and the aqueous phase was
extracted with diethyl ether (3×10 mL). The combined
extracts were washed with brine (15 mL) and dried
over Na2SO4, the solvent was removed under reduced
pressure, and the product was isolated by chromatog-
raphy using petroleum ether–ethyl acetate (25:1) as
eluent. Yield 0.16 g (70%), [α]D = –6.3° (c = 1.6,
CHCl3). IR spectrum, ν, cm–1: 3460, 1103, 1029.
1H NMR spectrum, δ, ppm: 0.87 d (3H, CHCH3, J =
6.9 Hz), 0.88 t (3H, CH2CH3, J = 6.9 Hz), 1.06 d.d.d
(1H, CHCH2CHOH, J = 13.3, 9.4, 3.8 Hz), 1.12–
1.34 m [6H, CH3(CH2)3CH], 1.49 d.d.d (1H,
CHCH2CHOH, J = 13.3, 9.4, 4.4 Hz), 1.61–1.70 m
(1H, CHCH3), 2.28 br.s (1H, OH), 3.30 d.d (1H,
CH2OBzl, J = 9.4, 7.9 Hz), 3.43 d.d (1H, CH2OBzl,
J = 9.4, 2.8 Hz), 3.90–3.94 m (1H, CHOH), 4.56 br.s
(2H, CH2Ph), 7.24–7.38 m (5H, Ph). 13C NMR spec-
trum, δC, ppm: 14.1, 19.2, 22.9, 28.9, 29.2, 37.5, 40.3,
68.3, 73.4, 75.3, 127.7 (3C), 128.5 (2C), 138.6. Found,
%: C 76.79; H 10.45. C16H26O2. Calculated, %:
C 76.75; H 10.47.
(5S,7S)-8-Benzyloxy-7-hydroxy-5-methyloctan-
3-one (XVII). Potassium hydroxide, 0.17 g
(3.0 mmol), was added to a solution of 0.40 g
(1.5 mmol) of cyclopropanol XVI in 3 mL of metha-
nol, and the mixture was heated for 1 h under reflux.
The mixture was diluted with water and extracted with
diethyl ether (3×10 mL), the combined extracts were
dried over Na2SO4, the solvent was removed under
reduced pressure, and the residue was subjected to
(3R)-3-Methylheptan-1-ol (XIX). Alcohol XVIII,
3.00 g (12.0 mmol), was dissolved in 50 mL of
methanol, 0.30 g of 5% Pd(OH)2/C was added, and the
mixture was vigorously stirred for 3 h in a hydrogen
atmosphere. The mixture was diluted with 50 mL of
methylene chloride, the catalyst was filtered off and
washed with 30 mL of methylene chloride, and the
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CYCLOPROPANE INTERMEDIATES IN THE SYNTHESIS OF CHIRAL ALCOHOLS
941
filtrate was combined with the washings and evaporat-
ed under reduced pressure. The residue was dissolved
in 20 mL of methanol, 4.67 g (14.5 mmol) of
PhI(OAc)2 was added, the mixture was stirred for
10 min and cooled to 0°C, 0.46 g (12.0 mmol) of
NaBH4 was added, and the mixture was stirred for 1 h.
It was then treated with a saturated aqueous solution of
NH4Cl (40 mL) and extracted with diethyl ether (3×
15 mL), the combined extracts were dried over MgSO4
and evaporated under reduced pressure, and the prod-
uct was isolated by chromatography on silica gel using
petroleum ether–ethyl acetate (20:1) as eluent. Yield
1.03 g (66% in 3 steps). The spectral parameters of
XIX coincided with those given in [62].
Pheromones from trans-2,2-Dichloro-3-methylcyclo-
propanecarboxylic and 3-Bromomethylbut-3-enoic
Acid Esters; state registry no. 20131542).
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