Cyclopropanol Methodology in the Synthesis of (4R)- and (4S)-4-Methyltetrahydro-2H-pyran-2-ones. Application in the Synthesis of Insect Pheromones with Methyl-Branched Carbon Skeleton

Article abstract of DOI:10.1134/S1070428015030094

A number of chiral methyl-branched building blocks have been synthesized starting from (4S)-4-methyltetrahydro-2H-pyran-2-one, and the possibility for using them for the preparation of mealworm beetle, rhinoceros beetle, and earth-boring dung beetle phero

Full text of DOI:10.1134/S1070428015030094

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 3, pp. 341–351. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © I.V. Mineeva, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 3, pp. 359–368.
Cyclopropanol Methodology in the Synthesis
of (4R)- and (4S)-4-Methyltetrahydro-2H-pyran-2-ones.
Application in the Synthesis of Insect Pheromones
with Methyl-Branched Carbon Skeleton
I. V. Mineeva
Belarusian State University, pr. Nezavisimosti 4, Minsk, 220030 Belarus
e-mail: i.mineyeva@yandex.ru
Received September 26, 2014
Abstract—A number of chiral methyl-branched building blocks have been synthesized starting from
(
4S)-4-methyltetrahydro-2H-pyran-2-one, and the possibility for using them for the preparation of mealworm
beetle, rhinoceros beetle, and earth-boring dung beetle pheromones and many other biologically active
compounds has been demonstrated.
DOI: 10.1134/S1070428015030094
Methyl-branched compounds are important inter-
mediate products in the synthesis of complex organic
molecules [1–3]. Such compounds are often available
in small amounts and are very expensive, while the use
of natural compounds is limited because of insufficient
optical purity of starting materials, accessibility of only
one optical isomer, multistep transformations, and the
necessity of expensive reagents and steps involving
enzymatic transformations [1].
acid afforded difunctional chiral block 4 [44]
(Scheme 1). Removal of the dimethyl acetal protection
from ester 4 and subsequent reduction of the aldehyde
group gave lactone (S)-5. Enantiomeric lactone (R)-5
was also synthesized as a result of a series of simple
transformations including hydride reduction of 4 and
oxidation of intermediate cyclic acetal.
(
4S)-4-Methyltetrahydro-2H-pyran-2-one (S-5) can
be obtained by crystallization of diastereoisomer mix-
ture formed in reactions of appropriate racemates with
chiral alcohols and amines [47–51], enzymatic cleav-
age of 3-methylglutaric acid dimethyl ester [52–59],
electrochemical [60–63] or enzymatic oxidation of ra-
cemic 3-methylpentane-1,5-diol [64–66], asymmetric
Michael addition [67–69], and other methods [70–73].
Methyl-substituted chiral centers are often created
with the aid of cyclopropane derivatives, such as
cyclopropyl ketones [4–10], vinyl- and divinylcyclo-
propanes [11–18], nonfunctional cyclopropane deriva-
tives [19–22], and optically active cyclopropylcar-
binols [23–29]. Of particular importance are syntheses
involving ring opening of cyclopropanol derivatives
(
4S)-4-Methyltetrahydro-2H-pyran-2-one (S-5) was
[
30–40]. Enantioselective syntheses of methyl-
used to synthesize many biologically active natural
compounds, in particular methanophenazine (6) [57],
macrolide tulearin C (7) [50], (+)-faranal (8, trail
pheromone of pharaoh’s ant Monomorium pharaonis)
branched compounds can be accomplished via cyclo-
propanation of chiral amino and hydroxy carboxylic
acid esters, followed by cyclopropyl–allyl isomeriza-
tion of the three-membered ring and diastereoselective
reduction of the double bond in the resulting unsat-
urated compound [41–45]. This cyclopropanol meth-
odology was also applied in the present work.
[55, 56], cytotoxic neopeltolide macrolactone (9) [58],
and perfume ingredients (R)-(–)-muscone (10) [49] and
(R,Z)-5-muscenone (11) [51] (Scheme 2).
The other enantiomer, (R)-5, can be obtained from
As shown previously, accessible 1-(2-diethoxy-
ethyl)cyclopropanol (1) can be converted into chiral
lactone 3 [43, 44] through intermediate allyl bromide 2
commercially available (R)-3-methylglutarate [57, 74–
77], by recrystallization of the reaction products of
3-methylglutaric acid or its anhydride with chiral
alcohol or amine [49, 78–80], by enzymatic hydrolysis
[
46]. Cleavage of lactone 3 in the presence of periodic
3
41

3
42
MINEEVA
Scheme 1.
Me
O
OEt OH
O
CH2
[
46]
[43, 44]
Br
EtO
MeO
OH
O
1
2
3
Me
O
(
(
1) Py·TsOH, Me CO, H O
2 2
2) NaBH , MeOH
4
O
O
Me
OMe
OMe
HIO ·2H O, MeOH [44]
(S)-5, 76%
4
2
MeO
Me
(
(
1) LiAlH , Et O
4 2
4
2) CrO , AcOH, CH Cl
3
2
2
O
O
(
R)-5, 68%
Scheme 2.
N
N
O
Me
Me
Me
Me
Me
6
C H
5
11
Me
O
[
57]
Me
Me
Me
Me
[
50]
[55, 56]
CHO
(
S)-5
O
Me
Me
OH HO
Me
8
[
49]
[51]
[58]
OH
OH
O
Me
7
O
Me
Me
O
O
O
Me
OMe
O
Me
1
0
11
9
or cleavage of appropriate substrate [53, 81–86], via
hetero-Diels–Alder reaction [87, 88], by asymmetric
Simmons–Smith reaction [89, 90], and by other meth-
ods [68, 71, 91–93]. It was used in the synthesis of
various compounds, including pheromone 12 of the
yellow scale Aonidiella citrina (Coquillett) [44, 85],
diterpenoids tanabalin (13) [93] and clavirolide C (14)
cytotoxic lactone amphidinolide H [44], lyconadins A
and B [77, 75], woody fragrances 18 and 19 related to
georgyone and arborone [76], (+)-nemorensic acid (20)
[74], methanophenazine (6) [57], and perfume ingre-
dients (R)-(–)-muscone (10) [49] and (4R)-rose oxide
(21) [91] (Scheme 3).
The present article describes a new synthesis of
(4R)- and (4S)-4-methyltetrahydro-2H-pyran-2-ones
starting from cyclopropanol derivatives and the use of
[
90], sesquiterpene (–)-β-vertivone (15) [92], (–)-ver-
rucarinolactone (16) [44, 81, 82], fragment 17 of the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 3 2015

CYCLOPROPANOL METHODOLOGY IN THE SYNTHESIS
343
Scheme 3.
OAc
Me
Me
O
Me
H
Me
Me
OAc
O
Me
Me
Me
Me
Me
O
Me
15
O
1
2
13
6
[
44, 85]
[92]
[57]
Me
O
Me
[93]
Me
O
Me
[91]
[44, 81, 82]
[49]
(
R)-5
O
Me
H
1
6
2
1
1
0
[
76]
[90]
O
[
74]
[44]
O
H
Me
Me
Me
Me
O
Me
Me
Me
Me
O
Me
O
Me
Me
O
O
Me
Me
COOH
Me
Me
Me
O
Me
O
Me
COOH
CH2
1
8
19
14
20
17
(
4S)-4-methyltetrahydro-2H-pyran-2-one for the pre-
anchorago) [97], and (2R,8R)- and (2S,8R)-8-methyl-
dec-2-yl propionates 28 (pheromones of the western
corn rootworm Diabrotica virgifera virgifera Le
Conte) [98].
paration of convenient building blocks necessary for
the development of new synthetic approaches to com-
pounds controlling insect behavior.
Treatment of lactone (S)-5 with triethylamine in
methanol solution, followed by tetrahydropyranyl
protection and subsequent reduction of the ester group
gave functionalized alcohol 22 (Scheme 4) which was
oxidized under mild conditions to aldehyde 23; the
latter was used previously in the synthesis of
Alcohol 22 may be an appropriate intermediate for
the preparation of building blocks 29 [94, 99–102] and
30 [57, 103–111] (Scheme 5) that are important for
practical organic synthesis.
Mesylation of 22 gave ester 31; the carbon chain of
the latter was extended via reaction with propylmagne-
sium bromide in the presence of copper(I) iodide, and
removal of the tetrahydropyranyl protecting group
afforded chiral alcohol 32 (Scheme 6). Successive
chain extension in 32 by one carbon via conventional
tosylation, nucleophilic replacement by cyano group,
and hydrolysis procedures led to the formation of
carboxylic acid 33 which was reduced to alcohol 34,
pheromone of the mealworm beetle Tenebrio molitor L
[105, 112–117]. The overall yield of 34 calculated on
(S)-5 was 44% in 10 steps. The enantiomeric excess
was estimated at 97% from the intensities of the
methoxy proton signals (δ 3.52 and 3.56 ppm) in the
(R)-(–)-muscone 10 [49]. Benzyl protection of the
hydroxy group in 22, removal of the tetrahydropyranyl
protecting group, and careful oxidation of the resulting
alcohol afforded aldehyde 24 which was used previ-
ously in the asymmetric synthesis of macrolactone 9
[
94] and yellow scale pheromone 12 [95].
Successive acylation of 22, deprotection, and
oxidation produced aldehyde 25 which is a starting
compound for the synthesis of (Z)-14-methylhexadec-
8
-enal (26, trogodermal, the aggregation pheromone of
the kharpa beetle Trogoderma granarium) [96], stereo-
isomeric 6,10,13-trimethyltetradecan-1-ols 27 (aggre-
gation pheromone of the predatory stink bug Stiretrus
1
H NMR spectrum of the acylation product of 34 with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 3 2015

3
44
MINEEVA
(
S)- and (R)-3,3,3-trifluoro-2-methoxy-2-phenylpro-
catalyzed by copper(I) iodide (Scheme 7). Alcohol 35
was oxidized to acid 36 according to the procedure
described in [132]; acid 36 is a component of abdo-
minal secretion of the male dung beetle Kheper
panoyl chloride (Mosher’s acid) [118].
Methanesulfonate 31 was used to obtain known
chiral alcohol 35 [119–131] by the Grignard reaction
Scheme 4.
O
Me
[49]
1
0
H
O
O
2
3, 90%
9
PDC, CH Cl
[94]
2
2
(
(
(
1) Et N, MeOH
2) DHP, Py·TsOH, CH Cl2
(1) NaH, PhCH Cl, DMSO
(2) Py·TsOH, MeOH
3
2
2
Me
Me
3) LiAlH , Et O
(3) PCC, CH Cl
4
2
2 2
(S)-5
CHO
BzlO
HO
O
O
2
2, 81%
24, 66%
(
(
(
1) AcCl, Py, CH Cl
2) Py·TsOH, MeOH
2
[
95]
3) PCC, CH Cl
2
2
CHO
(
)6
Me
12
Me
Me
( )5
Me
O
[96]
[98]
Me
CHO
Me
Me
(
)3
AcO
O
2
6
25, 75%
28
[97]
Me
(
Me
)3 ( )5
Me
OH
Me
2
7
Scheme 5.
Me
Me
2
2
CHO
PG O
PG O
OPG3
1
2
2
9
30
PG
1
, PG
2
, and PG
3
stand for various protecting groups.
Scheme 6.
Me
(1) PrMgBr, THF, CuI, –78°C
(2) Py·TsOH, MeOH
Me
MsCl, Et N, Et O
3
2
Me
2
2
(
)4
MsO
O
O
OH
3
1, 99%
32, 90%
(
(
(
(
1) TsCl, Py
2) NaCN, DMSO
3) NaOH, EtOH, H O
Me
2
Me
4) Concd. aq. HCl
Me
OH
LiAlH , THF
4
(
)4
Me
OH
(
)4
O
3
3, 66%
34, 93%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 3 2015

CYCLOPROPANOL METHODOLOGY IN THE SYNTHESIS
345
Scheme 7.
(
(
1) KMnO , AcOH, H O
2) Concd. aq. HCl
Me
O
4
2
Me
(
)3
OH
O
3
6, 80%
(
(
1) EtMgBr, THF, CuI, –78°C
2) Py·TsOH, MeOH
Me
(1) PDC, CH Cl
Me
2
2
(2) Ph P=CHCOOEt
3
Me
Me
3
1
(
)3
( )3
OH
OEt
3
5, 81%
37, 76%
(
(
(
(
1) TsCl, Py
2) NaCN, DMSO
3) NaOH, EtOH, H O
4) Concd. aq. HCl
Me
2
Me
OH
(
)3
O
3
8, 68%
nigroaeneus of the genus Scarabaeinae [127]. The
synthesis of acid 36 was the subject of numerous
studies [121–123, 127, 133–146]. In the proposed
scheme, the overall yield of 36 was 52% in 7 steps
starting from (S)-5.
a semi-micro method. All solvents were dried accord-
ing to standard procedures and distilled prior to use.
(
4S)-4-Methyltetrahydro-2H-pyran-2-one (S-5).
Pyridinium p-toluenesulfonate, 0.08 g (0.3 mmol), was
added to a solution of 0.89 g (4.7 mmol) of ester 4 in
a mixture of 10 mL of acetone and 3 mL of water, and
the mixture was stirred for 3 h on heating under reflux
until the reaction was complete (TLC). The solvent
was distilled off under reduced pressure, the residue
was dissolved in 40 mL of chloroform, the solution
was treated with a saturated aqueous solution of
Alcohol 35 was oxidized with pyridinium chloro-
chromate to the corresponding aldehyde whose Wittig
olefination gave building block 37. The latter was used
in the synthesis of β-amino acids for the treatment of
nervous system disorders [146]. Successive extension
of the carbon chain in 35 following the procedures
described above furnished acid 38, a pheromone of the
rhinoceros beetle of the genus Oryctes; acid 38 is also
an important fragrance component of Turkish tobacco
and Italian cheese [147–151]. The overall yield of 38
was 44% in 9 steps starting from (S)-5.
NaHCO (25 mL), and the organic phase was separated
3
and dried over MgSO . The solvent was removed
4
under reduced pressure, the residue was dissolved in
20 mL of methanol, 0.19 g (5.0 mmol) of sodium tetra-
hydridoborate was added, and the mixture was stirred
for ~12 h. The mixture was then treated with 20 mL of
a saturated aqueous solution of ammonium chloride
and extracted with diethyl ether (4×10 mL), the com-
bined extracts were dried over Na SO , the solvent was
Numerous examples of the use of cyclopropanol
intermediates in stereoselective syntheses of natural
methyl-branched compounds demonstrate their broad
synthetic potential and stimulate development of new
efficient methods for their preparation and application
in target-oriented synthesis without loss of optical
purity.
2
4
distilled off under reduced pressure, and the residue
was purified by column chromatography (petroleum
ether–ethyl acetate, 15:1). Yield 0.41 g (76%). The
spectral parameters and optical rotation of the product
were consistent with the data given in [51, 56].
EXPERIMENTAL
(
4R)-4-Methyltetrahydro-2H-pyran-2-one (R-5).
1
13
The H and C NMR spectra were recorded from
A solution of 1.33 g (7 mmol) of ester 4 in 3 mL of
anhydrous diethyl ether was added to a suspension of
solutions in CDCl on a Bruker AC 400 spectrometer
3
at 400 and 100 MHz, respectively. The IR spectra were
measured in carbon tetrachloride on a Bruker Vertex
0
.76 g (5 mmol) of lithium tetrahydridoaluminate in
20 mL of anhydrous diethyl ether, and the mixture was
heated for 2 h under reflux with uniform stirring. The
mixture was diluted with 20 mL of diethyl ether,
treated with 1 mL of water on cooling, and filtered
through a thin layer of silica gel, and the solvent was
removed under reduced pressure. The residue was
7
0 spectrometer. The optical rotations were determined
at room temperature on an SM-3 polarimeter with
a scale division of 0.05°. Pure compounds were iso-
lated by column chromatography on silica gel (70–
2
30 mesh). The elemental analyses were obtained by
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 3 2015

3
46
MINEEVA
dissolved in 25 mL of methylene chloride at room
temperature, a mixture of 4.08 g (40.8 mmol) of
chromium(VI) oxide, 7.0 mL of water, and 40 mL of
glacial acetic acid was added, and the mixture was
vigorously stirred for 12 h. The mixture was then
diluted with 50 mL of methylene chloride and passed
through a thin layer of silica gel, the organic phase was
washed with a saturated aqueous solution of NaHCO3
of anhydrous methylene chloride, and the mixture was
stirred for 10 h until the reaction was complete. The
mixture was filtered through a layer of silica gel, the
solvent was removed under reduced pressure, the
residue was dissolved in 50 mL of diethyl ether, the
solution was filtered again through a layer of silica gel,
and the solvent was removed under reduced pressure.
Yield 1.06 g (90%). The spectral parameters and op-
tical rotation of the product were consistent with the
data given in [49].
(
40 mL) and dried over MgSO , the solvent was
4
removed under reduced pressure, and the residue was
purified by column chromatography (petroleum ether–
ethyl acetate, 15:1). Yield 0.54 g (68%). The spectral
parameters and optical rotation of the product were
consistent with the data given in [80].
(
3R)-5-(Benzyloxy)-3-methylpentanal (24). Alco-
hol 22, 1.62 g (8 mmol), was added to a suspension of
.24 g (10 mmol) of sodium hydride in 15 mL of THF,
0
and the mixture was stirred for 20 min. A solution of
1.27 g (10 mmol) of benzyl chloride in 5 mL of THF
was then added, and the mixture was stirred for 8 h at
50°C, treated with 45 mL of a saturated aqueous
solution of ammonium chloride, and extracted with
diethyl ether (4×10 mL). The combined extracts were
(
3R)-3-Methyl-5-(tetrahydro-2H-pyran-2-yloxy)-
pentan-1-ol (22). Lactone (S)-5, 0.88 g (7.7 mmol),
was dissolved in 20 mL of methanol, 3.5 mL
(
25.3 mmol) of triethylamine was added, and the mix-
ture was kept for 48 h. Excess methanol and triethyl-
amine were removed under reduced pressure, the resi-
due was diluted with 20 mL of anhydrous methylene
chloride, 1.00 g (12 mmol) of dihydropyran and a cata-
lytic amount of pyridinium p-toluenesulfonate were
added, and the mixture was heated for 4 h under reflux.
When the reaction was complete (TLC), a catalytic
amount of triethylamine was added, the solvent was
distilled off, and the residue was added to a suspension
dried over Na SO , the solvent was removed under
2 4
reduced pressure, the residue was dissolved in 10 mL
of methanol, and a catalytic amount of pyridinium
p-toluenesulfonate was added. The mixture was heated
for 2 h at 50°C, the solvent was removed under
reduced pressure, the residue was dissolved in 10 mL
of anhydrous methylene chloride, the solution was
added in one portion to a suspension of 2.58 g
(12 mmol) of pyridinium chlorochromate (PCC) in
15 mL of anhydrous methylene chloride, and the mix-
ture was stirred for 1.5 h until the reaction was com-
plete. The mixture was filtered through a layer of silica
gel, the solvent was removed under reduced pressure,
and the residue was purified by silica gel column
chromatography (petroleum ether–ethyl acetate, 60:1).
of 0.23 g (6 mmol) of LiAlH in 20 mL of anhydrous
4
diethyl ether, cooled to 0°C. After 2 h, the mixture was
diluted with 20 mL of diethyl ether and treated with
1
mL of water on cooling. The mixture was filtered
through a thin layer of silica gel, the solvent was
removed under reduced pressure, and the residue was
purified by silica gel chromatography (petroleum
ether–ethyl acetate, 50:1). Yield 1.26 g (81%). IR
Yield 1.09 g (66%), [α] = +4.2° (c = 1.5, CHCl ).
D 3
–
1
1
–1
spectrum, ν, cm : 3428, 1074. H NMR spectrum, δ,
IR spectrum, ν, cm : 1708, 1454, 1408, 1277, 1178,
1096, 1027. H NMR spectrum, δ, ppm: 0.97 d (3H,
1
ppm: 0.94 d (3H, CHCH , J = 6.7 Hz), 1.40–1.84 m
3
(
12H, OCHCH CH CH , OH, HOCH CH , CHCH ,
CH CH, J = 6.8 Hz), 1.23–1.34 m and 1.38–1.45 m
2
2
2
2
2
3
3
O C H C H ) , 3 . 3 9 – 3 . 5 4 m ( 2 H , C H O H,
(1H each, CH CH CH), 2.02–2.09 m (CHCH ), 2.19–
2
2
2
2
2
3
CHCH CH OCH), 3.64–3.89 m [4H, CH OH,
2.24 m and 2.35–2.41 m (1H each, CH CHO), 3.42 t
2
2
2
2
CHCH CH OCH, (CH ) CH OCH], 4.55–4.60 m (1H,
(2H, CH CH O, J = 6.8 Hz), 4.46 s (2H, OCH Ph),
7.18–7.31 m (5H, Ph), 9.71 br.s (1H, CHO). C NMR
2
2
2 2
2
2
2
2
1
3
13
OCHO). C NMR spectrum, δ , ppm: 19.65, 19.77,
C
1
3
6
9.86, 19.97, 25.45 (2C), 26.79, 26.92, 30.75, 30.78,
6.56 (2C), 39.77, 39.92, 60.95, 60.99, 62.38, 62.56,
5.73, 65.89, 98.87, 99.22. Found, %: C 65.34;
spectrum, δ , ppm: 19.5, 26.8, 32.9, 50.5, 69.9, 72.5,
C
127.1, 127.2, 127.9, 138.2, 202.2. Found, %: C 75.73;
H 8.72. C H O . Calculated, %: C 75.69; H 8.80.
13
18
2
H 10.92. C H O . Calculated, %: C 65.31; N 10.96.
11
22
3
(
3R)-3-Methyl-5-oxopentyl acetate (25). Pyridine,
(
3S)-3-Methyl-5-(tetrahydro-2H-pyran-2-yloxy)-
0.8 g (10 mmol), and a solution of 0.47 g (6 mmol) of
acetyl chloride in 2 mL of anhydrous methylene
chloride were added in succession on cooling to 0.81 g
(4 mmol) of alcohol 22 in 10 mL of anhydrous
methylene chloride, and the mixture was stirred for
pentanal (23). A solution of 1.19 g (5.9 mmol) of
alcohol 22 in 10 mL of anhydrous methylene chloride
was added in one portion to a suspension of 3.22 g
(
8.8 mmol) of pyridinium dichromate (PDC) in 15 mL
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CYCLOPROPANOL METHODOLOGY IN THE SYNTHESIS
347
1
2 h. The mixture was treated with 40 mL of a satu-
37.34 (2C), 62.34, 62.42, 65.18, 65.31, 68.33 (2C),
98.84, 99.07. Found, %: C 51.44; H 8.60. C H O S.
rated aqueous solution of NaHCO and extracted with
3
12 24
5
methylene chloride (2×10 mL), the combined extracts
Calculated, %: C 51.40; H 8.63.
were dried over Na SO , and the solvent was removed
2
4
(3R)-3-Methyloctan-1-ol (32). A solution of
6.0 mmol of Grignard reagent prepared from 0.72 g
30 mmol) of magnesium turnings and 3.44 g
28 mmol) of propyl bromide in 70 mL of anhydrous
diethyl ether was added to a solution of 0.48 g
1.7 mmol) of methanesulfonate 31 in 30 mL of
under reduced pressure. The residue was dissolved in
0 mL of methanol, a catalytic amount of pyridinium
2
(
(
1
p-toluenesulfonate was added, and the mixture was
heated for 2 h at 50°C. The solvent was removed under
reduced pressure, the residue was dissolved in 5 mL of
anhydrous methylene chloride, the solution was added
in one portion to a suspension of 1.29 g (6 mmol) of
pyridinium chlorochromate in 10 mL of anhydrous
methylene chloride, and the mixture was stirred for
(
anhydrous THF, cooled to –78°C. A 0.1 M solution of
Li CuCl in THF, 4 mL, was then added, and the
2
4
mixture was allowed to warm up to room temperature
over a period of 2 h and stirred for 14 h. The mixture
was treated with 200 mL of a saturated aqueous solu-
tion of ammonium chloride and extracted with diethyl
ether (3×50 mL), and the combined extracts were
dried over Na SO and evaporated. The residue was
1
.5 h until the reaction was complete. The mixture was
filtered through a layer of silica gel, the solvent was
distilled off under reduced pressure, and the residue
was purified by silica gel column chromatography
2
4
(
(
petroleum ether–ethyl acetate, 60:1). Yield 0.47 g
75%), [α] = +5.2° (c = 1.9, CHCl ). IR spectrum, ν,
dissolved in 10 mL of methanol, a catalytic amount of
pyridinium p-toluenesulfonate was added, and the
mixture was heated for 2 h at 50°C. The solvent was
removed under reduced pressure, and the residue was
purified by silica gel column chromatography (petro-
leum ether–ethyl acetate, 50:1). Yield 0.22 g (90%).
The spectral parameters and optical rotation of the
product were consistent with the data given in [114].
D
3
–
1
cm : 3452, 1735, 1725, 1650, 1259, 1240, 1060.
1
H NMR spectrum, δ, ppm: 0.98 d (3H, CH CH, J =
3
6
.7 Hz), 1.42–1.75 m (2H, CH CH CH), 2.10–2.49 m
2 2
(
3H, CH CHO, CHCH ), 2.03 br.s (3H, CH CO),
2 3 3
3
.97–4.19 m (2H, CH OAc), 9.74 t (1H, CHO,
2
1
3
J = 1.6 Hz). C NMR spectrum, δ , ppm: 19.67,
C
2
0.88, 25.04, 35.15, 50.63, 62.14, 170.09, 201.99.
(
4R)-4-Methylnonanoic acid (33). p-Toluenesul-
fonyl chloride, 1.43 g (7.5 mmol), was added to 0.72 g
5.0 mmol) of alcohol 32 in 5 mL of pyridine, and the
Found, %: C 60.77; H 8.89. C H O . Calculated, %:
8
14
3
C 60.74; H 8.92.
3S)-3-Methyl-5-(tetrahydro-2H-pyran-2-yloxy)-
pentyl methanesulfonate (31). A solution of 0.81 g
4.0 mmol) of alcohol 22 in 10 mL of anhydrous
(
(
mixture was left to stand for 24 h at 0°C. The mixture
was treated with 15 mL of water and extracted with
diethyl ether (3×10 mL), the combined extracts were
washed with a 15% aqueous solution of sulfuric acid
(
diethyl ether was cooled to 0°C, 0.9 mL (6.3 mmol) of
triethylamine and 0.5 mL (5.0 mmol) of methane-
sulfonyl chloride in 5 mL of anhydrous diethyl ether
were added in succession, and the mixture was stirred
for 2 h. The mixture was treated with a saturated
(
15 mL) and dried over Na SO , and the solvent was
2 4
distilled off under reduced pressure. The residue was
dissolved in 5 mL of DMSO, 0.26 g (5 mmol) of
sodium cyanide was added, and the mixture was
heated for 5 h at 90°C. The mixture was diluted with
water (25 mL) and extracted with diethyl ether
(3×10 mL), the combined extracts were evaporated
under reduced pressure, 10 mL of ethanol and 2 g
(50 mmol) of sodium hydroxide in 20 mL of water
were added to the residue, and the mixture was heated
for 12 h under reflux. The mixture was diluted with
water (50 mL) and extracted with diethyl ether
(2×10 mL), and the aqueous phase was acidified to
pH 2 with concentrated aqueous HCl. Acid 33 was
extracted into diethyl ether (3×15 mL), the combined
extracts were dried over Na SO , and the solvent was
aqueous solution of NaHCO (15 mL), the organic
3
phase was separated, and the aqueous phase was
extracted with diethyl ether (3×10 mL). The extracts
were combined with the organic phase, washed with
brine (15 mL), and dried over Na SO , and the solvent
2
4
was removed under reduced pressure. Yield 1.11 g
–
1
(
99%). IR spectrum, ν cm : 1331, 1170, 1072, 1060.
1
H NMR spectrum, δ, ppm: 0.95 d (3H, CHCH , J =
3
6
.6 Hz), 1.43–1.88 m (11H, OCHCH CH CH ,
2 2 2
MsOCH CH , CHCH , OCH CH ), 3.34–3.55 m [2H,
2
2
3
2
2
(
CH ) CH OCH, CHCH CH OCH], 3.74–3.87 m [2H,
2 2 2 2 2
(
CH ) CH OCH, CHCH CH OCH], 4.22–4.31 m (2H,
2
2
2
2
2
2
4
1
3
CH OMs), 4.53–4.57 m (1H, OCHO). C NMR spec-
removed under reduced pressure. Yield 0.57 g (66%).
The spectral parameters and optical rotation of the
product were consistent with the data given in [114].
2
trum, δ , ppm: 19.23, 19.32, 19.60, 19.65, 25.41 (2C),
C
2
6.75 (2C), 30.71 (2C), 35.89, 36.00, 36.31, 36.37,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 3 2015

3
0
48
MINEEVA
(
4R)-4-Methylnonan-1-ol (34). A solution of
.86 g (5 mmol) of acid 33 in 3 mL of THF was added
purified by silica gel column chromatography (petro-
leum ether–ethyl acetate, 100:1). Yield 1.17 g (76%),
–
1
to a suspension of 0.19 g (5.0 mmol) of LiAlH in
[α] = –9.5° (c = 0.7, CHCl ). IR spectrum, ν, cm :
4
D 3
1
3
mL of THF, and the mixture was stirred for 3 h at
room temperature. The mixture was diluted with
0 mL of diethyl ether, 0.4 mL of water was added, the
1722, 1466, 1270, 1174. H NMR spectrum, δ, ppm:
0.87 t [3H, CH (CH ) , J = 7.1 Hz], 0.88 d (3H,
CH CH, J = 6.1 Hz), 1.28 t (3H, CH CH O, J =
3
2 3
3
3
3
2
ether layer was separated, and the precipitate was
washed with 10 mL of diethyl ether. The combined
extracts were dried over Na SO , the solvent was dis-
7.1 Hz), 1.11–1.33 m [6H, CH (CH ) ], 1.53–1.63 m
3 2 3
(CH CH), 1.98–2.06 m and 2.15–2.23 m (1H each,
3
CH CH=CH), 4.17 q (2H, CH CH O, J = 7.1 Hz),
2
4
2
3
2
tilled off under reduced pressure, and the residue was
purified by silica gel column chromatography (petro-
leum ether–ethyl acetate, 40:1). Yield 0.50 g (93%).
The spectral parameters and optical rotation of the
product were consistent with the data given in [114].
5.87 d (1H, CH=CHCO , J = 17.2 Hz), 6.89–6.98 m
2
1
3
(1H, CH=CHCO ). C NMR spectrum, δ , ppm:
2
C
13.97, 19.52, 22.58, 26.61, 31.97, 32.47, 36.54, 39.64,
60.05, 122.29, 148.42, 166.53. Found, %: C 72.71;
H 11.15. C H O . Calculated, %: C 72.68; H 11.18.
1
2
22
2
(
3R)-3-Methylheptan-1-ol (35) was synthesized as
(5R)-5-Methylnonanoic acid (38) was synthesized
as described above for acid 33. Yield 0.58 g (68%).
The spectral parameters and optical rotation of the
product were consistent with the data given in [150].
described above for alcohol 32. Yield 0.18 g (81%).
The spectral parameters and optical rotation of the
product were consistent with the data given in [131].
(
3R)-3-Methylheptanoic acid (36). A solution of
This study was performed under financial support
by the Belarusian Republican Foundation for Basic
Research (project no. Kh13M-039, 2013–2015:
“Enantioselective Synthesis of Methyl-Branched Insect
Pheromones from trans-2,2-Dichloro-3-methylcyclo-
propanecarboxylic and 3-Bromomethylbut-3-enoic
Acid Esters”; state registration no. 20131542).
0
.37 g (2.4 mmol) of KMnO in 6.7 mL of water was
added dropwise over a period of 2 h to a solution of
.23 g (1.8 mmol) of alcohol 35 in a mixture of 4 mL
4
0
of acetone and 0.7 mL of glacial acetic acid, and the
mixture was stirred for 12 h at room temperature. The
mixture was diluted with 10 mL of methylene chloride,
adjusted to pH 3 by adding concentrated aqueous HCl,
and extracted with methylene chloride (3×10 mL).
The combined extracts were dried over Na SO , the
solvent was distilled off under reduced pressure,
toluene was added to the residue, and the mixture was
evaporated; the addition of toluene and evaporation
were repeated to remove residual acetic acid. The
spectral parameters and optical rotation of the product
were consistent with the data given in [134, 136].
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