Sesterterpenoids and diterpenoids of the wax excreted by a scale insect, Ceroplastes pseudoceriferus

Article abstract of DOI:10.1021/np990170t

A new sesterterpene, (2Z,6Z,10E)-cericerene-15,24-diol (1), and its 30- hydroxytriacontanoate (2) were isolated from the wax exuded by the scale insect Ceroplastes pseudoceriferus, together with the acetates and 30- hydroxytriacontanoates of 3,15-dihydroxy- and 15,20-dihydroxylabda-7,13-diene (3-6). The absolute configurations of the labdadiene alcohols were antipodal to the ordinary labdanes isolated from terrestrial plants.

Full text of DOI:10.1021/np990170t

1504
J . Nat. Prod. 1999, 62, 1504-1509
Sester ter p en oid s a n d Diter p en oid s of th e Wa x Excr eted by a Sca le In sect,
Cer opla stes pseu d ocer ifer u s
Masahiko Toki, Takashi Ooi, and Takenori Kusumi*
Faculty of Pharmaceutical Sciences, Tokushima University, Tokushima 770-8505, J apan
Received April 16, 1999
A new sesterterpene, (2Z,6Z,10E)-cericerene-15,24-diol (1), and its 30-hydroxytriacontanoate (2) were
isolated from the wax exuded by the scale insect Ceroplastes pseudoceriferus, together with the acetates
and 30-hydroxytriacontanoates of 3,15-dihydroxy- and 15,20-dihydroxylabda-7,13-diene (3-6). The
absolute configurations of the labdadiene alcohols were antipodal to the ordinary labdanes isolated from
terrestrial plants.
The scale insects, harmful creatures of 6-9 mm size
infesting many orchard trees, exude waxy secretions, as a
result of which they are protected from predators. The
chemical components of the scale insects have been exten-
sively studied, and unique sesterterpenes and diterpenes
have been isolated from the wax.1
We have studied the chemical components of the wax
excreted by the scale insect Ceroplastes pseudoceriferus
Green (Coccidea), collected at the campus of this university
and have characterized one new sesterterpene and several
new diterpenoids. This report deals with the structure
elucidation of these new compounds and the absolute
configuration determination of the diterpenoids.
F igu r e 1. The structure of cericerene-15,24-diol and the new com-
pound (1). The arrows on 1 show the NOEs found in the NOESY
spectrum.
The 1H NMR spectrum of 2 was similar to that of 1
except for a large envelope due to aliphatic methylene
protons (δ 1.20-1.27, br s) and the signals of the methylene
protons bearing a hydroxyl group (δ 3.63, t, J ) 6.6 Hz),
as well as the methylene protons adjacent to a carbonyl
group (δ 2.30, t, J ) 7.7 Hz). The HOHAHA spectrum of 2
suggested that these protons were in the same proton
network, and that a long-chain hydroxy fatty acid was
linked to 1. The hydroxy fatty acid must be condensed with
the OH-24 group of 1, because CH2-24 appeared at δH 4.62
Resu lts a n d Discu ssion
The scale insect, C. pseudoceriferus, which feeds on the
host Laurus nobilis L. (Lauraceae) (a laurel), was collected
in 1996. The wax and the insect body were soaked in
chloroform, and the chloroform-soluble material was sepa-
rated from the insect debris. The evaporated residue was
methylated with diazomethane in diethyl ether and was
fractionated by repeated chromatography on Si gel to yield
two new sesterterpenoids (1 and 2), four diterpenoids
(3, 4, 6, and 7), and the methyl esters of three diterpenes
(9, 11, and 13).
The 1H NMR spectrum (400 MHz, CDCl3) of 1 showed
signals of a methyl attached to a carbon carrying a hydroxyl
group at δ 1.12 (s); four olefinic methyls at 1.55, 1.62, 1.64,
and 1.68 (each 3H, s); olefinic protons at 5.01-5.40 (4H);
and hydroxymethyl protons as a doublet (δ 4.06 and 4.23,
both 1H, d, J ) 11.6 Hz). The 13C NMR spectrum confirmed
the presence of four olefinic bonds (δ 124.6, 125.9, 126.4,
129.2, 131.6, 134.1, 134.2, and 136.4). Further analysis of
the COSY, HSQC, and HMBC spectra suggested that 1 had
a structure very similar to that of cericerene-15,24-diol (see
Figure 1).2 However, there are significant differences in the
NMR properties between 1 and cericerene-15,24-diol. The
NOESY spectrum carried out on 1 revealed that the three
olefins on the ring had 2Z, 6Z, and 10E configurations,
contrary to the 2E, 6E, and 10E configurations of cericerene-
15,24-diol. Accordingly, 1 was named (2Z,6Z,10E)-cericerene-
15,24-diol. The absolute configuration at C-14 has not been
clarified.
1
as an AB quartet in the H NMR spectrum.
The chain length of the hydroxy fatty acid was deter-
mined by GC-MS. The ester 2 was treated with sodium
methoxide in MeOH, followed by acetylation (Ac2O/pyri-
dine), and the product containing the ω-acetoxy fatty acid
methyl ester was subjected to GC-MS. In the GC, three
peaks in the ratio of 20:2:3 appeared, the MS of which
showed parent peaks (M+ - CH3O) at m/z 493, 465, and
437, respectively. From these data, it was concluded that
the hydroxy fatty acid moiety of the sesterterpenoid ester
2 consisted of 30-acetoxytriacontanoic, 28-acetoxyocta-
cosanoic, and 26-acetoxyhexacosanoic acids, in a 20:2:3
ratio.
1
The H NMR spectrum of 3 showed three sharp singlets
due to angular methyls (δ 0.74, 0.84, 0.95), two broad
singlets of olefinic methyls (δ 1.68, 1.69), as well as signals
assignable to two olefinic protons (δ 5.31, t, J ) 7.1 Hz,
5.38, br s), methylene protons (δ 4.57, d, J ) 7.0 Hz), and
a methine proton bearing a hydroxyl group (δ 3.22, dd, J
) 10.8, 4.8 Hz). Additional data, including the 13C NMR,
COSY, HSQC, and HMBC spectra, led to a labda-7,13-
diene-3,15-diol framework for this compound. The presence
of a large methylene signal (δ 1.21-1.32, br s) together with
a hydroxymethyl signal (δ 3.62, t, J ) 6.6 Hz) and a
* To whom correspondence should be addressed. Tel.: 81-88-633-7288.
Fax: 81-88-633-7288. E-mail: tkusumi@ph2.tokushima-u.ac.jp.
10.1021/np990170t CCC: $18.00
© 1999 American Chemical Society and American Society of Pharmacognosy
Published on Web 09/24/1999

Terpenoids from Insect Wax
J ournal of Natural Products, 1999, Vol. 62, No. 11 1505
F igu r e 2. The structure of 3 and 15. The arrows on 3 indicate the
NOEs found in the NOESY spectrum. The numbers on 3a correspond
to the ∆δ values obtained from the 1H chemical shifts of (R)- and (S)-
MTPA esters of 3.
methylene triplet (δ 2.28, t, J ) 7.5 Hz) suggested that a
hydroxy fatty acid was linked to either OH-3 or OH-15.
The downfield shift of CH2-15 (δ 4.57) indicated that the
hydroxy acid is connected to OH-15. The relative configu-
ration of the ring substituents of 3 was determined by
analyzing the NOESY spectrum. This stereochemistry is
the same as (-)-labda-7,13-diene-3,15-diol (15), which was
isolated by Naya et al.2
The absolute configuration of 3 was determined by the
modified Mosher’s method.3 Esterification of 3 with (R)-
and (S)-MTPA acids yielded the respective di-MTPA esters.
The ∆δ values (δS - δR) are shown in structure 3a (see
Figure 2). The positive and negative ∆δ values are oriented
on the right and left sides of the MTPA plane, which
indicated the R configuration of OH-3. Because the relative
configuration of 3 has been elucidated, the absolute con-
figuration of this compound was determined as shown in
the structure (3). Interestingly, the absolute configuration
thus determined is enantiomeric to that of 15.
F igu r e 3. Chemical reactions transforming 8 and 17. The numbers
on 19a correspond to the ∆δ values obtained from the 1H chemical
shifts of the (R)- and (S)-MTPA esters of (19).
the following NOEs: 17-Me T 18-Me, 19-Me T 5-H, 5-H
T 9-H, 17-Me T 11-H2, 15-H2 T 16-Me.
The hydroxy fatty acid moiety of both 3 and 6 was
composed of 30-hydroxytriacontanoic acid and 32-hydroxy-
dotriacontanoic acid (94:6), which was confirmed by mass
spectroscopy in the same way as described for 2.
The structure of 7 was deduced from its NMR data, and
eventually confirmed by hydrolysis to 8, which was identi-
cal with the product derived from 6. The optical rotation
of 8, [R]25 -9.9°, when obtained from both 6 and 7, was
D
identical, showing that they had the same absolute con-
figuration. Although the enantiomer of 8 is known, the
reported chiroptical property, [R]25 -2.2°, did not agree
D
with our data. Therefore, we focused on establishing the
absolute configuration of 8 obtained in this work.
The similar NMR analysis of 4 revealed that the hydroxy
fatty acid moiety at C-15 was replaced by an acetoxy group
in this compound. Hydrolysis (KOH-MeOH-H2O) of 3 and
4 afforded an identical labda-7,13-diene-3,15-diol (5). The
optical rotation of 5, [R]25D +5.9°, is opposite in sign to that
Because 8 does not possess a secondary hydroxyl group,
the modified Mosher’s method was not appropriate. Very
recently we have developed a new method using phenylg-
lycine methyl ester (PGME)4 that can determine the
absolute configuration of carboxylic acids having a chiral
center at the â-position (â-chiral carboxylic acids). The
outline of this extended PGME method is described in
Figure 4. The PGME amide of a â-chiral carboxylic acid
[A] exists in the most stable conformation [B]. The acid is
condensed with commercially available (R)- and (S)-PGME,
the proton chemical shifts of each diastereomer are as-
signed, and the absolute configuration is assigned using
the model [C; ∆δ ) δR - δS] in a manner similar to the
modified Mosher’s method.
The hydrolysate 8, prepared from 6 and 7, was acetylated
to give a diacetate. Reductive deacetoxylation (Ca/NH3)
produced the diene (16). Ozonolysis of 16 in MeOH at -78
°C and subsequent workup with H2O2 afforded a â-chiral
carboxylic acid 17, which was identified as its methyl ester
18. The â-chiral carboxylic acid 17 was condensed with (R)-
and (S)-PGME, and the ∆δ values were calculated for each
diastereomer of 19. The results are shown in 19a (see
Figure 3). The systematic arrangement of positive and
negative ∆δ values was observed, and these findings led
to the absolute configuration of 19, and, therefore, of 8, as
shown in their structures. The absolute configuration thus
of 15, [R]25 -2.1°, which confirmed the present result of
D
the modified Mosher’s method. The difference of the
absolute values between these two values might be due to
the presence of the enantiomer in the sample of 15. Our
compound (5) has been confirmed to be enantiomerically
pure, because the 1H NMR spectra of the (R)- and (S)-
MTPA esters of 3 indicated the complete absence of the
enantiomer. It should be noted that the enantiomer of 15
was found from the scale insect Ceroplastes ceriferus
Anderson living on Diospyros kaki Thunb.2
1
The H NMR spectrum of 6 showed three methyl groups
at δ 0.74, 0.84, and 0.87 (each 3H, s); an olefinic methyl at
δ 1.70 (3H, s); a hydroxymethyl at δ 3.97, 4.13 (each 1H,
d, J ) 12.0 Hz); another hydroxymethyl (δ 4.57, 2H, d, J
) 7.0 Hz) adjacent to an olefinic proton (δ 5.35, 1H, br t, J
) 7.0 Hz); and the other olefinic proton at δ 5.75 (1H, br
s), together with the signals ascribable to an ω-hydroxy
fatty acid chain [δ 1.21-1.36, (br s), 3.62, (t, J ) 6.6 Hz),
2.28 (t, J ) 7.5 Hz)]. These properties and the 2D NMR
analysis gave the labda-7,13-diene-15,20-diol structure 6.
The relative stereochemistry of the substituents was
deduced by analyzing the NOESY spectrum, which showed

1506 J ournal of Natural Products, 1999, Vol. 62, No. 11
Toki et al.
F igu r e 4. An outline of the extended PGME method to elucidate the
absolute configuration of â-chiral carboxylic acids [A]. The most stable
conformation [B] of a PGME amide is drawn. The absolute configu-
ration of [A] can be determined by using [C] in a similar way with the
modified Mosher’s method.
determined is compatible with that of 6 and 7, verifying
the use of the extended PGME method to this â-chiral
carboxylic acid.
Abietic acid (9) was isolated as its methyl ester 10. The
structure was confirmed by comparison of its 1H and 13C
NMR properties with the reported data. The absolute
configuration of 10 was identical with methyl (-)-abietate,
because its specific rotation ([R]25 -56.7°) was in good
D
agreement with the reported value, -61° (CHCl3).5
Neoabietic acid (11)6 and 15-hydroxyabieteic acid (13)7
were also isolated as their methyl esters, 12 and 14.
Although their structures were confirmed by comparison
of their NMR properties with those of the reported data,
their absolute configuration could not be determined
because of the limited quantity available.
evaporator to give a residue (63.9 g), which was subjected to
Si gel (Merck, Kieselgel 60) column chromatography eluted
by EtOAc-hexane (0, 10, 30, 50, 70, 90, and 100% EtOAc).
The fractions containing terpenoids (by NMR) were esterified
with excess diazomethane in diethyl ether, and the methylated
fractions were again separated by Si gel flash column chro-
matography (1:6 EtOAc-hexane) and were finally purified by
HPLC (Hibar RT250-25, LiChrosorb Si60) (1:8 EtOAc-
hexane) to give compounds 1 (11.7 mg), 2 (5.7 mg), 3 (47.7
mg), 4 (146.3 mg), 5 (15.4 mg), 6 (8.3 mg), 7 (5.2 mg), 8 (18.4
mg), 9 (4.7 mg), 12 (1 mg), and 14 (1 mg).
It is quite interesting that the abietic acid (9) obtained
from the insect wax is antipodal to the labdanes 3, 4, 6,
and 7, which are present in the same wax. Considering that
the present labdanes have absolute configurations opposite
those produced by terrestrial plants, we may assume that
the present labdanes have been biosynthesized by the scale
insect. The abietic acid (9), which has the common absolute
configuration, may be simply excreted by the insect without
digestion of the plant ingredient. An attempt to isolate the
labdane and abietane diterpenes from the laurel was
fruitless, because it resulted in inseparable mixtures of
terpenoids and glycerides.
(2Z,6Z,10E)-Cer icer en e-15,24-d iol (1): [R]D -51.5° (c
0.09, CHCl3); 1H NMR (CDCl3, 400 MHz) δ 1.12 (3H, s, H-22),
1.20 (1H, m, H-13a), 1.48 (3H, m, H-14, H-16), 1.55 (3H, s,
H-25), 1.62 (3H, s, H-21), 1.64 (3H, s, H-23), 1.68 (3H, s, H-20),
1.63-1.81 (2H, m, H-1a, H-13b), 2.00-2.17 (8H, m, H-4a, H-8a,
H-9, H-12, H-17), 2.28-2.35 (5H, m, H-1b, H-4b, H-5, H-8b),
4.06 (1H, d, J ) 11.6 Hz, H-24a), 4.23 (1H, d, J ) 11.6 Hz,
H-24b), 5.01 (1H, t, J ) 7.0 Hz, H-10), 5.12 (2H, m, H-6, H-18),
5.40 (1H, t, J ) 7.7 Hz, H-2); 13C NMR (CDCl3, 100 MHz) δ
15.4 (q, C-25), 17.6 (q, C-21), 22.1 (t, C-17), 22.1 (q, C-23), 23.6
(q, C-22), 24.3 (t, C-9), 24.5 (t, C-4), 25.6 (q, C-20), 28.1 (t, C-13),
29.0 (t, C-1) 30.2 (t, C-5), 35.1 (t, C-8), 38.9 (t, C-12), 39.7 (t,
C-16), 47.2 (d, C-14), 60.0 (t, C-24), 75.7 (s, C-15), 124.6 (d,
C-18), 125.9 (d, C-10), 126.4 (d, C-2), 129.2 (d, C-6), 131.6 (s,
C-19), 134.1 (s, C-7), 134.2 (s, C-3), 136.4 (s, C-11); GC-MS
m/z 356 [M+ - H2O] (8), 325 (4), 109 (75), 81 (100), 55 (63);
HREIMS m/z 374.3172 (calcd for C25H42O2, 374.3185).
Exp er im en ta l Section
Gen er a l Exp er im en ta l P r oced u r es. 1H NMR and 13C
NMR spectra were recorded on Hitachi R-90H and Bruker
ARX-400 NMR spectrometers. Chemical shifts are reported
in parts per million (ppm) relative to CHCl3 (δ 7.25), and
coupling constants are given in Hertz. The specific rotations
were measured on a J ASCO DIP-370 instrument. MS were
recorded on J EOL J MS-SX102A and J EOL J MS-AM150 mass
spectrometers. All reagents were commercially available and
used without purification.
An im a l Ma ter ia l. The scale insect C. pseudoceriferus Green
(155.3 g: voucher specimen preserved in this laboratory),
feeding on the host Laurus nobilis, was collected at the campus
of Tokushima University in November 1996.
24-(ω-Hyd r oxy fa tty a cid ) ester (2) of 1: [R]25 +9.5° (c
D
0.07, CHCl3); 1H NMR (CDCl3, 400 MHz) δ 1.13 (3H, s, H-22),
1.20-1.27 (51H, m, CH2), 1.46-1.51 (3H, m, H-14, H-16), 1.54
(3H, s, H-25), 1.53-1.56 (2H, quint, J ) 7.6 Hz, CH2), 1.59-
1.62 (2H, quint, J ) 7.0 Hz, CH2), 1.62 (6H, s, H-21, H-23),
1.68 (3H, s, H-20), 1.68-1.73 (1H, m, H-13a), 1.75-1.83 (1H,
dt, J ) 7.6 Hz, 13.7 Hz, H-1a), 1.99-2.15 (8H, m, H-4a, H-8a,
H-9, H-12, H-17), 2.20-2.23 (1H, m, H-8b), 2.27-2.31 (2H, t,
J ) 7.7 Hz, CH2), 2.31-2.37 (4H, m, H-1b, H-4b, H-5), 3.61-
3.64 (2H, t, J ) 6.6 Hz, CH2OH), 4.58-4.66 (2H, d, J ) 11.9
Hz, H-24), 5.00 (1H, t, J ) 7.0 Hz, H-10), 5.11 (1H, t, J ) 7.0
Hz, H-18), 5.20 (1H, t, J ) 7.4 Hz, H-6), 5.39 (1H, t, J ) 7.6
Hz, H-2); 13C NMR (CDCl3, 100 MHz) δ 15.3 (q, C-25), 17.6
Extr a ction a n d Isola tion . Whole insect bodies were
soaked in CHCl3 (500 mL) overnight with occasional shaking.
The solid residues were filtered off and the filtrate washed
with H2O. The CHCl3 layer was concentrated on a rotary

Terpenoids from Insect Wax
J ournal of Natural Products, 1999, Vol. 62, No. 11 1507
(q, C-21), 22.0 (t, C-17), 22.1 (q, C-23), 24.0 (q, C-22), 24.4 (t,
C-9), 24.8 (t, C-4), 24.9 (t), 25.6 (q, C-20), 25.6 (t), 28.3 (t, C-13),
29.1 (t), 29.2 (t), 29.3 (t), 29.4 (t), 29.5 (t), 29.6 (t), 30.0 (t, C-5),
32.7 (t), 34.3 (t), 35.8 (t, C-8), 39.1 (t, C-12), 39.6 (t, C-16), 47.3
(d, C-14), 61.5 (t, C-24), 63.0 (t), 75.5 (s, C-15), 124.6 (d, C-18),
125.5 (d, C-10), 126.3 (d, C-2), 131.6 (s, C-7, C-19), 132.0 (d,
C-6), 134.0 (s, C-3), 134.5 (s, C-11), 173.9 (s, CO2); FABMS
showed no distinct peaks above m/z 400.
Meth a n olysis of 2 F ollow ed by Acetyla tion . Into a 20-
mL two-necked flask were placed 2 (1.6 mg; 1.3 mmol), sodium
methoxide (1.0 mg; 18.5 mmol), and dry MeOH (5 mL). The
mixture was stirred at room temperature for 2 h under argon.
The reaction mixture was acidified with 12 M HCl, extracted
with EtOAc, and dried over Na2SO4. The hydrolyzed product
was directly treated with acetic anhydride (0.2 mL) and
pyridine (0.2 mL) at room temperature for 2 h, and the mixture
was concentrated to give a mixture of ω-acetoxy fatty acid
methyl esters (0.3 mg): 1H NMR (CDCl3, 90 MHz) δ 1.25 (br
s, CH2), 2.02 (3H, s, CH3CO2), 3.65 (3H, s, OCH3), 4.04 (t, J )
7 Hz, AcOCH2); GC-MS, see text.
(3H, s, H-17), 0.80 (3H, s, H-19), 0.86 (3H, s, H-18), 1.18-1.34
(53H, m, CH2), 1.47-1.49 (1H, m, H-11), 1.57-1.64 (2H, m,
CH2), 1.69 (3H, s, H-20), 1.70 (3H, s, H-16), 1.73-1.77 (1H, br
dd, H-2a), 1.80-1.84 (1H, m, H-2b), 1.88-2.00 (3H, m, H-1a,
H-6a, H-12a), 2.19-2.27 (1H, br td, H-12b), 2.27-2.31 (2H, t,
J ) 7.5 Hz, CH2), 3.54 (3H, s, OCH3), 3.56 (3H, s, OCH3), 4.27-
4.34 (2H, m, CH2), 4.58 (2H, d, J ) 7.0 Hz, H-15), 4.71-4.75
(1H, dd, J ) 4.3 Hz, 11.6 Hz, H-3), 5.31-5.35 (1H, t, J ) 7.0
Hz, H-14), 5.38 (1H, br s, H-7) 7.38-7.40 (6H, m, Ar-H), 7.50-
7.55 (4H, m, Ar-H); 13C NMR (CDCl3, 100 MHz) δ 13.5 (q,
C-17), 15.9 (q, C-18), 16.4 (q, C-16), 21.9 (q, C-20), 23.1 (t),
23.7 (t, C-6), 24.9 (t, C-11), 25.6 (t, C-2), 27.4 (q, C-19), 28.2
(t), 29.0 (t), 29.1 (t), 29.2 (t), 29.3 (t), 29.4 (t), 29.5 (t), 31.8 (s,
C-10), 34.3 (t), 36.3 (s, C-4), 36.7 (t, C-1), 41.7 (t, C-12), 49.6
(d, C-5), 53.9 (d, C-9), 55.3 (q, OCH3), 60.9 (t, C-15), 66.5 (t),
84.2 (d, C-3), 118.8 (d, C-14), 121.8 (d, C-7), 127.2 (d, Ar-C),
128.2 (d, Ar-C), 128.3 (d, Ar-C), 129.4 (d, Ar-C), 129.5 (d,
Ar-C), 132.3 (s, Ar-C), 132.6 (s, Ar-C), 134.9 (s, C-8), 142.1
(s, C-13), 166.0 (s, CO2), 166.5 (s, CO2), 173.8 (s, CO2).
15-Aceta te (4) of la bd a -7,13-d ien e-3,15-d iol: 1H NMR
(CDCl3, 400 MHz) δ 0.75 (3H, s, H-17), 0.84 (3H, s, H-18), 0.87
(3H, s, H-19), 1.12 (1H, td, J ) 4.7 Hz, 13.0 Hz, H-1a), 1.18
(1H, dd, J ) 6.5 Hz, 10.4 Hz, H-5), 1.27-1.32 (1H, m, H-11a),
1.49-1.66 (4H, m, H-2, H-9, H-11b), 1.65 (3H, s, H-20), 1.66
(3H, s, H-16), 1.86 (1H, dt, J ) 3.4 Hz, 13.3 Hz, H-1b), 1.96-
2.00 (3H, m, H-6, H-12a), 2.05 (3H, s, CH3CO2), 2.19-2.26 (1H,
br td, H-12b), 3.21-3.25 (1H, dd, J ) 4.8 Hz, 11.0 Hz, H-3),
4.57 (2H, d, J ) 7.0 Hz, H-15), 5.33 (1H, t, J ) 6.7 Hz, H-14),
5.39 (1H, br s, H-7); 13C NMR (CDCl3, 100 MHz) δ 13.5 (q,
C-17), 14.9 (q, C-18), 16.4 (q, C-16), 20.9 (q, CH3CO2), 21.9 (q,
C-20), 23.4 (t, C-6), 25.3 (t, C-11), 27.3 (t, C-2), 27.8 (q, C-19),
36.5 (s, C-10), 37.1 (t, C-1), 38.6 (s, C-4), 41.8 (t, C-12), 49.5
(d, C-5), 54.1 (d, C-9), 61.3 (t, C-15), 79.0 (d, C-3), 118.4 (d,
C-14), 122.1 (d, C-7), 134.9 (s, C-8), 142.5 (s, C-13), 171.0 (s,
CO2); HREIMS m/z 348.2611 (calcd for C22H36O3, 348.2664).
(+)-La bd a -7,13-d ien e-3,15-d iol (5) fr om 3. A solution of
3 (28.3 mg; 23.3 mmol) in 9:1 MeOH-H2O (20 mL) containing
10% KOH was stirred at room temperature for 1 h. The
reaction mixture was extracted with diethyl ether. The ethe-
real layer was dried over Na2SO4, and the ether was removed
to give 5 (5.7 mg, 76%): [R]25D +5.68° (c 0.15, CHCl3); 1H NMR
(CDCl3, 90 MHz) δ 0.76 (3H, s, H-17), 0.84 (3H, s, H-18), 0.95
(3H, s, H-19), 1.69 (6H, br s, H-16, H-20), 3.14-3.33 (1H, br
dd, H-3), 4.11-4.16 (2H, br d, H-15), 5.28-5.47 (2H, m, H-7,
H-14).
(+)-La bd a -7,13-d ien e-3,15-d iol (5) fr om 4. Into a 30-mL
flask was placed 14.6 mg (11.6 mmol) of 4 in a 10% solution of
KOH in 9:1 MeOH-H2O (10 mL). The mixture was stirred at
room temperature for 1 h. The reaction mixture was extracted
with diethyl ether. After drying the ether layer over Na2SO4
and concentration, 5 (5.4 mg, 49%) was obtained: [R]25D +5.89°
(c 0.14, CHCl3); 1H NMR (CDCl3, 90 MHz) δ 0.74 (3H, s, H-17),
0.83 (3H, s, H-18), 0.95 (3H, s, H-19), 1.67 (6H, br s, H-16,
H-20), 3.14-3.31 (1H, br dd, H-3), 4.09-4.16 (2H, br d, H-15),
5.30-5.45 (2H, m, H-7, H-14).
15-(ω-Hyd r oxy fa tty a cid ) ester (6) of la bd a -7,13-d ien e-
15,20-d iol: [R]25D -12.0° (c 0.78, CHCl3); 1H NMR (CDCl3, 400
MHz) δ 0.74 (3H, s, H-17), 0.85 (3H, s, H-18), 0.87 (3H, s,
H-19), 0.91-0.98 (1H, td, J ) 3.8 Hz, 13.0 Hz, H-1a), 1.12-
1.17 (1H, br td, H-3), 1.18-1.21 (1H, t, J ) 6.1 Hz, H-5), 1.21-
1.36 (53H, m, CH2), 1.39-1.43 (1H, br dt, H-3b), 1.43-1.47
(1H, m, H-2a), 1.50-1.61 (3H, m, H-2b, H-11), 1.70 (3H, s,
H-16), 1.81-2.07 (4H, m, H-1b, H-6, H-9), 2.26-2.30 (2H, t, J
) 7.5 Hz, CH2), 2.31-2.34 (1H, br td, H-12), 3.62 (2H, t, J )
6.6 Hz, CH2OH), 3.97 (1H, d, J ) 12.2 Hz, H-20a), 4.13 (1H,
d, J ) 12.0 Hz, H-20b), 4.57 (2H, d, J ) 7.0 Hz, H-15), 5.35
(1H, br t, J ) 7.0 Hz, H-14), 5.75 (1H, br s, H-7); 13C NMR
(CDCl3, 100 MHz) δ 13.5 (q, C-17), 16.5 (q, C-16), 18.7 (t, C-2),
21.7 (q, C-18), 23.6 (t, C-6), 24.9 (t, C-11), 25.6 (t), 29.1 (t),
29.2 (t), 29.3 (t), 29.4 (t), 29.5 (t), 29.6 (t), 32.7 (t), 32.9 (s, C-4),
33.0 (q, C-19), 34.3 (t), 36.6 (s, C-10), 39.0 (t, C-1), 41.0 (t, C-12),
42.1 (t, C-3), 49.8 (d, C-5), 51.4 (d, C-9), 61.0 (t, C-15), 62.9 (t),
65.8 (t, C-20), 119.0 (d, C-14), 125.5 (d, C-7), 139.2 (s, C-8),
142.5 (s, C-13), 173.8 (s, CO2); FABMS, no peaks above m/z
400.
15-(ω-Hyd r oxy fa tty a cid ) ester (3) of (-)-la bd a -7,13-
d ien e-3,15-d iol: 1H NMR (CDCl3, 400 MHz) δ 0.74 (3H, s,
H-17), 0.84 (3H, s, H-18), 0.95 (3H, s, H-19), 1.06-1.12 (1H,
td, J ) 4.8 Hz, 12.9 Hz, H-1a), 1.15-1.19 (1H, dd, J ) 6.5 Hz,
10.5 Hz, H-5), 1.21-1.32 (52H, m, CH2), 1.48-1.65 (8H, m,
CH2), 1.68 (3H, s, H-20), 1.69 (3H, s, H-16), 1.83-1.88 (1H,
dt, J ) 3.5 Hz, 13.3 Hz, H-1b), 1.91-1.99 (3H, m, H-6, H-12a),
2.18-2.25 (1H, br td, J ) 4.5 Hz, 10.5 Hz, H-12b), 2.27 (2H, t,
J ) 7.5 Hz, CH2), 3.20-3.24 (1H, dd, J ) 4.8 Hz, 10.8 Hz,
H-3), 3.62 (2H, t, J ) 6.6 Hz, CH2OH), 4.57 (2H, d, J ) 7.0
Hz, H-15), 5.32 (1H, t, J ) 7.1 Hz, H-14), 5.38 (1H, br s, H-7);
13C NMR (CDCl3, 100 MHz) δ 13.5 (q, C-17), 14.9 (q, C-18),
16.4 (q, C-16), 21.9 (q, C-20), 23.4 (t, C-6), 24.9 (t), 25.3 (t, C-11),
25.6 (t), 27.3 (t, C-2), 27.8 (q, C-19), 29.0 (t), 29.2 (t), 29.3 (t),
29.4 (t), 29.5 (t), 29.6 (t), 32.7 (t), 34.3 (t), 36.5 (s, C-4), 37.1 (t,
C-1), 38.6 (s, C-10), 41.8 (t, C-12), 49.5 (d, C-5), 54.2 (d, C-9),
61.0 (t, C-15), 62.9 (t), 79.0 (d, C-3), 118.6 (d, C-14), 122.1 (d,
C-7), 134.9 (s, C-8), 142.3 (s, C-13), 173.8 (s, CO2).
(R)-MTP A Ester of 3. Into a 10-mL two-necked flask were
placed 3 (2.3 mg; 2.9 mmol), (R)-MTPA acid (8.4 mg; 15.6
mmol), 2,4,6-trinitrochlorobenzene (4.3 mg; 7.8 mmol), and dry
pyridine (distilled from CaH2) (0.1 mL). The mixture was
stirred at room temperature for 22 h. Aqueous NaHCO3 (5%)
and Et2O were added to the reaction mixture, and it was
stirred for 1 h until the yellow precipitate of pyridine picrate
formed. The ether layer was washed with H2O until the yellow
color of the ethereal solution was no longer detected, and with
saturated aqueous Cu(II) sulfate and H2O. After drying the
organic layer over Na2SO4, concentration of the solution, and
purification of the residue by preparative TLC (20% EtOAc in
hexane), the (R)-MTPA ester (10, 3.4 mg, 91%) was obtained:
1H NMR (CDCl3, 400 MHz) δ 0.76 (3H, s, H-17), 0.87 (3H, s,
H-18), 0.89 (3H, s, H-19), 1.17-1.22 (1H, m, H-1a), 1.22-1.33
(53H, m, CH2), 1.46-1.51 (2H, m, H-11), 1.59-1.66 (2H, m,
H-2a, H-9), 1.69 (3H, s, H-20), 1.70 (3H, s, H-16), 1.74-1.78
(1H, br dq, H-2b), 1.87-1.93 (1H, dt, J ) 3.4 Hz, 13.2 Hz,
H-1b), 1.93-1.98 (3H, m, H-6, H-12a), 2.19-2.24 (1H, br dt,
H-12b), 2.27-2.31 (2H, t, J ) 7.2 Hz, CH2), 3.51 (3H, s, OCH3),
3.55 (3H, s, OCH3), 4.27-4.34 (2H, m, CH2), 4.58 (2H, d, J )
6.8 Hz, H-15), 4.68-4.72 (1H, dd, J ) 4.2 Hz, 11.6 Hz, H-3),
5.33 (1H, br t, J ) 6.4 Hz, H-14), 5.38 (1H, br s, H-7) 7.37-
7.41 (6H, m, Ar-H), 7.50-7.54 (4H, m, Ar-H); 13C NMR
(CDCl3, 100 MHz) δ 13.5 (q, C-17), 16.0 (q, C-18), 16.4 (q, C-16),
21.9 (q, C-20), 23.1 (t, C-6), 23.4 (t, C-2), 24.9 (t), 25.6 (t, C-11),
27.8 (q, C-19), 28.2 (t), 29.0 (t), 29.1 (t), 29.2 (t), 29.3 (t), 29.4
(t), 29.5 (t), 34.3 (t), 36.3 (s, C-10), 36.6 (t, C-1), 37.5 (s, C-4),
41.7 (t, C-12), 49.6 (d, C-5), 53.9 (d, C-9), 55.2 (q, OCH3), 55.3
(q, OCH3), 61.0 (t, C-15), 66.5 (t), 84.4 (d, C-3), 118.7 (d, C-14),
121.8 (d, C-7), 127.2 (d, Ar-C), 127.5 (d, Ar-C), 128.3 (d, Ar-
C), 129.4 (d, Ar-C), 129.5 (d, Ar-C), 132.2 (s, Ar-C), 132.3
(s, Ar-C), 135.0 (s, C-8), 142.1 (s, C-13), 166.3 (s, CO2), 166.5
(s, CO2), 173.8 (s, CO2).
(S)-MTP A Ester of 3. The procedure was the same as
described above. From 1.1 mg of 3, 0.8 mg (62%) of the (S)-
MTPA ester were obtained: 1H NMR (CDCl3, 400 MHz) δ 0.78

1508 J ournal of Natural Products, 1999, Vol. 62, No. 11
Toki et al.
15-Aceta te (7) of la bd a -7,13-d ien e-15,20-d iol: 1H NMR
(CDCl3, 400 MHz) δ 0.74 (3H, s, H-17), 0.86 (3H, s, H-18), 0.88
(3H, s, H-19), 0.90-0.98 (1H, td, J ) 3.5 Hz, 13.0 Hz, H-1a),
1.12 (1H, br t, J ) 11.4 Hz, H-3a), 1.18-1.22 (1H, dd, J ) 4.8
Hz, 12.1 Hz, H-9), 1.31-1.36 (1H, m, H-6a), 1.40-1.51 (3H,
m, H-2, H-3b), 1.54-1.57 (1H, m, H-6b), 1.71 (3H, s, H-16),
1.82-1.85 (2H, m, H-1b, H-5), 1.91-1.94 (1H, br d, H-11a),
2.02-2.08 (2H, m, H-11b, H-12a), 2.04 (3H, s, CH3CO2), 2.28-
2.37 (1H, m, H-12b), 3.96-4.00 (1H, br dd, J ) 3.3 Hz, 12.0
Hz, H-20a), 4.11-4.16 (1H, br dd, J ) 5.9 Hz, 11.8 Hz, H-20),
4.57 (2H, d, J ) 7.1 Hz, H-15), 5.36 (1H, t, J ) 6.0 Hz, H-14),
5.75 (1H, br s, H-7); 13C NMR (CDCl3, 100 MHz) δ 13.5 (q,
C-17), 16.5 (q, C-16), 18.7 (t, C-2), 20.9 (q, CH3CO2), 21.7 (q,
C-19), 23.6 (t, C-6), 24.9 (t, C-11), 32.9 (s, C-4), 33.0 (q, C-18),
36.6 (s, C-10), 38.9 (t, C-1), 40.9 (t, C-12), 42.1 (t, C-3), 49.8 (d,
C-5), 51.4 (d, C-9), 61.3 (t, C-15), 65.9 (t, C-20), 118.3 (d, C-14),
125.6 (d, C-7), 139.2 (s, C-8), 142.6 (s, C-13), 171.0 (s, CO2);
HREIMS m/z 348.2656 (calcd for C22H36O3, 348.2664).
(3H, br s, H-16), 2.03 (6H, br s, CH3CO2), 4.54 (4H, br d, H-15,
H-20), 5.32 (1H, br t, H-14), 5.80 (1H, br s, H-7).
The diacetate (35.5 mg) in dry THF (1.0 mL) was placed in
a two-necked flask equipped with a stirrer and a dropping
funnel. The flask was cooled with a mixture of dry ice and
acetone. Ammonia was introduced from the dropping funnel
into the flask to concentrate it into liquid (ca. 10 mL), then
calcium (98 mg) was added. The mixture was stirred for 30
min. The excess of calcium was destroyed by dropwise addition
of aqueous NH4Cl (0.2 mL), and the ammonia was allowed to
evaporate. After warming to room temperature, the product
was taken up in Et2O and dried over Na2SO4. The organic layer
was concentrated to give an oily residue (42.4 mg). Purification
by preparative TLC (50% EtOAc in hexane) gave 18.2 mg
(73%) of 16: 1H NMR (CDCl3, 90 MHz) δ 0.75 (3H, s, H-17),
0.87 (6H, br s, H-18, H-19), 1.60 (9H, br s, H-15, H-16, H-20),
5.02-5.44 (2H, m, H-7, H-14); HREIMS m/z 274.2670 (calcd
for C20H34, 274.2661).
Ozon olysis of 16. To a solution of 16 (20.4 mg) in MeOH
(1.0 mL) cooled to -78 °C, ozone gas was bubbled in for 5 min.
After addition of H2O2 (1.0 mL), acetic acid (0.5 mL), and 1
drop of 12 M HCl, and after stirring for 20 h, the reaction
mixture was extracted with H2O and Et2O. The ether extract
was washed with 5% NaHCO3. The aqueous layer was acidified
to pH 2 with 12 M HCl, and the acidic material was taken up
in diethyl ether. Drying the ethereal solution over Na2SO4 and
concentration afforded the carboxylic acid (17, 17.1 mg, 74%):
1H NMR (CDCl3, 90 MHz) δ 0.92 (3H, s, H-17), 0.97 (6H, br s,
H-18, H-19), 2.05 (3H, s, H-16), 2.08 (3H, s, H-20).
Meth yl Ester of 17. The â-chiral carboxylic acid (17, 1.6
mg) was methylated with an excess of diazomethane in diethyl
ether at room temperature for 1 h. The excess of diazomethane
was destroyed by dropwise addition of acetic acid. The organic
layer was concentrated on a rotary evaporator to give a crude
methyl ester (2.1 mg). Purification by preparative TLC (20%
EtOAc in hexane) gave 1.0 mg (56%) of the methyl ester 18:
1H NMR (CDCl3, 90 MHz) δ 0.93 (3H, s, H-17), 0.96 (6H, br s,
H-18, H-19), 2.05 (3H, s, H-16), 2.08 (3H, s, H-20), 3.33 (3H,
s, OCH3); GC-MS m/z [M]+ (7), 324 (7), 235 (8), 197 (50), 181
(26), 128 (98), 123 (94), 43 (100); HREIMS m/z 324.2336 (calcd
for C19H32O4, 324.2301).
(-)-La bd a -7,13-d ien e-15,20-d iol (8). Hydrolysis of 6 with
10% KOH in 9:1 MeOH-H2O afforded 91% yield of 8: [R]25
D
1
-9.9° (c 0.07, CHCl3); H NMR (90 MHz, CDCl3) δ 0.72 (3H,
s, H-17), 0.83 (6H, br s, H-18, H-19), 1.64 (3H, br s, H-16),
4.15 (4H, br t, H-15, H-20), 5.38 (1H, br t, H-14), 5.67 (1H, br
s, H-7); GC-MS m/z 306 [M]+ (2), 286 (16), 244 (40), 148 (37),
119 (33), 81 (70), 55 (78), 43 (100); hydrolysis of 7 afforded
the same product with [R]25 -10.9° (c 0.13, CHCl3).
D
(-)-Abietic a cid m eth yl ester (10): [R]25D -56.7° (c 0.41,
CHCl3); 1H NMR (CDCl3, 400 MHz) δ 0.81 (3H, s, H-18), 0.99
(3H, d, J ) 6.9 Hz, H-17), 1.00 (3H, d, J ) 6.8 Hz, H-16), 1.14-
1.22 (2H, m, H-1a, H-11a), 1.24 (3H, s, H-19), 1.53-1.61 (3H,
m, H-2, H-6a), 1.72-1.81 (3H, m, H-3a, H-6b, H-11b), 1.84-
1.87 (1H, br d, H-1b), 1.91-1.95 (1H, br d, H-9), 2.03-2.08
(4H, m, H-3b, H-12, H-5), 2.21 (1H, sept, J ) 6.8 Hz, H-15),
3.61 (3H, s, CO2CH3), 5.35 (1H, br s, H-7), 5.76 (1H, br s, H-14);
13C NMR (CDCl3, 100 MHz) δ 13.9 (q, C-18), 16.9 (q, C-19),
18.0 (t, C-2), 20.7 (q, C-17), 21.3 (q, C-16), 22.4 (t, C-11), 25.6
(t, C-3), 27.4 (t, C-12), 34.5 (s, C-10), 34.8 (d, C-15), 37.1 (t,
C-6), 38.3 (t, C-1), 45.1 (d, C-5), 46.5 (s, C-4), 50.9 (d, C-9),
51.7 (q, CO2CH3), 120.5 (d, C-7), 122.3 (d, C-14), 135.5 (s, C-8),
145.2 (s, C-13), 178.9 (s, C-20).
Neoa bietic a cid m eth yl ester (12): 1H NMR (CDCl3, 400
MHz) δ 0.77 (3H, s, H-18), 1.10-1.15 (2H, m, H-1a, H-6a), 1.19
(3H, s, H-19), 1.33-1.38 (1H, dt, J ) 3.7 Hz, 13.2 Hz, H-11a),
1.44-1.48 (1H, dd, J ) 5.0 Hz, 12.7 Hz, H-6b), 1.50-1.61 (3H,
m, H-2, H-3), 1.69 (3H, s, H-16), 1.73 (3H, s, H-17), 1.70-1.79
(3H, m, H-1b, H-11b, H-12a), 1.82-1.88 (1H, br t, H-12b),
1.91-1.94 (1H, dd, J ) 2.5 Hz, 12.5 Hz, H-5), 1.95-1.97 (1H,
m, H-9a), 2.16-2.24 (1H, br d, H-7a), 2.29-2.33 (1H, br dd,
H-7b), 2.48-2.53 (1H, dt, J ) 4.2 Hz, 14.1 Hz, H-9b), 3.65 (3H,
s, CO2CH3), 6.18 (1H, br s, H-14); 13C NMR (CDCl3, 100 MHz)
δ 15.2 (q, C-18), 16.9 (q, C-19), 18.1 (t, C-2), 19.6 (q, C-17),
20.2 (q, C-16), 22.2 (t, C-11), 24.8 (t, C-6), 25.7 (t, C-12), 35.5
(t, C-7), 36.9 (t, C-3), 37.7 (s, C-10), 38.4 (t, C-1), 47.5 (s, C-4),
48.9 (d, C-5), 51.4 (d, C-9), 51.8 (q, CO2CH3), 122.0 (d, C-14),
123.3 (s, C-15), 128.2 (s, C-13), 138.4 (s, C-8), 179.3 (s, C-20).
15-Hyd r oxya bieteic a cid m eth yl ester (14): 1H NMR
(CDCl3, 400 MHz) δ 0.79 (3H, s, H-20), 1.13-1.21 (4H, m, H-1a,
H-6, H-11a), 1.25 (3H, s, H-19), 1.31 (3H, s, H-17), 1.33 (3H,
s, H-16), 1.55-1.62 (3H, m, H-2, H-3a), 1.73-1.77 (1H, m,
H-3b), 1.81-1.89 (2H, m, H-1b, H-11b), 1.92-1.96 (1H, br d,
H-5), 2.03-2.09 (2H, m, H-9, H-12a), 2.28-2.33 (1H, br dt,
H-12b), 3.62 (3H, s, CO2CH3), 5.46 (1H, br s, H-7), 6.05 (1H,
br s, H-14); 13C NMR (CDCl3, 100 MHz) δ 13.9 (q, C-19), 16.9
(q, C-18), 18.0 (t, C-2), 22.4 (t, C-11), 25.5 (t, C-12), 25.7 (t,
C-6), 28.5 (q, C-16), 28.6 (q, C-17), 34.4 (s, C-10), 37.0 (t, C-3),
38.2 (t, C-1), 44.9 (d, C-9), 46.5 (s, C-4), 50.6 (d, C-5), 51.8 (q,
CO2CH3), 122.3 (d, C-14), 122.9 (d, C-7), 134.9 (s, C-13), 144.5
(s, C-8), 178.9 (s, C-20).
(S)-P GME Am id e (19) of 17. To a stirred solution of
carboxylic acid (17) (9.4 mg, 0.031 mmol) and (S)-PGME (7.6
mg, 0.038 mmol) in dry DMF (0.5 mL), were successively added
1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluo-
rophosphate (19.7 mg, 0.038 mmol), 1-hydroxybenzotriazole
(5.1 mg, 0.038 mmol), and triethylamine (12.8 mL) at 0 °C.
After the mixture was stirred at room temperature for 4 h,
EtOAc was added, and the resulting solution was successively
washed with 5% HCl, saturated NaHCO3 solution, and brine.
The organic layer was dried over anhydrous Na2SO4 and
concentrated to give a residue (15.1 mg), which was purified
by preparative TLC (20% EtOAc in hexane) to afford the (S)-
PGME amide (19) (0.6 mg, 3.8%): 1H NMR (CDCl3, 400 MHz)
δ 0.79 (3H, s, H-19), 0.89 (3H, s, H-18), 0.91 (3H, s, H-17),
1.09-1.19 (1H, m, H-3a), 1.30-1.36 (1H, m, H-3b), 1.38-1.50
(4H, m, H-1, H-2), 1.82-1.90 (4H, m, H-11, H-12), 2.00-2.02
(1H, t, J ) 4.8 Hz, H-5), 2.08 (3H, s, H-16), 2.17 (3H, s, H-20),
2.23-2.27 (2H, dd, J ) 4.8 Hz, 12.0 Hz, H-6), 2.54-2.57 (1H,
dd, J ) 2.8 Hz, 11.6 Hz, H-9), 3.72 (3H, s, CO2CH3), 5.54-
5.56 (1H, d, J ) 7.2 Hz, Ca-H), 6.52-6.54 (1H, d, J ) 7.2 Hz,
NH), 7.31-7.38 (5H, m, Ar-H).
(R)-P GME Am id e (19) of 17. Condensation of (R)-PGME
(5.4 mg, 0.027 mmol) with 17 (7.0 mg, 0.021 mmol) in a similar
way as described above gave a residue (11.3 mg), which was
purified by preparative TLC (20% EtOAc in hexane) to afford
the (R)-PGME amide (19) (2.3 mg, 21%): 1H NMR (CDCl3, 400
MHz) δ 0.89 (9H, s, H-17, H-18, H-19), 1.18-1.23 (1H, m,
H-3a), 1.38-1.51 (5H, m, H-1, H-2, H-3b), 1.65-1.79 (4H, m,
H-8, H-9), 1.92 (3H, s, H-16), 2.01-2.03 (1H, t, J ) 4.4 Hz,
H-5), 2.05 (3H, s, H-20), 2.20-2.24 (1H, br dd, H-7), 2.24-
2.27 (2H, dd, J ) 4.0 Hz, 8.8 Hz, H-6), 3.71 (3H, s, CO2CH3),
5.51-5.53 (1H, d, J ) 6.8 Hz, Ca-H), 6.71-6.73 (1H, d, J )
6.8 Hz, NH), 7.29-7.40 (5H, m, Ar-H); 13C NMR (CDCl3, 100
MHz) δ 17.9 (t, C-2), 20.5 (q, C-17), 21.7 (t, C-11), 22.7 (q, C-18),
La bd a -7,15-d ien e. Acetic anhydride (0.5 mL) was added
to a solution of 8 (32.5 mg) in pyridine (0.5 mL), and the
reaction mixture was allowed to stand at room temperature
for 4 h. The excess reagent and pyridine were removed in vacuo
to yield 35.5 mg (86%) of the diacetate: 1H NMR (CDCl3, 90
MHz) δ 0.76 (3H, s, H-17), 0.86 (6H, br s, H-18, H-19), 1.69

Terpenoids from Insect Wax
J ournal of Natural Products, 1999, Vol. 62, No. 11 1509
(3) (a) Dale, J . A.; Mosher, H. S. J . Am. Chem. Soc. 1973, 95, 512-519.
(b) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J . Am. Chem.
Soc. 1991, 113, 4092-4096.
29.5 (q, C-16), 32.6 (t, C-1), 33.7 (q, C-19), 33.8 (t, C-6), 34.1
(q, C-20), 34.8 (s, C-10), 40.2 (s, C-4), 41.4 (t, C-3), 41.8 (t, C-12),
44.5 (d, C-5), 52.8 (q, OCH3), 56.5 (d), 59.5 (d, C-9), 127.3 (d,
Ar-C), 128.4 (d, Ar-C), 128.9 (d, Ar-C), 137.1 (s, Ar-C), 171.4
(s, CO2), 172.4 (s, CONH), 208.4 (s, C-13), 213.1 (s, C-8).
(4) (a) Nagai, Y.; Kusumi, T. Tetrahedron Lett. 1995, 36, 1853-1856.
(b) Yabuuchi, Y.; Ooi, T.; Kusumi, T.; Chirality 1997, 9, 550-555. (c)
Yabuuchi, T.; Kusumi, T.; J . Org. Chem., submitted. As a preliminary
report, see Yabuuchi, T.; Ooi, T.; Kusumi, T. 41st Symposium on the
Chemistry of Terpenes, Essential Oils and Aromatics (Iwate, J apan,
10-12 October 1997), Summary Paper 2I08 (p 251).
Refer en ces a n d Notes
(5) Tabacik, C.; Poisson, C. Phytochemistry 1971, 10, 1639-1645.
(6) Schuller, W. H.; Lawrence, R. V. J . Am. Chem. Soc. 1961, 83, 2563-
2570.
(1) (a) Miyamoto, F.; Naoki, H.; Takemoto, T.; Naya, Y. Tetrahedron 1979,
35, 1913-1917. (b) Kusumi, T.; Kinoshita, T.; Fujita, K.; Kakisawa,
H. Phyto 1979, 1129-1132.
(2) Miyamoto, F.; Naoki, H.; Naya, Y.; Nakanishi, K. Tetrahedron 1980,
36, 3481-3487.
(7) Carman, R. M.; Marty, R. A. Aust. J . Chem. 1970, 23, 1457-1464.
NP990170T