Synthesis of corn rootworm pheromones from commercial diols

Article abstract of DOI:10.1515/chempap-2015-0027

A mixture of stereoisomers of the corn rootworm pheromones was synthesised via the Grignard coupling of protected bromohydrins with alkylcuprate as a key step. The synthesis of 8-methyldec-2- yl propanoate (I), the northern corn rootworm Diabrotica longicornis Say pheromone, was achieved from pentane-1,5-diol in four steps with an overall yield of 35.1 % and 10-methyltridecan-2-one (II), the southern corn rootworm Diabrotica undecimpunctata howardi Barber pheromone, was synthesised from octane-1,8-diol as commercially available starting material in five steps with an overall yield of 28.7 %.

Full text of DOI:10.1515/chempap-2015-0027

Chemical Papers 69 (2) 380–384 (2015)
DOI: 10.1515/chempap-2015-0027
SHORT COMMUNICATION
Synthesis of corn rootworm pheromones from commercial diols
a
b
a
a,bThanh-Danh Nguyen*, Cong-Hao Nguyen, Chan Im, Chi-Hien Dang*
aDepartment of Pharmaceutical Chemistry Technology, Institute of Chemical Technology,
Vietnam Academy of Science and Technology, 1 Mac Dinh Chi Street, District 1, Ho Chi Minh City, Vietnam
bDepartment of Chemistry, Konkuk University, 1 Hwayang-dong, Gwangjin-gu, Seoul 143-701, Republic of Korea
Received 10 April 2014; Revised 27 May 2014; Accepted 1 June 2014
A mixture of stereoisomers of the corn rootworm pheromones was synthesised via the Grignard
coupling of protected bromohydrins with alkylcuprate as a key step. The synthesis of 8-methyldec-2-
yl propanoate (I ), the northern corn rootworm Diabrotica longicornis Say pheromone, was achieved
from pentane-1,5-diol in four steps with an overall yield of 35.1 % and 10-methyltridecan-2-one
(II ), the southern corn rootworm Diabrotica undecimpunctata howardi Barber pheromone, was
synthesised from octane-1,8-diol as commercially available starting material in five steps with an
overall yield of 28.7 %.
c
ꢀ 2014 Institute of Chemistry, Slovak Academy of Sciences
Keywords: Diabrotica longicornis Say, Diabrotica undecimpunctata howardi Barber, Grignard cou-
pling, pheromone, bromohydrin, diol
The northern corn rootworm, D. longicornis Say
and the southern corn rootworm, D. undecimpunctata
howardi Barber are widely distributed polyphagous
insects found on maize, peanuts, legumes and corns
in the North American and Asian continents. Their
pheromones are shown in Fig. 1. The sex pheromone
of D. longicornis Say was isolated and identified by
Krysan et al. (1986) as 8-methyldec-2-yl propanoate,
with two chiral centres at C-2 and C-8. The (2S,8R)
isomer has proved strongly attractive to males of
the insect over the other isomers. Meanwhile, 10-
methyltridecan-2-one (II ) with a chiral centre at C-10
was identified as the sex pheromone of D. undecim-
Fig. 1. Structures of northern corn rootworm Diabrotica longi-
punctata howardi Barber by Guss et al. (1983). Males
of the beetle exhibited a strong preference for the R
over the S enantiomer.
cornis Say (I) and southern corn rootworm Diabrotica
undecimpunctata howardi Barber (II) pheromones.
The synthesis of racemic 8-methyldec-2-yl pro-
panoate was first reported from methyl cyclopropyl
ketone via seven steps (Guss et al., 1983, 1988)
or from nona-1,8-diene (Chow & Kitching, 2001)
as the starting material. Mori (2010) introduced
four different ways from three to nine steps for
the synthesis of racemic 8-methyldec-2-yl propanoate
with 19 % to 40 % overall yields. All four iso-
mers of this propanoate system were synthesised
by exploiting the selectivity of an alcohol dehy-
drogenase (TBADH) catalyst in the reduction of
nonane-2,8-dione (Keinan et al., 1992). Another enan-
tiomer (2R,8R) was synthesised by transformations
*Corresponding author, e-mail: danh5463bd@yahoo.com; dangchihien@gmail.com
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T. D. Nguyen et al./Chemical Papers 69 (2) 380–384 (2015)
381
of the bisepoxides and epoxydiols (Chow & Kitching,
2002).
(monitored by GC). This process was repeated four
times. The combined organic layers were washed suc-
cessively with a 5 % aqueous solution of NaHCO3,
water and brine and dried with MgSO4. The sol-
vents were evaporated under diminished pressure to
afford 8.0 g of the crude product. A mixture of the
crude product (6.0 g, 36 mmol), 3,4-dihydro-2H-pyran
(7.0 g, 70 mmol) and pyridinium p-toluenesulphonate
(PPTS) (105 mg) in dry dichloromethane (DCM)
(21 mL) was stirred overnight. Next, the solution
was diluted with ether and washed once with half-
saturated brine to remove the catalyst. The ethereal
solution was dried, concentrated and the product was
distilled under reduced pressure (b.p. 120◦C/0.8 kPa)
to afford a colourless liquid (9.28 g, 64.9 % yield in
two steps); n2D8 = 1.4402.
2-((8-Bromooctyl)oxy)tetrahydro-2H-pyran (IVb)
(IUPAC name: 2-((8-bromooctyl)oxy)oxan was syn-
thesised in the manner reported for IVa, using octane-
1,8-diol as a starting material (yield 62.5 %; b.p.
158◦C/0.267 kPa; n2D8 = 1.4420. The physical and
spectral data of IVa and IVb were in accordance with
those already published for authentic samples.
7-Methylnonan-1-ol (Va) was synthesised as fol-
lows: the Grignard reagent solution obtained from
1-bromo-2-methylbutane (15.1 g, 0.1 mol) and mag-
nesium (2.0 g, 0.1 mol) in anhydrous THF (30 mL)
was slowly added drop-wise using a syringe to a so-
lution of (IVa) (12.55 g, 50 mmol) in THF (30 mL)
containing a catalytic amount of Li2CuCl4 (0.2 M so-
lution in THF, 10 mL, 2 mmol) at 20◦C. After stir-
ring overnight at ambient temperature, the mixture
was poured into an aqueous solution of NH4Cl and
extracted with diethyl ether. The organic layer was
washed with an aqueous solution of NaHCO3, wa-
ter and brine, then dried with anhydrous MgSO4 and
concentrated under reduced pressure to afford 11.0 g
of the crude product. A mixture of the crude prod-
uct (10 g, 41 mmol), p-toluenesulphonic acid (PTSA)
(300 mg) and methanol (200 mL) was stirred at 50◦C
for 2 h. The mixture was then concentrated to half-
volume, poured into the NaHCO3 solution and the
product was extracted with diethyl ether. The com-
bined organic layers were washed with brine, dried
(MgSO4) and the solvent was evaporated to afford
7-methylnonan-1-ol (5.83 g, 81.8 % yield in two steps)
which was purified by distillation under reduced pres-
sure (b.p. 89◦C/1.33 kPa; n2D8 = 1.4292).
With the aid of the pheromones, effective and
cost-efficient control of the insect populations can
be foreseen, hence several total syntheses of the 10-
methyltridecan-2-one enantiomer have been published
(Rossi et al., 1985; Senda & Mori, 1983; Nguyen et
al., 1987). Most recently, (R)-II was synthesised by an
asymmetric Michael addition using enantiomerically
pure (4S)-benzylthiazolidinethione as a chiral auxil-
iary (Lu et al., 2009). Shikichi and Mori (2012) em-
ployed Grubbs’ catalyst efficiently in the synthesis of
(R)-II from (S)-3-hydroxy-2-methyl propanoate. The
synthesis of racemic 10-ethyltridecan-2-one has been
also carried out from methyl cyclopropyl ketone (Guss
et al., 1984) or from furan-2-carbaldehyde (Kovalev et
al., 1994).
A low-cost method of synthesis is particularly nec-
essary in the practical use of the pheromones. In ad-
dition, the data of synergism or inhibition were in-
sufficiently scrutinised when various mixtures of the
stereoisomers of the pheromones were tested. Accord-
ingly, it was decided to synthesise a racemic mixture
of 8-methyldec-2-yl propanoate and 10-ethyltridecan-
2-one for monitoring the population of the insects in
Asia, including Vietnam. Herein, an efficient proce-
dure for synthesising two pheromones from commer-
cial diols is reported, using Grignard coupling of the
protected bromohydrins as a key step.
All manipulations were performed under a dry
nitrogen atmosphere using Schlenk techniques. The
starting pentane-1,5-diol and octane-1,8-diol were
purchased from Merck (Germany) and other reagents
were purchased from Aldrich. THF was dried with
Na/benzophenone and freshly distilled prior to use.
The other solvents were purchased from Fluka and
used without further purification. Column chromatog-
raphy was performed with Merck Kieselgel 60. IR
spectra were recorded on a BRUKER EQUINOX
55 IR spectrophotometer. 1H (500 MHz) and 13C
(125 MHz) NMR were recorded on a BRUKER
AVANCE 500 NMR spectrometer using CDCl3 as sol-
vent and tetramethylsilane (TMS) as internal stan-
dard. Chemical shifts are reported in δ relative to
TMS. GC-MS analyses were carried out using an Ag-
ilent Technologies 6890N (USA). Refractive indices
(nD) were measured with an ABBE refractometer
Way-2S.
2-((5-Bromopentyl)oxy)tetrahydro-2H-pyran
9-Methyldodecan-1-ol (Vb) was prepared in a sim-
ilar manner to that reported for Va, using IVb and
2-bromopentane as a starting material (yield 80.9 %;
b.p. 115◦C/0.533 kPa; n2D9 = 1.4280).
7-Methylnonanal (VIa) was synthesised using a
method reported previously (Kovalev et al., 1993),
with a slight modification, as follows: a solution of
(Va) (5.05 g, 32 mmol) in DCM (25 mL) was added
to a suspension of pyridinium chlorochromate (PCC)
(10.5 g, 48.75 mmol) in anhydrous DCM (50 mL) and
(IVa) (IUPAC name: 2-((5-bromopentyl)oxy)oxan)
was prepared following the method reported previ-
ously, with a slight modification, as follows: a mix-
ture of pentane-1,5-diol (IIIa, 6.76 g, 65 mmol), ace-
tone (40 mL) and HBr (40 %, 11.45 mL, 78 mmol) in
petroleum ether (100 mL) was heated under reflux for
4 h using Dean-Stark equipment. The organic layer
was separated, hexane (100 mL) was added and the
mixture was refluxed continuously for a further 4 h
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382
T. D. Nguyen et al./Chemical Papers 69 (2) 380–384 (2015)
Fig. 2. Synthetic strategy of pheromones.
Fig. 3. Synthesis of pheromones I and II. Reaction conditions: i) 1. HBr/petroleum ether/acetone, 2. 3,4-dihydro-2H-pyran, DCM,
PPTS, 4 h; ii) 1. Mg, Li2CuCl4/THF, 0–5◦C, 1-bromo-2-methylbutane or 2-bromopentane, 2. PTSA, MeOH, 50◦C; iii)
PCC, DCM, r.t.; iv) 1. CH3MgI/THF, 0◦C, 2. (EtCO)2O/THF, r.t.; v) CH3MgI/Et2O, 0◦C; vi) Jones reagent.
the mixture was stirred at ambient temperature for
2.5 h (monitored by GC) followed by dilution with
hexane (100 mL) and filtration through a short col-
umn of silica gel (15 g), using hexane/diethyl ether (ϕr
= 9 : 1) as eluent. The combined filtrate and eluents
were concentrated and the crude product was purified
by distillation under reduced pressure to afford VIa
(4.1 g, 82.1 %; b.p. 88◦C/1.6 kPa; n2D9 = 1.4218).
9-Methyldodecanal (VIb) was prepared in a similar
manner to that reported for VIa, using Vb as a starting
drous MgSO4 and concentrated under reduced pres-
sure. The residue was purified on a column of silica gel
using hexane/EtOAc (ϕr = 5 : 1) to afford I (4.6 g,
80.7 %; n3D0 = 1.4230).
10-Methyltridecan-2-ol (VII ) was prepared in a
similar manner to that reported for I, except for the
addition of propionic anhydride into the reaction mix-
ture. The yield was 87.9 %; b.p. 84◦C/66.7 Pa; nD29.5
= 1.4317.
10-Methyltridecan-2-one (II ) was prepared (79.3 %
yield) in the manner reported by Senda and Mori
(1983).
material (yield 81.7 %; b.p. 101◦C/133.3 Pa; nD28
=
1.4241).
8-Methyldecan-2-yl propanoate (I ) was synthe-
sised using a method reported previously (Kovalev
et al., 1993), with modification follows: a solution of
(VIa) (3.9 g, 25 mmol) in anhydrous THF (30 mL)
cooled to 0◦C was slowly added drop-wise using a sy-
ringe to the Grignard reagent prepared from methyl
iodide (7.1 g, 50 mmol) and magnesium (1.2 g,
50 mmol) in anhydrous THF (30 mL), then the mix-
ture was stirred at ambient temperature for 6 h (mon-
itored by GC). After cooling to 0–5◦C, propionic an-
hydride (3.25 g, 25 mmol) in THF (10 mL) was
added drop-wise and the mixture was stirred overnight
at ambient temperature. The reaction mixture was
poured into an aqueous solution of NH4Cl and the
product was extracted with diethyl ether. The com-
bined organic layers were washed with an aqueous so-
lution of NaHCO3, water and brine, dried with anhy-
The synthetic strategy used is shown by the ret-
rosynthetic analysis outlined in Fig. 2. The impor-
tant key intermediates of both pheromones are the
respective alcohols which have a similar structure.
These alcohols can be formed by the Grignard reac-
tion between the respective aldehydes and the Grig-
nard reagent obtained from iodomethane. The alde-
hydes can be divided into two fragments, fragment A,
containing a branched alkyl, and fragment B, contain-
ing a functional group. Fragment B can be prepared
from commercial diols, pentane-1,5-diol (for the syn-
thesis of I ) and nonane-1,9-diol (for the synthesis of
II ). However, for the synthesis of VII, an economical
way was selected designed from octane-1,8-diol and
2-bromopentane.
The synthetic pathway is shown in Fig. 3. The
diols were converted to bromohydrins by treating
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T. D. Nguyen et al./Chemical Papers 69 (2) 380–384 (2015)
Table 1. Spectral data of prepared compounds
383
Compound
Spectral data
IR, νmax/cm−1: 726, 772, 807, 878, 922, 1006, 1082, 1126, 1193 (s, C—O), 1274, 1337, 1377, 1462, 1737 (s, C O),
—
—
I
2858, 2930, 2961
1H NMR (500 MHz, CDCl3), δ: 0.79–0.88 (6H, m), 1.13 (3H, t, J = 7.8 Hz), 1.20 (3H, d, J = 6.0 Hz), 1.26–1.65
(13H, m), 2.29 (2H, q, J = 7.5 Hz), 4.87–4.93 (1H, m)
13C NMR (125 MHz, CDCl3), δ: 9.22, 11.37, 19.19, 19.99, 25.44, 26.98, 27.97, 29.48, 29.81, 34.38, 35.99, 36.52,
70.80, 174.14
MS, m/z: 228 (M+
)
II
IR, νmax/cm−1: 1162, 1359, 1462, 1718, 2855, 2926, 2956
1H NMR (500 MHz, CDCl3), δ: 0.84 (3H, d, J = 7.0 Hz), 0.88 (3H, t, J = 7.0 Hz), 1.06–1.40 (17H, m), 2,13 (3H,
s), 2.39–2.42 (2H, t, J = 7.5 Hz)
13C NMR (125 MHz, CDCl3), δ: 14.38, 19.65, 20.13, 23.91, 27.00, 29.20, 29.43, 29.79, 29.81, 32.47, 37.05, 39.42,
43.83, 209.26
MS, m/z: 212 (M+
)
Va
IR, νmax/cm−1: 724, 770, 896, 1057 (s, C—O), 1125, 1205, 1377, 1461, 2856, 2927, 3339 (br, OH)
1H NMR (500 MHz, CDCl3), δ: 0.84–0.88 (6H, m), 1.06–1.38 (11H, m), 1.54–1.59 (2H, quint, J = 7.0 Hz), 1.84 (1H,
s), 3,63 (2H, t, J = 6.7 Hz)
13C NMR (125 MHz, CDCl3), δ: 11.36, 19.19, 25.79, 27.05, 29.48, 29.79, 32.80, 34.39, 36.56, 62.98
MS, m/z: 158 (M+
)
Vb
IR, νmax/cm−1: 722, 1056, 1125, 1377, 1463, 2854, 2925, 3338
1H NMR (500 MHz, CDCl3), δ: 0.83 (3H, m), 0.88 (3H, d, J = 7.0 Hz), 1.26–1.68 (19H, m), 3.63 (2H, t, J = 7.0 Hz)
13C NMR (125 MHz, CDCl3), δ: 14.39, 19.66, 20.14, 25.77, 27.05, 29.46, 29.95, 32.49, 32.82, 37.07, 39.44, 63.05
MS, m/z: 200 (M+
)
—
VIa
IR, νmax/cm−1: 727, 771, 856, 968, 1132, 1378, 1462, 1728 (s, C O), 2715, 2857, 2929, 2960
—
1H NMR (500 MHz, CDCl3), δ: 0.86–0.9 (6H, m), 1.06–1.67 (11H, m), 2.40–2.43 (2H, dt, J = 1.8 Hz, J = 7.3 Hz),
9.76 (1H, t, J = 1.8 Hz)
13C NMR (125 MHz, CDCl3), δ: 11.37, 19.17, 22.15, 26.82, 29.47, 29.53, 34.35, 36.37, 43.93, 202.93
MS, m/z: 156 (M+
)
VIb
VII
IR, νmax/cm−1: 723, 1027, 1235, 1389, 1461, 1724, 2854, 2929
1H NMR (500 MHz, CDCl3), δ: 0.89 (3H, m), 0.96 (3H, d, J = 7.0 Hz), 1.26–1.68 (17H, m), 2.42 (2H, m), 9.76 (1H,
t, J = 1.8 Hz)
13C NMR (125 MHz, CDCl3), δ: 14.39, 19.65, 20.13, 25.52, 26.97, 29.39, 29.51, 29.77, 32.47, 37.03, 39.41, 43.92,
202.93
MS, m/z: 198 (M+
)
IR, νmax/cm−1: 1118, 1375, 1462, 2854, 2926, 2959, 3356
1H NMR (500 MHz, CDCl3), δ: 0.83–0.89 (6H, m), 1.10 (2H, m), 1.18–1.21 (17H, m), 1.41–1.45 (3H, m), 4.05 (1H,
m)
13C NMR (125 MHz, CDCl3), δ: 14.38, 19.64, 20.12, 23.43, 25.78, 27.04, 29.66, 29.94, 29.93, 32.47, 37.06, 39.37,
39.42, 68.14
MS, m/z: 214 (M+
)
with hydrobromic acid in a mixture of petroleum
ether/acetone (Trivedi et al., 1999). These bromo-
hydrins were treated with 3,4-dihydro-2H-pyran in
DCM to give the corresponding O-tetrahydropyranyl-
protected alkyl bromides IVa or IVb with yields of over
60 % in two steps. Next, a coupling between the Grig-
nard reagent prepared from 1-bromo-2-methylbutane
or 2-bromopentane with IVa or IVb was performed
as a crucial step. The Grignard coupling reaction
was carried out at ambient temperature in the pres-
ence of dilithium tetrachlorocuprate followed by de-
tetrahydropyranylation with PTSA in methanol at
50◦C to give the corresponding alcohols with yields
of over 80 % in two steps. Oxidation of Va and Vb
with PCC afforded the aldehydes VIa (82.1 % yield)
and VIb (81.7 % yield), respectively. Next, a reaction
of the Grignard reagent (prepared from iodomethane)
with aldehyde VIb gave alcohol VII with a yield of
87.9 %. Finally, alcohol VII was treated with the Jones
chromic acid reagent to afford ketone II with a yield
of 79.3 % while ester I was prepared with a yield of
80.7 % following the method devised by Iwamoto et
al. (1983) by the reaction of methylmagnesium io-
dide with aldehyde VIa and propionic anhydride in
THF.
All products were characterised by IR and NMR
spectra (Table 1) which were in accordance with those
reported previously (Mori, 2010; Lu et al., 2009).
In conclusion, this work demonstrates a short, sim-
ple and efficient synthetic route to a stereoisomer
mixture of the sex pheromones. Compounds I and
II, the sex pheromones of D. longicornis Say and
D. undecimpunctata howardi Barber, were synthesised
with overall yields of 35.1 % (four steps) and 28.7 %
(five steps) calculated on starting pentan-1,5-diol and
octan-1,8-diol, respectively. These results contribute
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384
T. D. Nguyen et al./Chemical Papers 69 (2) 380–384 (2015)
to the methodology to further advance the practical
use of pheromones as environmentally benign tools for
pest control.
Kovalev, B. G., Nasser, F. A., Sorochinskaya, A. M. (1993).
Synthesis of the racemic propionate of 8-methyl-2-decanol,
the sex hormone of the several leaf-eating bugs Diabrotica
(Chrysomelidae). Russian Journal of Organic Chemistry, 29,
1651–1653.
Supplementary data
Kovalev, B. G., Nasser, F. A.,
& Sorochinskaya, A. M.
(1994). Synthesis of racemic 10-methyltridecan-2-one, the
sex pheromone of Diabrotica undecimpunctata. Chemistry of
Natural Compounds, 30, 515–517. DOI: 10.1007/bf00630412.
Krysan, J. L., Wilkin, P. H., Tumlinson, J. H., Sonnet, P. E.,
Carney, R. L., & Guss, P. L. (1986). Responses of Diabrotica
lemniscata and D. longicornis (Coleoptera: Chrysomelidae)
to stereoisomers of 8-methyl-2-decyl-propanoate and studies
on the pheromone of D. longicornis. Annals of the Entomo-
logical Society of America, 79, 742–746.
Supplementary data (1H and 13C NMR spectra)
associated with this article can be found in the online
version of this paper (DOI: 10.1515/chempap-2015-
0027).
References
Lu, C. F., Zhang, S. B., Li, Y., Yang, G. C., & Chen, Z. X.
(2009). Stereoselective synthesis of (R)-10-methyltridecan-2-
one, the sex pheromone of the southern corn rootworm, us-
ing (4S)-benzylthiazolidinethione as a chiral auxiliary. Tetra-
hedron: Asymmetry, 20, 2267–2269. DOI: 10.1016/j.tetasy.
2009.09.014.
Mori, K. (2010). New syntheses of 1,7-dimethylnonyl propano-
ate, the western corn rootworm pheromone, in four different
ways via cross metathesis, alkylation and coupling reactions.
Bioscience, Biotechnology, and Biochemistry, 74, 595–600.
DOI: 10.1271/bbb.90805.
Nguyen, C. H., Mavrov, M. V., & Serebryakov, E. P. (1987).
Pheromones of Coleoptera. 10. Synthesis of the chiral
pheromones of the southern corn rootworm (Coleoptera:
Chrysamelidae). Izvestiya Akademii Nauk SSSR, Seriya
Khimicheskaya, 9, 2083–2085.
Rossi, R., Carpita, A., & Chini, M. (1985). Synthesis of the
two enantiomers of the sex pheromone of Diabrotica un-
decimpunctata Howardi and of chiral precursors of other
pheromones starting from enantiomerically pure methyl hy-
drogen (R)-3-methylglutarate. Tetrahedron, 41, 627–633.
DOI: 10.1016/s0040-4020(01)96510-x.
Chow, S., & Kitching, W. (2001). Hydrolytic kinetic resolution
of mono- and bisepoxides as a key step in the synthesis of
insect pheromones. Chemical Communication, 2001, 1040–
1041. DOI: 10.1039/b102181h.
Chow, S., & Kitching, W. (2002). Hydrolytic kinetic reso-
lution of terminal mono- and bis-epoxides in the synthe-
sis of insect pheromones: routes to (–)-(R)- and (+)-(S)-
10-methyldodecyl acetate, (–)-(R)-10-methyl-2-tridecanone,
(–)-(R)-(Z )-undec-6-en-2-ol (Nostrenol), (–)-(1R,7R)-1,7-
dimethylnonyl propanoate, (–)-(6R,12R)-6,12-dimethylpen-
tadecan-2-one, (–)-(2S,11S)-2,11-diacetoxytridecane and
(+)-(2S,12S)-2,12-diacetoxytridecane. Tetrahedron: Asym-
metry, 13, 779–793. DOI: 10.1016/s0957-4166(02)00175-1.
Guss, P. L., Tumlinson, J. H., Sonnet, P. E., & McLaughlin, J.
R. (1983). Identification of a female-produced sex pheromone
from the southern corn rootworm, Diabrotica undecimpunc-
tata howardi Barber. Journal of Chemical Ecology, 9, 1363–
1375. DOI: 10.1007/bf00994805.
Guss, P. L., Tumlinson, J. H., Sonnet, P. E., & McLaughlin, J.
R. (1984). U.S. Patent No. 4474991. Washington, DC, USA:
U.S. Patent and Trademark Office.
Guss, P. L., Tumlinson, J. H., Sonnet, P. E., & Proveaux, A.
T. (1988). U.S. Patent No. 4734524. Washington, DC, USA:
U.S. Patent and Trademark Office.
Iwamoto, M., Takagi, Y., Kogami, K., & Hayashi, K. (1983).
Synthesis of characteristic flavor constituents of K¯ogyoku
apple (Jonathan) essential oil. Agricultural and Biological
Chemistry, 47, 117–119. DOI: 10.1271/bbb1961.47.117.
Keinan, E., Sinha, S. C., & Sinha-Bagchi, A. (1992). Ther-
mostable enzymes in organic synthesis. 7. Total synthesis of
the western corn rootworm sex pheromone 8-methyldec-2-yl
propanoate using a TBADH-generated C2-bifunctional chi-
ron. The Journal of Organic Chemistry, 57, 3631–3636. DOI:
10.1021/jo00039a023.
Senda, S., & Mori, K. (1983). Synthesis of (R)-(–)-10-methyl-2-
tridecanone, the pheromone of the southern corn rootworm.
Agricultural and Biological Chemistry, 47, 795–798. DOI:
10.1271/bbb1961.47.795.
Shikichi, Y., & Mori, K. (2012). Metathesis-mediated synthe-
sis of (R)-10-methyl-2-tridecanone, the southern corn root-
worm pheromone. Bioscience, Biotechnology, and Biochem-
istry, 76, 407–409. DOI: 10.1271/bbb.110738.
Trivedi, S. V., Subbaraman, A. S., Chattopadhyay, S., & Mam-
dapur, V. R. (1999). Convenient synthesis of two mango al-
lergens. Molecules, 4, 245–254. DOI: 10.3390/40900245.
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