A New Asymmetric Synthesis of (S)-14-Methyloctadec-1-ene, the Sex Pheromone of the Peach Leafminer Moth

Article abstract of DOI:10.1134/S1070428020060196

Abstract: An asymmetric synthesis of 14-methyl-1-octadecene, the sex pheromone of thepeach leafminer moth has been achieved. Based on the asymmetric methylation ofchiral (S)-4-benzyloxazolidin-2-one, thecarbon chain of the target molecule was assembled through aC₁+C₁₀+C₄+C₃procedure. The γ-lactone was transformed into 4-(benzyloxy)butanoic acid andthen, with the induction of Evan’s template, a chiral methyl group wasintroduced to the position of the carboxylic group in 97percent de. After reduction and a couple of chemicaloperations, the designed key intermediate A1was obtained. The synthesis of another moiety was started from decane-1,10-diolwhich was selectively protected and oxidized. The long carbon chain wasinstalled according to a Wittig protocol. After deprotection, oxidization, andmethylenation, the target molecule was synthesized in 7 linear steps with anoverall yield of 30.3percent.

Full text of DOI:10.1134/S1070428020060196

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 6, pp. 1089–1095. © Pleiades Publishing, Ltd., 2020.
A New Asymmetric Synthesis of (S)-14-Methyloctadec-1-ene,
the Sex Pheromone of the Peach Leafminer Moth
Liang Weia, Guo-Guo Hea, Lu Liub, Meng Tangb, Tao Zhangb,
Hongjin Baia,*, and Zhen-Ting Dub,c,d,**
a Xinjiang Production & Construction Corps Key Laboratory of Protection and Utilization of Biological Resources
in Tarim Basin, Tarim University, Alar, 843300 China
b College of Chemistry and Pharmacy, Northwest A&F University, Yangling, 712100 China
c Key Laboratory of Functional Small Organic Molecules, Ministry of Education,
Jiangxi Province, Nanchang, 330027 China
d Key Laboratory of Botanical Pesticide R&D in Shaanxi Province, Yangling, 712100 China
e-mail: *bhj67@163.com; **duzt@nwsuaf.edu.cn
Received January 30, 2020; revised March 22, 2020; accepted March 26, 2020
Abstract—An asymmetric synthesis of 14-methyl-1-octadecene, the sex pheromone of the peach leafminer
moth has been achieved. Based on the asymmetric methylation of chiral (S)-4-benzyloxazolidin-2-one, the
carbon chain of the target molecule was assembled through a C1+C10+C4+C3 procedure. The γ-lactone was
transformed into 4-(benzyloxy)butanoic acid and then, with the induction of Evan’s template, a chiral methyl
group was introduced to the position of the carboxylic group in 97% de. After reduction and a couple of
chemical operations, the designed key intermediate A1 was obtained. The synthesis of another moiety was
started from decane-1,10-diol which was selectively protected and oxidized. The long carbon chain was
installed according to a Wittig protocol. After deprotection, oxidization, and methylenation, the target molecule
was synthesized in 7 linear steps with an overall yield of 30.3%.
Keywords: 14-methyloctadec-1-ene, pheromone synthesis, peach leafminer moth
DOI: 10.1134/S1070428020060196
Pheromones are substances produced as messengers
that affect the behaviour of other insects [1]. Insect
pheromones can be mainly divided into the following
groups by function: trace pheromones (to locate a food
source or to share something), aggregation pheromones
(to find individuals of the same species), alarm phero-
mones (to warn of any sort of danger), and sex phero-
mones (to attract adults of the opposite sex for mating).
Among them, sex pheromones have been studied most
thoroughly and used to control the overall population.
The peach leafminer moth Lyonetia clerkella [2] is one
of the most destructive pests in the peach orchards of
East Asia. It causes defoliation when the leaves are
infested by only a few larvae of this insect. Tradition-
ally, highly toxic pesticides have been adopted by
Chinese farmers to prevent it. In the context of in-
tegrated pest management (IPM)), a promising method
is to kill them physically, e.g., by using a high-voltage
electrical shock, drowning in water, or collecting them
into a designated container after using its sex phero-
mone to seduce them and disrupt their mating process.
Sugie et al. [2] were the first to identify the sex
pheromone of the moth as (S)-14-methyloctadec-1-
ene (1). Some early syntheses of 1 in the racemic form
have been reported by several teams [3, 4]. The asym-
metric synthesis of 1 has been reported by Mori [5],
Kharisov [6], and Tai [7] who used expensive chiral
starting materials through a chiral pool strategy. Sonnet
[8] and Sankaranarayanan [9] described a synthesis
through resolution methodology. Recently, a carbon
coupling strategy has been developed by us, but if the
carbon chain is long (more than 10 carbon atoms), the
coupling reaction was generally sluggish. Therefore,
the existing synthetic pathways have some drawbacks
CH2
Me
Me
(S)-14-Methyloctadec-1-ene (1)
1089

LIANG WEI et al.
1090
Scheme 1.
CH2
Me
Wittig reaction
Me
Wittig reaction, hydrogenation
O
Me
Br– Ph3P
OTBS
Me
A1
O
Br
OTBS
O
OH
A2
such as too many chemical operations or lack of cost-
effectiveness. So, there is high demand to develop an
economical synthesis of the natural stereoisomer of 1.
As a continuation of our research in new agrichemicals
and “green” pesticides [10–15], we are interested in
utilizing chiral methylation and the Wittig reaction in
efficient and convenient formation of these kinds of
sex pheromones. Herein, we report a new synthesis of
(S)-1 by chiral template induction and Wittig reactions.
The retrosynthetic analysis of compound 1 is shown
in Scheme 1. The molecule was disconnected into
chiral synthon A1 and C10 moiety. The chiral synthon
Scheme 2.
O
O
O
O
i
HN
Bn
O
O
O
+
OH
N
O
Bn
2
O
O
ii
iii
O
O
N
O
OH
Me
Me
Bn
3
4
Me
iv
v
Me
O
BnO
O
Me
Me
5
6
Me
Me
vi
vii
Me
HO
O
7
A1
Reagents and conditions: i: Et3N, Trimethylacetyl chloride, LiCl, THF, –78°C, 87%; ii: NaHMDS, THF, –78°C, MeI, 50%, 98% de;
iii: LiAlH4, –10°C, 86%; iv: PCC, CH2Cl2, 0°C to room temp., 88%; v: triphenyl(propyl)phosphonium bromide, n-BuLi, THF, –30°C
to room temp., 98%; vi: H2, Pt/C, Pd/C, MeOH, 45°C, 84%; vii: PCC, CH2Cl2, 0°C to room temp., 65%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 6 2020

A NEW ASYMMETRIC SYNTHESIS OF (S)-14-METHYLOCTADEC-1-ENE
1091
A1 could be furnished from 4-(benzyloxy)butanoic
acid, while the C10 moiety A2 can be obtained from
decane-1,10-diol.
propyl(triphenyl)phosphonium bromide gave the C8
moiety 6 in 98% yield with an E/Z ratio of 8:1. It
should be noted that the geometry of the double bond
did not matter in the subsequent transformations. In
order to prevent palladium-catalyzed allylic racemiza-
tion, the hydrogenation was carried out over Pt/C in
one-pot fashion, and alcohol 7 was obtained in 84%
yield. Alcohol 7 was then subjected to oxidation with
PCC, and subunit A1 was smoothly prepared.
With the basic synthetic plan in hand, as shown in
Scheme 2, our synthesis commenced with (S)-4-ben-
zyloxazolidin-2-one and 4-(benzyloxy)butanoic acid
which could be prepared through literature procedures
[16, 17]. After activation with a mixed anhydride,
4-(benzyloxy)butanoic acid was connected to
(S)-4-benzyloxazolidin-2-one to give 2 in 87% yield
[18]. Compound 2 was deprotonated in the presence of
NaHMDS at –78°C and then methylated to afford 3.
Because of the induction by the chiral benzyl group in
the oxazolidine ring, the methyl group was directed to
the d-face with 98% de and 50% yield. Then the Wittig
reaction with phosphorus ylide produced the key inter-
mediate A1 in 65% yield in two steps. The chiral
oxazolidine was removed by reduction with LiAlH4 at
–10°C to give alcohol 4. Alcohol 4 was treated with
PCC in methylene chloride, and aldehyde 5 was thus
obtained in 88% yield. The Wittig reaction with
Then, as shown in Scheme 3, decane-1,10-diol was
selectively brominated in a way similar to a literature
method [19]. The remaining hydroxyl group was
effectively protected as tert-butyl(dimethyl)silyl ether
which was converted to triphenylphosphonium
bromide and then coupled with A1 under the Wittig
reaction protocol to form 10 in 78% yield. Thus, the
main carbon chain of the target molecule was con-
structed successfully. Afterwards, the TBS protecting
group was removed by the action of tetrabutylammo-
nium fluoride in tetrahydrofuran. The subsequent con-
ventional oxidation and another Wittig reaction with
Scheme 3.
i
OH
Br
HO
HO
8
ii
PPh3 Br–
TBSO
9
iii
OTBS
OTBS
OH
Me
Me
10
iv
Me
Me
11
v
Me
Me
12
O
vi
Me
Me
13
CH2
vii
Me
Me
1
Reagents and conditions: i: 48% HBr, benzene, reflux, 89%; ii:(1) TBSCl, imidazole, CH2Cl2, 0°C to room temp., 94%; (2) PPh3,
MeCN, reflux, 91%; iii: A1, n-BuLi, THF, –10°C to room temp., 78%; iv: H2, Pt/C, MeOH, 45°C, 84%; v: TBAF, CH2Cl2, 0°C to
room temp., 86%; vi: PCC, CH2Cl2, 0°C to room temp., 65%; vii: (1) PCC, CH2Cl2, 0° to room temp., 88%; (2) methyl(triphenyl)-
phosphonium bromide, NaHMDS, THF, –30°C to room temp., 85%.
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LIANG WEI et al.
1092
methyl(triphenyl)phosphonium bromide afforded the
target (S)-1 in 50% yield. Thus, the asymmetric total
synthesis of (S)-1 was achieved in 6 linear steps with
an overall yield of 30.3%.
(5H, Harom), 7.34–7.29 m (2H, CH2), 7.23 d ( 2H, CH2,
J = 7.0 Hz), 4.65 d.d.t (1H, Harom, J = 10.3, 7.0,
3.4 Hz), 4.56 s (1H, CH), 4.29–3.99 m (1H, CH),
3.63 t (1H, CH, J = 6.2 Hz), 3.32 d.d (1H, CH, J =
13.4, 3.2 Hz), 3.11 d (1H, CH, J = 7.5 Hz), 2.75 d.d
(1H, CH, J = 13.4, 9.7 Hz), 2.09 d.q (1H, CH, J = 13.5,
7.0 Hz). 13C NMR spectrum, δC, ppm: 173.10, 153.50,
138.49, 135.41, 129.43, 128.96, 128.39, 127.73,
127.59, 127.33, 72.93 (CH2), 69.28 (CH2), 66.17
(CH2), 55.20 (CH2), 37.93 (CH2), 24.54 (CH2).
In summary, we have completed the asymmetric
total synthesis of the sex pheromone of the peach
leafminer moth, (S)-14-methyloctadec-1-ene, through
Evan’s template induction and Wittig reaction. Com-
pared with other methods, this process has several
advantages such as high yield, easy operation, and
cost-effectiveness. Further biological study is in prog-
ress, and this may be a promising way for orchardists
to produce “green” fruits in the future. Further
applications in modern agriculture will be reported
elsewhere.
(S)-4-Benzyl-3-[(S)-4-(benzyloxy)-2-methylbuta-
noyl]oxazolidin-2-one (3). A three-necked flask was
charged under argon with compound 2 (23 g,
65.08 mmol) and anhydrous THF (300 mL), the mix-
ture was cooled to –78°C and kept for 15 min at that
temperature, NaHMDS (65.08 mL, 130.16 mmol) was
added dropwise, and the mixture was stirred at –78°C
for 30 min. Methyl iodide (32.07 mL, 325.39 mmol)
was slowly recondensed to the mixture, and the mix-
ture was stirred for 2 h at –78°C, adjusted to –50°C,
and left overnight. The mixture was then quenched
with NH4Cl at –50°C, and the product was isolated as
EXPERIMENTAL
Tetrahydrofuran (THF) was dried by sodium and
distilled before use. Methylene chloride was dried by
calcium hydride and distilled before use. The reactions
were monitored by thin-layer chromatography (TLC)
on glass plates coated with silica gel containing
a fluorescent indicator. Flash chromatography was
performed on silica gel (200–300 mesh) with petro-
leum ether–ethyl acetate as eluent. The NMR spectra
were recorded on a Bruker AC-500 instrument
(Madison, WI, USA) at 500 MHz for 1H. The chemical
shifts were referenced to tetramethylsilane as internal
a colorless oily liquid. Yield 12.12 g (50.18%), [α]D20
=
1
+73.81° (c = 0.22, n-hexane). H NMR spectrum, δ,
ppm: 7.41–7.35 m (5H, Harom), 7.34–7.29 m (2H,
CH2), 7.23 d ( 2H, CH2, J = 7.0 Hz), 4.65 d.d.t (1H,
CH, J = 10.3, 7.0, 3.4 Hz), 4.56 s (2H, CH2), 4.20–
4.09 m (2H, CH2), 3.63 t (2H, CH2, J = 6.0 Hz),
3.32 d.d (1H, CH, J = 13.5, 3.0 Hz), 3.12 t (2H, CH2,
J = 7.3 Hz), 2.75 d.d (1H, CH, J = 13.4, 9.7 Hz),
2.09 d.q (2H, CH2, J = 13.5, 7.0 Hz), 1.31 d (3H, CH3,
J = 7.0 Hz). 13C NMR spectrum, δC, ppm: 173.10,
153.50, 138.49, 135.41, 130.25–125.56, 72.93 (CH2),
69.28 (CH2), 66.17 (CH2), 55.20 (CH2), 37.93 (CH2),
32.52 (CH2), 24.54(CH3).
1
standard for H or CDCl3 (δC 77.16 ppm) for 13C.
The high-resolution mass spectra were measured on
a Thermo Fisher Scientific (LTQ-Orbitrap-XL, ESI,
GER) instrument. The optical rotations were measured
on a Digipol-P910 polarimeter (Shanghai JIAHANG)
with a sodium lamp.
(S)-4-Benzyl-3-[4-(Benzyloxy)butanoyl]oxazoli-
din-2-one (2). Triethylamine (31.58 mL, 0.22 mol)
was added dropwise to a solution of 4-benzyloxy-
butyric acid (22 g, 0.11 mol) in THF (440 mL)
under argon at –78°C, and trimethylacetyl chloride
(16.64 mL, 0.14 mol) was then added. The mixture was
stirred at –78°C for 20 min and allowed to warm up
to room temperature over a period of 1 h. The mixture
was cooled again to –78°C, lithium chloride (14.40 g,
0.33 mol) was added, and a solution of (S)-4-benzyl-
oxazolidin-2-one (22.08 g, 0.12 mol) in anhydrous
THF was slowly added dropwise. The mixture was
stirred for 1 h at –78°C, allowed to spontaneously
warm up to room temperature, and left overnight.
A yellow oily liquid was obtained. Yield 35.45 g
(S)-4-(Benzyloxy)-2-methylbutan-1-ol (4). A flask
was charged under argon with LiAlH4 (4.54 g,
0.12 mol) in anhydrous THF, and a solution of 3 (11 g,
29.94 mmol) in anhydrous THF was slowly added
dropwise from a dropping funnel at –10°C. The tem-
perature was naturally raised to 0°C and stirred over-
night. The mixture was quenched in succession with
water and 10% aqueous sodium hydroxide. The prod-
uct was a colorless oily liquid. Yield 5.14 g (84.58%),
[α]D20 = +7.85° (c = 0.2, n-hexane). 1H NMR spectrum,
δ, ppm: 7.39 d (4H, Harom, J = 4.2 Hz), 7.37–7.29 m
(1H, Harom), 5.38 d.t (1H, CH, J = 10.6, 7.3 Hz),
5.16 d.t (1H, CH, J = 20.5, 10.3 Hz), 4.67–4.41 m (1H,
CH), 3.60–3.41 m (1H, CH), 2.79–2.64 m (1H, CH),
2.09 t.t (1H, CH, J = 14.5, 7.2 Hz), 1.73 t.d (1H, J =
12.9, 7.2 Hz), 1.52 d.d.d (1H, CH, J = 14.0, 9.1,
1
(87.43%). H NMR spectrum, δ, ppm: 7.42–7.34 m
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A NEW ASYMMETRIC SYNTHESIS OF (S)-14-METHYLOCTADEC-1-ENE
1093
6.1 Hz), 1.06–0.96 m (3H, CH3). 13C NMR spectrum,
δC, ppm: 138.74, 130.81, 128.36, 127.67, 127.48,
73.03 (CH2), 68.85 (CH2), 37.30, 28.56 (CH2), 21.57
(CH2), 20.75 (CH3). HRMS (ESI): m/z 195.13756
[M + H]+. Calculated for C12H19O2+: 195.13796.
refilled with hydrogen, and the mixture was stirred at
room temperature for 24 h. After completion of the
reaction (TLC), the mixture was filtered with suction,
and the filtrate was concentrated under reduced pres-
sure. A colorless oily liquid was obtained. Yield 1.51 g
(83.83%), [α]D20 = +1.5° (c = 0.16, n-hexane). 1H NMR
spectrum, δ, ppm: 3.82–3.62 m (2H, CH2), 1.74–
1.51 m (1H, CH), 1.42 d.t (4H, CH2, J = 13.0, 6.5 Hz),
1.36–1.26 m (4H, CH2), 1.21–1.10 m (2H, CH2),
0.93 d.d (3H, CH3, J = 6.5, 4.0 Hz). 13C NMR
spectrum, δC, ppm: 61.52 (CH2), 40.27 (CH2),
37.10 (CH2), 29.62, 22.98 (CH2), 20.15 (CH2), 19.92
(CH3), 14.38 (CH3).
(S)-4-(Benzyloxy)-2-methylbutanal (5). Com-
pound 4 (9 g, 46.33 mmol) was dissolved in methylene
chloride under argon, the solution was cooled in an ice
bath, 9 g of silica gel was added, pyridinium chloro-
chromate (11.98 g, 55.59 mmol) was then added, and
the mixture was allowed to warm up to room tempera-
ture. A colorless oily liquid was obtained. Yield 5.14 g
(87.58%), [α]D20 = +8.65° (c = 0.2, n-hexane). 1H NMR
spectrum, δ, ppm: 9.69 d (1H, CH, J = 1.7 Hz), 7.46–
7.28 m (5H, Harom), 4.58–4.47 m (2H, CH2), 3.66–
3.48 m (2H, CH2), 2.59 d.d.d (1H, CH, J = 13.7, 7.0,
1.6 Hz), 2.10 d.t.d (2H, CH2, J = 12.6, 7.0, 5.6 Hz),
1.86–1.62 m (2H, CH2), 1.21 d (6H, CH3, J = 7.1 Hz).
13C NMR spectrum, δC, ppm: 204.74 (C=O), 138.22,
128.43, 127.68, 73.09 (CH2), 67.42 (CH2), 43.78
(CH2), 30.86 (CH2), 13.29 (CH3). HRMS (ESI):
m/z 193.12201 [M + H]+. Calculated for C12H17O2+:
193.12231.
(S)-3-Methylheptanal (A1). Compound 7 (1.5 g,
11.52 mmol) was dissolved in methylene chloride
under argon, the solution was cooled in an ice bath,
an equal amount of silica gel was added, pyridinium
chlorochromate (2.98 g, 13.82 mmol) was then added,
and the mixture was allowed to return to room tem-
perature. A colorless oily liquid was obtained. Yield
0.95 g (64.94%). [α]D20 = +7.58° (c = 0.12, n-hexane).
1H NMR spectrum, δ, ppm: 9.80 t (1H, CHO, J =
2.0 Hz), 2.48–2.34 m (2H, CH2), 2.31–1.94 m (4H,
CH2), 1.64–1.14 m (6H, CH2), 1.19–0.67 m (6H, CH3).
13C NMR spectrum, δC, ppm: 203.25 (CH), 51.11
(CH2), 36.62 (CH2), 29.16 (CH2), 28.18 (CH), 22.78
(CH2), 20.01 (CH3), 14.05 (CH3).
(S,E)-{[(3-Methylhept-4-en-1-yl)oxy]methyl}ben-
zene (6). A three-necked flask was charged under
argon with triphenyl(propyl)phosphonium bromide
(7.86 g, 25.75 mmol) in anhydrous THF, and the mix-
ture was flushed with argon. n-Butyllithium (9.83 mL,
23.58 mmol) was added on cooling with an ice bath,
the mixture was stirred for 30 min at room temperature
and cooled again with an ice bath, a solution of 5
(4.50 g, 23.41 mmol) in THF was slowly added drop-
wise, and the mixture was stirred at room temperature
overnight. A colorless oily liquid was obtained. Yield
5.02 g (97.84%), [α]D20 = +9.57° (c = 0.14, n-hexane).
1H NMR spectrum, δ, ppm: 7.44–7.28 m (5H, Harom),
5.41–5.30 m (1H, CH), 5.14 t (1H, CH, J = 10.3 Hz),
4.59–4.48 m (2H, CH2), 3.63–3.42 m (2H, CH2), 2.78–
2.61 m (1H, CH), 2.17–2.00 m (2H, CH2), 1.73 m (2H,
J = 12.9, 7.2 Hz), 1.07–0.95 m (6H, CH3). 13C NMR
spectrum, δC, ppm: 138.74 (C=C), 134.92, 130.81
(C=C), 128.36, 127.67, 127.48, 73.03 (CH2), 68.85
(CH2), 37.30, 28.56 (CH2), 21.57 (CH2), 20.75 (CH2),
14.58 (CH3). HRMS (ESI): m/z 219.17393 [M + H]+.
Calculated for C15H23O+: 219.17434.
Bromodecan-1-ol (8). Decane-1,10-diol (5 g,
28.69 mmol) was dissolved in toluene, 48% aqueous
HBr (3.73 mL, 32.99 mmol) was added, and the mix-
ture was refluxed for 24 h. A yellow oily liquid was
obtained. Yield 6.12 g (88.93%). 1H NMR spectrum, δ,
ppm: 3.80–3.59 m (1H, CH), 1.71–1.54 m (1H, CH),
1.50–1.12 m (4H, CH2), 0.93 d.d (3H, CH2, J = 6.5,
4.0 Hz). 13C NMR spectrum, δC, ppm: 61.25 (CH2),
40.01 (CH2), 36.83 (CH2), 29.51 (CH2), 29.20 (CH2),
22.97 (CH2), 19.66 (CH2), 14.11 (CH2).
10-{[(tert-Butyl)dimethylsilyl]oxy}decyl(triphe-
nyl)phosphonium bromide (9). A solution of com-
pound 8 (5 g, 21.08 mmol) in methylene chloride was
cooled in an ice bath, imidazole (2.87 g, 41.26 mmol)
was added, a solution of TBSCl (3.81 g, 25.30 mmol)
in methylene chloride was then added, and the mix-
ture was stirred overnight. A colorless oily liquid,
[(10-bromodecyl)oxy](tert-butyl)dimethylsilane, was
1
(S)-3-Methylheptan-1-ol (7). Compound 6 (3 g,
13.74 mmol) was dissolved in 50 mL of methanol, Pt/C
(10 mol % of the substrate) was added, and the mixture
was stirred in a hydrogen atmosphere at room tempera-
ture for 24 h. To continue the reaction, Pd/C (10 mol %
of the substrate) was added, the reaction vessel was
obtained. Yield 7.02 g (94.21%). H NMR spectrum,
δ, ppm: 3.64 t (2H, CH2, J = 6.5 Hz), 3.45 t (2H, CH2,
J = 7.0 Hz), 2.00–1.84 m (2H, CH2), 1.54 d.d (2H,
CH2, J = 13.5, 6.5 Hz), 1.46 d.d (2H, CH2, J = 14.0,
7.0 Hz), 1.33 s (10H, CH2), 0.94 s (9H, CH3), 0.09 s
(6H, CH3). 13C NMR spectrum, δC, ppm: 34.00 (CH2),
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LIANG WEI et al.
1094
32.90, 32.87 (CH2), 29.52 (CH2), 29.40 (CH2), 28.77
(CH2), 28.20 (CH2), 26.01 (CH2), 25.81 (CH2), 25.72
(CH2), 18.40 (CH3), –5.23 (CH3). HRMS (ESI):
m/z 351.17099 [M + H]+. Calculated for C16H36BrOSi+:
351.17133.
monium fluoride (3.12 mL, 3.12 mmol) was added
dropwise with cooling, and the mixture was allowed to
slowly warm up to room temperature. A colorless oily
liquid was obtained. Yield 0.65 g (85.72%), [α]D20
=
1
+0.75° (c = 0.08, n-hexane). H NMR spectrum, δ,
ppm: 3.68 t (2H, CH2, J = 6.5 Hz), 1.67–1.55 m (1H,
CH), 1.45–1.17 m (26H, CH2), 1.18–1.05 m (2H,
CH2), 0.98–0.84 m (6H, CH3). 13C NMR spectrum,
δC, ppm: 63.12 (CH2), 37.13 (CH2), 36.80 (CH2),
32.85 (CH), 32.76 (CH2), 30.05 (CH2), 29.74 (CH2),
29.70 (CH2), 29.68 (CH2), 29.63 (CH2), 29.62 (CH2),
29.46 (CH2), 29.36 (CH2), 27.11 (CH2), 25.77 (CH2),
25.72 (CH2), 25.66 (CH2), 23.06 (CH2), 19.74 (CH3),
14.16 (CH3).
[(10-Bromodecyl)oxy](tert-butyl)dimethylsilane
(5 g, 14.82 mmol), was dissolved in toluene, and
triphenylphosphine (4.66 g, 17.17 mmol) was added.
The mixture was refluxed for 24 h, cooled, and filtered
with suction, and the filtrate was evaporated. Yield of 9
7 g (90.88%), white solid.
(S,E)-tert-Butyl(dimethyl)[(13-methylheptadec-
10-en-1-yl)oxy]silane (10). A solution of compound 9
(8.11 g, 15.6 mmol) in THF was cooled in an ice bath,
n-butyllithium (3.90 mL, 9.75 mmol) was added under
argon, and the mixture was allowed to warm up to
room temperature and stirred for 2 h. (S)-3-Methyl-
heptanal (A1, 1 g, 7.80 mmol) was added with cooling
in an ice bath, and the mixture was stirred at room
temperature overnight. It was then quenched with
NH4Cl. Yield 2.15 g (77.65%), colorless oily liquid,
[α]D20 = +1.25° (c = 0.12, n-hexane). 1H NMR spectrum,
δ, ppm: 5.42 q.d (2H, CH2, J = 11.0, 5.6 Hz), 3.64 t
(2H, CH2, J = 6.5 Hz), 2.11–1.99 m (2H, CH2),
1.90 d.d (1H, CH, J = 13.9, 7.2 Hz), 1.72–1.10 m (22H,
CH2), 0.97–0.80 m (15H, CH3), 0.09 s (3H, CH3).
13C NMR spectrum, δC, ppm: 130.64 (C=C), 128.47
(C=C), 63.35 (CH2), 36.43 (CH2), 34.55 (CH), 33.46
(CH2), 32.92 (CH2), 29.76 (CH2), 29.63 (CH2), 29.52
(CH2), 29.46 (CH2), 29.45 (CH2), 29.35 (CH2), 27.35
(CH2), 26.00 (CH2), 25.83 (CH2), 23.01 (CH3), 19.64
(CH2), 18.39 (CH3), 14.15 (CH3), –5.24 (CH3).
(S)-14-Methyloctadec-1-ene (1). Compound 12
(0.4 g, 1.48 mmol) was treated under argon with
a solution of pyridinium chlorochromate (0.38 g,
1.77 mmol) in methylene chloride with cooling in
an ice bath. The corresponding aldehyde (13) was iso-
lated by column chromatography. Hexamethyldisila-
zane sodium salt (2.1 mL, 4.19 mmol) was added
dropwise under argon to a solution of methyl(tri-
phenyl)phosphonium bromide (1.8 g, 5.03 mmol) in
THF, and the mixture was stirred at room temperature
for 2 h. A solution of aldehyde 13 (0.9 g, 3.35 mmol) in
THF was added dropwise on cooling with ice, and the
mixture was stirred overnight. After a conventional
workup, (S)-14-methyloctadec-1-ene (1) was isolated
as an oily material. Yield 0.76 g (85.07%), [α]D20
=
+1.82° (c = 0.2, n-hexane). 1H NMR spectrum, δ, ppm:
5.86 d.d.t (1H, CH, J = 17.0, 10.0, 7.0 Hz), 5.01 d.d.d
(2H, CH2, J = 13.5, 11.0, 1.2 Hz), 2.09 q (2H, CH2,
J = 7.0 Hz), 1.49–1.07 m (27H, CH2), 0.97–0.83 m
(3H, CH3), 0.89 d (3H, CH3, J = 6.5 Hz). 13C NMR
spectrum, δC, ppm: 139.28 (C=C), 114.08 (C=C),
37.14 (CH2), 36.82 (CH2), 33.85 (CH2), 32.77 (CH),
30.06 (CH2), 29.75 (CH2), 29.71 (CH2), 29.70 (CH2),
29.65 (CH2), 29.54 (CH2), 29.37 (CH2), 29.19 (CH2),
28.99 (CH2), 27.12 (CH2), 23.07 (CH2), 19.74 (CH3),
14.17 (CH3).
(S)-tert-Butyl(dimethyl)[(13-methylheptadecyl)-
oxy]silane (11). Compound 10 (3 g, 13.74 mmol) was
dissolved in methanol (50 mL), Pt/C (10 mol % of the
substrate) was added, and the mixture was stirred in
a hydrogen atmosphere at room temperature for 24 h.
A colorless oily liquid was obtained. Yield 2.75 g
1
(83.56%), [α]D20 = +1.57° (c 0.14, n-hexane). H NMR
spectrum, δ, ppm: 3.64 t (2H, CH2, J = 6.5 Hz), 1.68–
1.48 m (1H, CH), 1.38–1.03 m (28H, CH2), 1.02–
0.83 m (15H, CH3), 0.10 s (6H, CH3). 13C NMR spec-
trum, δC, ppm: 63.37 (CH2), 37.13 (CH2), 36.81 (CH2),
32.93, 32.77, 30.06 (CH2), 29.75 (CH2), 29.71 (CH2),
29.69 (CH2), 29.67 (CH2), 29.64 (CH2), 29.47 (CH2),
29.37 (CH2), 27.12 (CH2), 26.01 (CH2), 25.84 (CH2),
23.07 (CH3), 19.74 (CH2), 18.39 (CH3), 14.17 (CH3),
–5.24 (CH3).
ACKNOWLEDGMENTS
The authors thank Liang Zhu Huang for the hydrogena-
tion steps, technician Hong Li Zhang for the NMR analysis,
and Yao-Xiang Duan for HRMS detection.
FUNDING
(S)-13-Methylheptadecan-1-ol (12). Compound 11
(1 g, 2.6 mmol) was dissolved in THF, the solution was
cooled in an ice bath, a 1 M solution of tetrabutylam-
This research was funded by an NSFC grant number
[31301712, 31760639]. Partial financial support from the
Jiangxi technological normal university is greatly appre-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 6 2020

A NEW ASYMMETRIC SYNTHESIS OF (S)-14-METHYLOCTADEC-1-ENE
1095
ciated. Zhen-Ting Du thanks Opening Funds of Key
Laboratory of Synthetic Chemistry of Natural Substances,
Shanghai Institute of Organic Chemistry, and the Chinese
Academy of Sciences for partial financial support.
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CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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