Stereoselective synthesis of optically active 3-hydroxy-7,8-dihydro-β- ionol-glucosides

Article abstract of DOI:10.1248/cpb.51.878

A stereocontrolled synthesis of optically active β-D-glucopyronosides 6a, b and 11a, b was accomplished via the 7,8-saturated alcohols 4a, b, efficiently prepared by an asymmetric transfer hydrogenation of the α,β-acetylenic ketone 1 and subsequent cataly

Full text of DOI:10.1248/cpb.51.878

878
Notes
Chem. Pharm. Bull. 51(7) 878—882 (2003)
Vol. 51, No. 7
Stereoselective Synthesis of Optically Active 3-Hydroxy-7,8-dihydro-
b
-ionol-glucosides
Yumiko YAMANO, Yuka SHIMIZU, and Masayoshi ITO*
Kobe Pharmaceutical University; Motoyamakita-machi, Higashinada-ku, Kobe 658–8558, Japan.
Received February 24, 2003; accepted April 16, 2003
A stereocontrolled synthesis of optically active b-D-glucopyronosides 6a, b and 11a, b was accomplished via
the 7,8-saturated alcohols 4a, b, efficiently prepared by an asymmetric transfer hydrogenation of the a,b-
acetylenic ketone 1 and subsequent catalytic hydrogenation. Simultaneous separation of these four glucosides by
HPLC was also performed. This work is useful not only in order to confirm the stereochemistries of the trace
amount of glucosides in plants but also to clarify their biosynthesis.
Key words 3-hydroxy-7,8-dihydro-b-ionol; b-D-glucopyronoside; stereocontrolled synthesis; HPLC separation
C13-Norisoprenoid-glucosides 3, 6, 11 (Chart 1) have been
isolated from rose petals1) and have been suggested2) to be
produced through biodegradation of carotenoids in plants. In
these glucosides, the acetylenic diol-glucoside 3 was consid-
ered2) to be an important progenitor of damascenone, the key
flavor compound in an essential oil of rose flowers. Their C-3
hydroxy groups are considered to be of b-configuration, be-
cause most natural xantophylls have b-configuration for C-3
hydroxy groups. However, their stereochemistries at C-9
were not confirmed.
the stereoselective synthesis of (3R,9S)- and (3R,9R)-9-O-b-
D-glucopyranosides 6a, b and (3R,9S)- and (3R,9R)-3-O-b-D-
glucopyranosides 11a, b via hydrogenation of the chiral in-
termediates 2a, b, in order to clarify the stereochemistries of
the trace amount of glucosides in plants.
Results and Discussion
A catalytic hydrogenation of a-acetylenic alcohols 2a and
2b over palladium carbon in ethanol under a hydrogen at-
mosphere at room temperature (rt) provided the 7,8-saturated
alcohols 4a (78%) and 4b (58%), respectively. b-Glucosida-
tion3,4) of 4a, b was achieved (5a: 66%, 5b: 87%) by use of
tetra-O-pivaloyl (Piv)-a-D-glucopyranosyl bromide6) possess-
ing a sterically bulky acyloxy group at C-2 position as a glu-
cosyl donor and silver triflate as an activator in the presence
of N,N-tetramethylurea. The acyl groups of 5a, b were re-
Recently, we reported3,4) stereocontrolled synthesis of
(3R,9S)- and (3R,9R)-9-O-b-D-glucopyranosides 3a and 3b
utilizing an asymmetric transfer hydrogenation5) of the a,b-
acetylenic ketone 1 catalyzed by chiral ruthenium complexes
as the key step, leading to the confirmation of the stereo-
chemistries of natural glucosides. We now wish to describe
Chart 1
To whom correspondence should be addressed. e-mail: m-ito@kobepharma-u.ac.jp
© 2003 Pharmaceutical Society of Japan

July 2003
879
Table 1. Characteristic 1H- and 13C-NMR Spectral Data (d: ppm, in CDCl3) for Pentaacetates 7a, b and 12a, b
9-O-Glucosides
3-O-Glucosides
12b (3R,9R)
Glucocside from
Glucocside from
7a (3R,9S)
7b (3R,9R)
12a (3R,9S)
rose petals1)
rose petals1)
9-CH3
9-H
8-H2
1.26
3.68
1.43
1.59
1.92
2.06
4.57
1.13
3.75
1.54
1.14
3.75
1.52
1.23
4.88
1.54
1.64
1.98
1.23
4.88
1.56
1.23
4.87
1.54
7-H2
1.88
2.19
4.55
1.93
2.07
4.55
1.89
2.06
4.63
1.95
2.05
4.63
1Ј-H
4.63
9-CH3
C7
C8
C9
C1Ј
21.60
24.11
37.26
79.21
101.24
19.53 or 19.54
23.73
19.6
23.7
37.2
76.4
99.2
19.69 or 19.76
23.91
19.79
23.96
36.34
71.32
99.43
19.8
23.9
36.2
71.3
99.6
37.36
76.20
99.17
36.28
71.34
99.43
Table 2. Characteristic 1H- and 13C-NMR Spectral Data (d: ppm, in CD3OD) for Pentaols 6a, b and 11a, b
9-O-Glucosides
3-O-Glucosides
11b (3R,9R)
Glucocside from
Glucocside from
Linaria
6a (3R,9S)
6b (3R,9R)
Linaria
11a (3R,9S)
japonica7)
japonica7)
9-CH3
9-H
8-H2
1.26
3.83
1.52
1.20
3.88
1.54
1.19
ca. 3.85
1.54
ca. 1.67
1.95
1.17
3.70
1.45
1.53
2.02
2.12
4.42
1.16
3.70
1.49
1.16
3.69
ca. 1.48
ca. 1.66
2.06
ca. 1.64
1.95
7-H2
1.92
2.21
4.42
1.93
2.20
4.42
2.15
4.34
2.24
4.34
2.24
4.34
1Ј-H
9-CH3
C7
C8
C9
C1Ј
21.77
25.02
38.81
19.75
25.34
38.99
76.12
102.24
19.8
25.3
39.0
76.2
102.2
23.24
25.54
40.67
69.17
102.33
23.28
25.56
40.74
69.20
102.35
23.3
25.6
40.8
69.2
102.4
77.87 or 77.88
103.88
moved under basic conditions to give the free alcohols 6a thetic (3R,9R)-glucosides 7b and 12b. The stereochemistry at
(70%) and 6b (98%). Since natural glucosides in rose petals C-9 of acetylenic diol-glucoside isolated from rose petals
were isolated1) as pentaacetates, pentaols 6a, b were then was already confirmed3,4) to be R. Therefore, it is presumed
acetylated to provide pentaacetates 7a (97%) and 7b (92%), that there are some enzymes catalyzing stereoselective reduc-
respectively.
tion of ketones to (R)-alcohols in rose flowers.
3-O-b-D-Glucopyranosides 10a (48%) and 10b (96%)
On the other hand, these glucosides were previously iso-
were also prepared by the similar glucosidation of alcohols lated7) from Linaria japonica as free alcohols. Their absolute
9a, b, which were derived (9a: 84%, 9b: 99%) by pivaloyla- configurations were proposed to be R at both C-3 and C-9 by
tion of 4a, b and subsequent deacetylation. Treatment of the the application of an empirical rule8,9) of b-D-glucosylation-
pentapivaloate 10a under the basic conditions used to cleave induced shift trends. By comparison with 13C-NMR data be-
acyl groups of 5a, b provided only the tetraol (95%), because tween glucosides and their aglycone alcohols, the absolute
of stability of C-9-pivaloate. This mono C-9-pivaloate was stereochemistries at the carbon possessing the glycosylated
treated with lithium hydroxide in refluxing methanol to give hydroxy group can be confirmed. However, determination of
the pentaol 11a in 74% (70% from 10a). Thus, the pentapi- the absolute configuration at the carbon having the free hy-
valoate 10b was treated with lithium hydroxide in refluxing droxy group (C-9 configuration of 3-O-glucoside as well as
methanol to yield directly the pentaol 11b in 70%. Finally, C-3 configuration of 9-O-glucoside) is difficult by the appli-
pentaols 11a, b were acetylated to afford pentaacetates 12a cation of this empirical rule. In this time, stereochemistries
(93%) and 12b (93%).
of both the 3-O-glucoside and the 9-O-glucoside isolated
1H- and 13C-NMR spectra of 9-O-glucosides 7a, b indi- from Linaria japonica could be confirmed to be of (3R,9R)-
cated characteristic differences around C-9 as shown in Table configuration by comparison of spectral data for our syn-
1, while those of 3-O-glucosides 12a, b were similar to each thetic glucosides 6a, b and 11a, b as shown in Table 2.
other but showed slight differences in protons at C-7 and C-
In order to facilitate the confirmation of stereochemistries
8. Spectral data of pentaacetylated 9-O- and 3-O-glucosides of natural glucosides, separation of synthetic four isomers
isolated1) from rose petals were identical with those of syn- 6a, b and 11a, b by HPLC was investigated. Since these glu-

880
Vol. 51, No. 7
was filtered off, the filtrate was evaporated to give a residue, which was puri-
fied by short-CC (acetone–hexane, 15 : 85) to give the 3-hydroxy compound
9a (727 mg, 84% from 4a). The compound 9b was prepared (99%) in the
same manner as described above.
1
9a: Colorless oil; H-NMR (300 MHz, CDCl3) d: 1.01, 1.06 (each 3H, s,
gem-Me), 1.21 (3H, d, Jϭ6.5 Hz, 9-Me), 1.21 (9H, s, tert-Bu), 1.42 (1H, t,
Jϭ12 Hz, 2ax-H), 1.53—1.68 (2H, m, 8-H2), 1.62 (3H, s, 5-Me), 1.71 (1H,
ddd, Jϭ12, 3.5, 2 Hz, 2eq-H), 1.96 (1H, br dd, Jϭ16, 10 Hz, 4ax-H), 2.00
(2H, t, Jϭ8.5 Hz, 7-H2), 2.23 (1H, ddd, Jϭ16, 5, 2 Hz, 4eq-H), 3.92 (1H, m,
3-H), 4.87 (1H, sext-like, Jϭ6 Hz, 9-H). IR (CHCl3) cmϪ1: 3606, 3480
(OH), 1715 (OCO). EI-MS m/z: 296.2359 [Calcd for C18H32O3 (Mϩ)
296.2350]. [a]D25 Ϫ60.0° (cϭ0.95, MeOH).
1
9b: Colorless oil; H-NMR (300 MHz, CDCl3) d: 1.02, 1.04 (each 3H, s,
gem-Me), 1.21 (3H, d, Jϭ6.5 Hz, 9-Me), 1.21 (9H, s, tert-Bu), 1.42 (1H, t,
Jϭ12 Hz, 2ax-H), 1.55—1.62 (2H, m, 8-H2), 1.62 (3H, s, 5-Me), 1.71 (1H,
ddd, Jϭ12, 3.5, 2 Hz, 2eq-H), 1.89 (1H, m, 7-H), 1.97 (1H, br dd, Jϭ16,
10 Hz, 4ax-H), 2.11 (1H, m, 7-H), 2.23 (1H, ddd, Jϭ16, 5.5, 2 Hz, 4eq-H),
Fig. 1. HPLC Elution Profile of a Mixture of Glucosides 8a, 8b, 13a and
13b
3.93 (1H, m, 3-H), 4.86 (1H, sext-like, Jϭ6 Hz, 9-H). IR (CHCl3) cmϪ1
:
Column: CHIRALPAK AD-H 0.46ϫ25 cm; eluent: ethanol–hexane (15 : 85); flow
rate: 0.7 ml/min; UV detection: 230 nm.
3606, 3467 (OH), 1715 (OCO). EI-MS m/z: 296.2350 [Calcd for C18H32O3
(Mϩ) 296.2350]. [a]D29 Ϫ32.8° (cϭ0.98, MeOH).
b-Glucosidation of Alcohols 4a, b and 9a, b Under a nitrogen stream,
AgOTf (2.41 g, 9.37 mmol) was added to a stirred suspension of tetra-O-pi-
cosides did not show a remarkable UV absorption, they were
detected as pentabenzoates 8a, b and 13a, b (Chart 1), re- valoyl-a-D-glucosyl bromide6) (4.21 g, 7.52 mmol), (3R,9S)-9-hydroxy com-
pound 4a (955 mg, 3.76 mmol), N,N-tetramethylurea (1.8 ml, 15 mmol) and
spectively. Simultaneous separation using a chiral column
(CHIRALPAK AD-H; DAICEL) was performed as shown in
Fig. 1. Works to determine streochemistries of trace amount
of glucosides in plants are now in progress.
powdered molecular sieves 4A (10 g) in dry CH2Cl2 (40 ml) at 0 °C. After
being stirred at 0 °C for 30 min and rt for 2 h, the reaction was quenched
with saturated aq. NaHCO3. The reaction mixture was diluted with AcOEt
and filtered through Celite. The organic layer of the filtrate was washed with
brine, dried and evaporated to give a residue, which was purified by CC
(CH2Cl2–hexane–ether, 5 : 4 : 0.7) to afford the b-glucoside 5a (1.87 g, 66%).
The glucosides 5b (87%), 10a (48%) and 10b (96%) were prepared in the
same manner as described above.
Experimental
General 1H- and 13C-NMR spectra were obtained with a Varian Gem-
ini-300 or a Varian VXR-500 superconducting FT-NMR spectrometer and
the chemical shifts were referenced to tetramethylsilane. IR spectra were
measured on a Perkin Elmer FT-IR spectrometer, model Paragon 1000. Mass
spectra were taken on a Hitachi M-4100 spectrometer. Optical rotations were
determined on a JASCO DIP-181 polarimeter. Column chromatography
(CC) was performed on silica gel (Merck Art. 7734). Short-CC was con-
ducted on silica gel (Merck Art. 7739) under reduced pressure. Evaporation
of the extract or the filtrate was carried out under reduced pressure. Ether
refers to diethyl ether, and hexane to n-hexane. NMR assignments are given
using the retinoid numbering system.
5a: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 1.03, 1.04 (each 3H,
s, gem-Me), 1.11, 1.14, 1.16, 1.22 (each 9H, s, tert-Buϫ4), 1.26 (3H, d,
Jϭ6 Hz, 9-Me), 1.42 (1H, m, 8-H), 1.51 (1H, t, Jϭ12 Hz, 2ax-H), 1.57 (3H,
s, 5-Me), 1.61 (1H, m, 8-H), 1.71 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-H), 1.96—
2.06 (3H, m, 4ax-H, 7-H2), 2.04 (3H, s, OAc), 2.29 (1H, br dd, Jϭ16, 6 Hz,
4eq-H), 3.67 (1H, sext, Jϭ6 Hz, 9-H), 3.73 (1H, ddd, Jϭ9.5, 6.5, 2 Hz, 5Ј-
H), 4.00 (1H, dd, Jϭ12, 6.5 Hz, 6Ј-H), 4.23 (1H, dd, Jϭ12, 2 Hz, 6Ј-H), 4.59
(1H, d, Jϭ8 Hz, 1Ј-H), 4.98 (1H, m, 3-H), 5.03 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H),
5.05 (1H, t, Jϭ9.5 Hz, 4Ј-H), 5.33 (1H, t, Jϭ9.5 Hz, 3Ј-H). IR (CHCl3)
cmϪ1: 1739 (OCO). SIMS m/z: 775.4603 [Calcd for C41H68O12Na (MϩϩNa)
775.4604]. [a]D26 Ϫ32.0° (cϭ1.00, CHCl3).
(1R)-4-[(3S/R)-3-Hydroxybutyl]-3,5,5-trimethylcyclohex-3-enyl
Ac-
etate (4a/b) Catalytic hydrogenation of the (9S)-a-acetylenic alcohol 2a3,4)
(1.23 g, 4.92 mmol) over 10% palladium carbon (250 mg) in EtOH (25 ml)
under a hydrogen atmosphere at rt for 3 h and purification of the crude prod-
uct by short-CC (ether–hexane, 1 : 2) gave the (9S)-7,8-saturated alcohol 4a
(970 mg, 78%). The compound 4b was prepared (58%) in the same manner
as described above.
5b: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 1.04 (6H, s, gem-
Me), 1.11 (3H, d, Jϭ6 Hz, 9-Me), 1.11 (9H), 1.15 (18H), 1.21 (9H) (each s,
tert-Buϫ4), 1.50 (1H, t, Jϭ12 Hz, 2ax-H), ca. 1.52 (2H, m, 8-H2), 1.58 (3H,
s, 5-Me), 1.70 (1H, ddd, Jϭ12, 3.5, 1.5 Hz, 2eq-H), 1.87 (1H, br td, Jϭ12,
5.5 Hz, 7-H), 2.03 (3H, s, OAc), 2.00 (1H, br dd, Jϭ16.5, 9.5 Hz, 4ax-H),
2.22 (1H, br td, Jϭ12, 6.5 Hz, 7-H), 2.28 (1H, br dd, Jϭ16.5, 5.5 Hz, 4eq-H),
3.70 (1H, ddd, Jϭ9.5, 5.5, 2 Hz, 5Ј-H), 3.78 (1H, sext, Jϭ6 Hz, 9-H), 4.01
(1H, dd, Jϭ12.5, 5.5 Hz, 6Ј-H), 4.24 (1H, dd, Jϭ12.5, 2 Hz, 6Ј-H), 4.59 (1H,
d, Jϭ8 Hz, 1Ј-H), 4.99 (1H, m, 3-H), 5.01 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.12
1
4a: Colorless oil; H-NMR (300 MHz, CDCl3) d: 1.07 (6H, s, gem-Me),
1.22 (3H, d, Jϭ6.5 Hz, 9-Me), 1.41—1.59 (2H, m, 8-H2), 1.53 (1H, t,
Jϭ12 Hz, 2ax-H), 1.62 (3H, s, 5-Me), 1.71 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-
H), 1.96—2.17 (3H, m, 4ax-H, 7-H2), 2.04 (3H, s, OAc), 2.30 (1H, br dd,
Jϭ16.5, 5 Hz, 4eq-H), 3.80 (1H, sext-like, Jϭ6 Hz, 9-H), 5.00 (1H, m, 3-H).
IR (CHCl3) cmϪ1: 3610, 3459 (OH), 1724 (OCO). EI-MS m/z: 254.1885
[Calcd for C15H26O3 (Mϩ) 254.1881]. [a]D26 Ϫ44.6° (cϭ0.96, MeOH).
(1H, t, Jϭ9.5 Hz, 4Ј-H), 5.32 (1H, t, Jϭ9.5 Hz, 3Ј-H). IR (CHCl3) cmϪ1
:
1739 (OCO). SIMS m/z: 775.4603 [Calcd for C41H68O12Na (MϩϩNa)
775.4604]. [a]D27 Ϫ41.8° (cϭ1.00, MeOH).
1
10a: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 0.99, 1.03 (each
3H, s, gem-Me), 1.11 (9H), 1.16 (18H), 1.20 (9H), 1.21 (9H) (each s, tert-
Buϫ5), 1.20 (3H, d, Jϭ6.5 Hz, 9-Me), 1.46 (1H, t, Jϭ12 Hz, 2ax-H), 1.50—
1.68 (2H, m, 8-H2), 1.59 (3H, s, 5-Me), 1.78 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-
H), 1.94 (1H, br dd, Jϭ16, 5 Hz, 4eq-H), 1.98 (2H, br t, Jϭ8.5 Hz, 7-H2),
2.17 (1H, br dd, Jϭ16, 5 Hz, 4eq-H), 3.74 (1H, ddd, Jϭ9.5, 6.5, 2 Hz, 5Ј-H),
3.93 (1H, m, 3-H), 4.00 (1H, dd, Jϭ12.5, 6.5 Hz, 6Ј-H), 4.25 (1H, dd,
Jϭ12.5, 2 Hz, 6Ј-H), 4.67 (1H, d, Jϭ8 Hz, 1Ј-H), 4.86 (1H, sext-like,
Jϭ6.5 Hz, 9-H), 5.00 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.07 (1H, t, Jϭ9.5 Hz, 4Ј-
H), 5.33 (1H, t, Jϭ9.5 Hz, 3Ј-H). IR (CHCl3) cmϪ1: 1739 (OCO). SIMS m/z:
817.5051 [Calcd for C44H74O12Na (MϩϩNa) 817.5074]. [a]D25 Ϫ45.5°
(cϭ1.05, CHCl3).
4b: Colorless oil; H-NMR (300 MHz, CDCl3) d: 1.06, 1.07 (each 3H, s,
gem-Me), 1.22 (3H, d, Jϭ6.5 Hz, 9-Me), 1.47—1.55 (2H, m, 8-H2), 1.53
(1H, t, Jϭ12 Hz, 2ax-H), 1.62 (3H, s, 5-Me), 1.72 (1H, ddd, Jϭ12, 3.5,
2 Hz, 2eq-H), ca. 1.92 (1H, m, 7-H), 2.03 (1H, br dd, Jϭ16, 10 Hz, 4ax-H),
2.04 (3H, s, OAc), ca. 2.19 (1H, m, 7-H), 2.30 (1H, br dd, Jϭ16, 6 Hz, 4eq-
H), 3.80 (1H, m, 9-H), 5.00 (1H, m, 3-H). IR (CHCl3) cmϪ1: 3611, 3468
(OH), 1724 (OCO). EI-MS m/z: 254.1895 [Calcd for C15H26O3 (Mϩ)
254.1881]. [a]D25 Ϫ53.0° (cϭ0.98, MeOH).
(1R)-4-[(3S/R)-3-(2,2-Dimethyl-1-oxopropyloxy)]-3,5,5-trimethylcyclo-
hex-3-enol (9a/b) The (9S)-alcohol 4a (740 mg, 2.9 mmol) was dissolved
in pyridine (1 ml), then pivaloyl chloride (0.72 ml, 6.1 mmol) was added to
it. After being stirred under an argon atmosphere at rt for 15 h, the reaction
mixture was poured into ice-water and extracted with ether. The extracts
were washed successively with aq. 5% HCl, saturated aq. NaHCO3, and
brine. Evaporation of the dried extracts gave the pivaloate, which without
purification was dissolved in MeOH (35 ml) and NaOMe (1 M in MeOH;
3.5 ml, 3.5 mmol) was added to it. The reaction mixture was stirred under an
argon atmosphere at rt for 2 h. To this mixture was added Dowex 50W-X8
(Hϩ) (3.5 g) and stirring continued at rt for a further 10 min. After Dowex
10b: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 0.99, 1.02 (each
3H, s, gem-Me), 1.111, 1.157, 1.160, 1.202, 1.213 (each 9H, s, tert-Buϫ5),
1.20 (3H, d, Jϭ6.5 Hz, 9-Me), 1.46 (1H, t, Jϭ12 Hz, 2ax-H), 1.51—1.63
(2H, m, 8-H2), 1.59 (3H, s, 5-Me), 1.78 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-H),
1.88 (1H, br dt, Jϭ13, 8 Hz, 7-H), 1.94 (1H, br dd, Jϭ16.5, 10 Hz, 4ax-H),
2.07 (1H, m, 7-H), 2.17 (1H, br dd, Jϭ16.5, 5 Hz, 4eq-H), 3.74 (1H, ddd,
Jϭ9.5, 6.5, 2 Hz, 5Ј-H), 3.92 (1H, m, 3-H), 4.00 (1H, dd, Jϭ12.5, 6.5 Hz,

July 2003
881
(C6). SIMS m/z: 373.2244 [Calcd for C19H33O7 (MϪϪH) 373.2223]. [a]D25
Ϫ53.2° (cϭ1.00, MeOH).
6Ј-H), 4.25 (1H, dd, Jϭ12.5, 2 Hz, 6Ј-H), 4.67 (1H, d, Jϭ8 Hz, 1Ј-H), 4.85
(1H, sext, Jϭ6.5 Hz, 9-H), 5.00 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.07 (1H, t,
Jϭ9.5 Hz, 4Ј-H), 5.33 (1H, t, Jϭ9.5 Hz, 3Ј-H). IR (CHCl3) cmϪ1: 1740
(OCO). SIMS m/z: 817.5087 [Calcd for C44H74O12Na (MϩϩNa) 817.5073].
[a]D25 Ϫ11.8° (cϭ1.01, CHCl3).
(1R)-4-[(3R)-3-Hydroxybutyl]-3,5,5-trimethylcyclohex-3-enyl-b-D-glu-
copyranoside (11b)
A solution of the pentapivaloate 10b (1.17 g,
1.47 mmol) in MeOH (25 ml) containing LiOH·H2O (450 mg, 10.7 mmol)
was refluxed under an argon atmosphere for 20 h. To this mixture was added
Dowex 50W-X8 (Hϩ) (6.5 g) and stirring continued at rt for a further 10 min.
After Dowex was filtered off, the filtrate was evaporated to give a residue,
which was purified by short-CC (MeOH–CH2Cl2, 15 : 85) to afford the pen-
(1S/R)-3-[(4R)-4-Hydroxy-2,6,6-trimethylcyclohex-1-enyl]-1-methyl-
propyl-b-D-glucopyranoside (6a/b) To a solution of the tetrapivaloate 5a
(2.36 g, 3.14 mmol) in MeOH (50 ml) was added LiOH·H2O (300 mg,
7.14 mmol) and the mixture was stirred under an argon atmosphere at rt for
20 h. To this mixture was added Dowex 50W-X8 (Hϩ) (8 g) and stirring con-
tinued at rt for a further 10 min. After Dowex was filtered off, the filtrate was
evaporated to give a residue, which was purified by short-CC (MeOH–
CH2Cl2, 15 : 85) to afford the pentaol 6a (820 mg, 70%). The compound 6b
1
taol 11b (403 mg, 73%). H- and 13C-NMR data of the synthetic (3R,9R)-3-
O-glucoside 11b were in agreement with those of the 3-O-glucoside
isolated7) from Linaria japonica.
1
11b: Colorless foams; H-NMR (300 MHz, CD3OD) d: 1.05, 1.06 (each
1
was prepared (98%) in the same manner as described above. H- and 13C-
3H, s, gem-Me), 1.16 (3H, d, Jϭ6 Hz, 9-Me), 1.49 (2H, m, 8-H2), 1.49 (1H,
t, Jϭ12 Hz, 2ax-H), 1.65 (3H, s, 5-Me), 1.83 (1H, ddd, Jϭ12, 3.5, 2 Hz,
2eq-H), 1.92 (1H, m, 7-H), 2.01 (1H, br dd, Jϭ16, 9.5 Hz, 4ax-H), 2.21 (1H,
m, 7-H), 2.34 (1H, br dd, Jϭ16, 5 Hz, 4eq-H), 3.15 (1H, dd, Jϭ9, 8 Hz, 2Ј-
H), 3.29 (2H, m, 4Ј-H, 5Ј-H), 3.36 (1H, t, Jϭ9 Hz, 3Ј-H), 3.67 (1H, dd,
Jϭ12, 5 Hz, 6Ј-H), 3.70 (1H, sext, Jϭ6 Hz, 9-H), 3.86 (1H, dd, Jϭ12, 2 Hz,
6Ј-H), 4.06 (1H, m, 3-H), 4.42 (1H, d, Jϭ8 Hz, 1Ј-H). 13C-NMR (75 MHz,
CD3OD) d: 20.05 (5-CH3), 23.28 (9-CH3), 25.56 (C7), 28.84, 30.31 (gem-
CH3), 38.80 (C1), 39.80 (C4), 40.74 (C8), 47.51 (C2), 62.76 (C6Ј), 69.20
(C9), 71.69 (C4Ј), 73.28 (C3), 75.21 (C2Ј), 77.90 (C5Ј), 78.16 (C3Ј), 102.35
(C1Ј), 125.12 (C5), 138.54 (C6). SIMS m/z: 373.2236 [Calcd for C19H33O7
(MϪϪH) 373.2223]. [a]D25 Ϫ67.7° (cϭ0.96, MeOH).
NMR data of the synthetic (3R,9R)-9-O-glucoside 6b were in agreement
with those of the 9-O-glucoside isolated7) from Linaria japonica.
6a: Colorless foams; 1H-NMR (500 MHz, CD3OD) d: 1.04, 1.07 (each
3H, s, gem-Me), 1.26 (3H, d, Jϭ6 Hz, 9-Me), 1.38 (1H, t, Jϭ12 Hz, 2ax-H),
1.52 (1H, m, 8-H), 1.64 (3H, s, 5-Me), ca. 1.66 (1H, m, 8-H), 1.67 (1H, ddd,
Jϭ12, 3.5, 2 Hz, 2eq-H), 1.92 (1H, br dd, Jϭ16, 10 Hz, 4ax-H), 2.06, 2.15
(each 1H, br td, Jϭ13, 5 Hz, 7-H2), 2.18 (1H, br dd, Jϭ16, 5.5 Hz, 4eq-H),
3.16 (1H, dd, Jϭ9, 8 Hz, 2Ј-H), 3.24 (1H, ddd, Jϭ9, 5.5, 2 Hz, 5Ј-H), 3.28
(1H, t, Jϭ9 Hz, 4Ј-H), 3.34 (1H, t, Jϭ9 Hz, 3Ј-H), 3.66 (1H, dd, Jϭ12,
5.5 Hz, 6Ј-H), 3.83 (1H, sext, Jϭ6 Hz, 9-H), ca. 3.84 (1H, m, 3-H), 3.85
(1H, dd, Jϭ12, 2 Hz, 6Ј-H), 4.34 (1H, d, Jϭ8 Hz, 1Ј-H). 13C-NMR
(125 MHz, CD3OD) d: 20.08 (5-CH3), 21.77 (9-CH3), 25.02 (C7), 28.90,
30.30 (gem-CH3), 37.96 (C1), 38.81 (C8), 42.96 (C4), 49.53 (C2), 62.83
(C6Ј), 65.68 (C3), 71.72 (C4Ј), 75.33 (C2Ј), 77.87, 77.88 (C5Ј, C9), 78.29
(C3Ј), 103.88 (C1Ј), 125.43 (C5), 138.36 (C6). SIMS m/z: 373.2222 [Calcd
for C19H33O7 (MϪϪH) 373.2223]. [a]D23 Ϫ74.2° (cϭ0.97, MeOH).
Acetylation of Pentaols 6a, b and 11a, b To a solution of the pentaol
6a (220 mg, 0.59 mmol) in pyridine (3.8 ml) was added Ac2O (0.96 ml) and
the mixture was stirred under an argon atmosphere at rt for 20 h, poured into
ice-water and extracted with AcOEt. The extracts were washed successively
with aq. 5% HCl, saturated aq. NaHCO3, and brine. Evaporation of the dried
extracts gave a residue, which was purified by CC (ether–CH2Cl2, 15 : 85) to
afford the pentaacetate 7a (334 mg, 97%). The compounds 7b (92%), 12a
(93%) and 12b (93%) were prepared in the same manner as described above.
1H- and 13C-NMR data of the synthetic (3R,9R)-9-O-glucoside 7b and
(3R,9R)-3-O-glucoside 12b were in agreement with those of glucosides iso-
lated1) from rose petals.
6b: Colorless foams; 1H-NMR (500 MHz, CD3OD) d: 1.03, 1.05 (each
3H, s, gem-Me), 1.20 (3H, d, Jϭ6 Hz, 9-Me), 1.37 (1H, t, Jϭ12 Hz, 2ax-H),
1.54 (1H, tt, Jϭ13, 5.5 Hz, 8-H), 1.63 (3H, s, 5-Me), ca. 1.64 (1H, m, 8-H),
1.67 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-H), 1.92 (1H, br dd, Jϭ16, 10 Hz, 4ax-
H), 1.95 (1H, br td, Jϭ13, 5 Hz, 7-H), 2.17 (1H, br dd, Jϭ16, 5 Hz, 4eq-H),
2.24 (1H, br td, Jϭ13, 4.5 Hz, 7-H), 3.15 (1H, dd, Jϭ9, 8 Hz, 2Ј-H), 3.25
(1H, ddd, Jϭ9, 5.5, 2 Hz, 5Ј-H), 3.29 (1H, t, Jϭ9 Hz, 4Ј-H), 3.36 (1H, t,
Jϭ9 Hz, 3Ј-H), 3.67 (1H, dd, Jϭ12, 5.5 Hz, 6Ј-H), ca. 3.84 (1H, m, 3-H),
3.85 (1H, dd, Jϭ12, 2 Hz, 6Ј-H), 3.88 (1H, sext, Jϭ6 Hz, 9-H), 4.34 (1H, d,
Jϭ8 Hz, 1Ј-H). 13C-NMR (125 MHz, CD3OD) d: 19.75 (9-CH3), 20.08 (5-
CH3), 25.34 (C7), 28.91, 30.40 (gem-CH3), 38.84 (C1), 38.99 (C8), 42.99
(C4), 49.55 (C2), 62.96 (C6Ј), 65.73 (C3), 71.86 (C4Ј), 75.24 (C2Ј), 76.12
(C9), 77.89 (C5Ј), 78.25 (C3Ј), 102.24 (C1Ј), 125.39 (C5), 138.49 (C6).
SIMS m/z: 373.2223 [Calcd for C19H33O7 (MϪϪH) 373.2223]. [a]D27 Ϫ64.5°
(cϭ0.99, MeOH).
7a: Colorless foams; 1H-NMR (500 MHz, CDCl3) d: 1.03, 1.04 (each 3H,
s, gem-Me), 1.26 (3H, d, Jϭ6 Hz, 9-Me), 1.43 (1H, tt, Jϭ13.5, 4.5 Hz, 8-H),
1.51 (1H, t, Jϭ12.5 Hz, 2ax-H), 1.58 (3H, s, 5-Me), 1.59 (1H, m, 8-H), 1.71
(1H, ddd, Jϭ12.5, 3.5, 2 Hz, 2eq-H), 1.92 (1H, br td, Jϭ13.5, 4.5 Hz, 7-H),
2.004, 2.018, 2.027, 2.032, 2.079 (each 3H, s, OAcϫ5), 2.02 (1H, 4ax-H),
2.06 (1H, 7-H), 2.29 (1H, br dd, Jϭ16.5, 5.5 Hz, 4eq-H), 3.68 (1H, m, 9-H),
3.71 (1H, ddd, Jϭ10, 5.5, 2.5 Hz, 5Ј-H), 4.14 (1H, dd, Jϭ12, 2.5 Hz, 6Ј-H),
4.25 (1H, dd, Jϭ12, 5.5 Hz, 6Ј-H), 4.57 (1H, d, Jϭ8 Hz, 1Ј-H), 4.98 (1H, m,
3-H), 5.00 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.06 (1H, t, Jϭ9.5 Hz, 4Ј-H), 5.21
(1H, t, Jϭ9.5 Hz, 3Ј-H). 13C-NMR (125 MHz, CDCl3) d: 19.61 (5-CH3),
20.61 20.62, 20.74, 20.75, 21.46 (CH3COϫ5), 21.60 (9-CH3), 24.11 (C7),
28.27, 29.45 (gem-CH3), 37.26 (C8), 37.44 (C1), 38.14 (C4), 44.18 (C2),
62.26 (C6Ј), 68.59, 68.67 (C3, C4Ј), 71.69, 71.75 (C2Ј, C5Ј), 73.07 (C3Ј),
79.21 (C9), 101.24 (C1Ј), 123.90 (C5), 136.86 (C6), 169.17, 169.44, 170.37,
170.68, 170.85 (COϫ5). IR (CHCl3) cmϪ1: 1755 (OCO). SIMS m/z:
607.2739 [Calcd for C29H44O12Na (MϩϩNa) 607.2728]. [a]D25 Ϫ28.5°
(cϭ0.95, MeOH).
(1R)-4-[(3S)-3-Hydroxybutyl]-3,5,5-trimethylcyclohex-3-enyl-b-D-glu-
copyranoside (11a) In the same manner as described for the preparation
of the pentaols 6a, b, the pentapivaloate 10a (876 mg) was treated with
LiOH·H2O (112 mg, 2.67 mmol) to afford the mono 9-O-pivaloate (479 mg,
95%); 1H-NMR (300 MHz, CDCl3) d: 1.01, 1.02 (each 3H, s, gem-Me), 1.20
(3H, d, Jϭ6.5 Hz, 9-Me), 1.20 (9H, s, tert-Bu), 1.50 (1H, t, Jϭ12.5 Hz, 2ax-
H), 1.56 (2H, m, 8-H2), 1.60 (3H, s, 5-Me), 1.80 (1H, br d, Jϭ12.5 Hz, 2eq-
H), 1.99 (2H, br t, Jϭ8.5 Hz, 7-H2), 2.03 (1H, br dd, Jϭ16.5, 10.5 Hz, 4ax-
H), 2.29 (1H, br dd, Jϭ16.5, 5 Hz, 4eq-H), 3.31 (1H, br d, Jϭ9 Hz, 5Ј-H),
3.40 (1H, br t, Jϭ9 Hz, 2Ј-H), 3.56 (1H, br t, Jϭ9.5 Hz, 4Ј-H), 3.66 (1H, br t,
Jϭ9.5 Hz, 3Ј-H), 3.85 (2H, m, 6Ј-H2), 3.97 (1H, m, 3-H), 4.46 (1H, d,
Jϭ7.5 Hz, 1Ј-H), 4.86 (1H, sext, Jϭ6.5 Hz, 9-H). SIMS m/z: 457.2808
[Calcd for C24H41O8 (MϪϪH) 457.2799]. A solution of this mono 9-O-pival-
oate (479 mg) in MeOH (15 ml) containing LiOH·H2O (120 mg, 2.86 mmol)
was refluxed under an argon atmosphere for 20 h. Work-up gave a residue,
which was purified by short-CC (MeOH–CH2Cl2, 15 : 85) to give the pentaol
11a (290 mg, 74%; 70% from 10a).
7b: Colorless foams; 1H-NMR (500 MHz, CDCl3) d: 1.04, 1.05 (each 3H,
s, gem-Me), 1.13 (3H, d, Jϭ6.5 Hz, 9-Me), 1.51 (1H, t, Jϭ12 Hz, 2ax-H),
1.54 (2H, ddd, Jϭ9, 7.5, 6.5 Hz, 8-H2), 1.59 (3H, s, 5-Me), 1.70 (1H, ddd,
Jϭ12, 3.5, 2 Hz, 2eq-H), 1.88 (1H, br dt, Jϭ15, 7.5 Hz, 7-H), ca. 2.01 (1H,
4ax-H), 2.006, 2.026, 2.030, 2.034, 2.066 (each 3H, s, OAcϫ5), 2.19 (1H,
br dt, Jϭ15, 9 Hz, 7-H), 2.28 (1H, br dd, Jϭ16.5, 5.5 Hz, 4eq-H), 3.68 (1H,
ddd, Jϭ9.5, 5, 3 Hz, 5Ј-H), 3.75 (1H, sext, Jϭ6.5 Hz, 9-H), 4.14 (1H, dd,
Jϭ12, 3 Hz, 6Ј-H), 4.23 (1H, dd, Jϭ12, 5 Hz, 6Ј-H), 4.55 (1H, d, Jϭ7.5 Hz,
1Ј-H), 4.96 (1H, dd, Jϭ9.5, 7.5 Hz, 2Ј-H), 4.99 (1H, m, 3-H), 5.09 (1H, t,
Jϭ9.5 Hz, 4Ј-H), 5.21 (1H, t, Jϭ9.5 Hz, 3Ј-H). 13C-NMR (125 MHz, CDCl3)
d: 19.53, 19.54 (9-CH3, 5-CH3), 20.62, 20.65, 20.66, 20.70, 21.47
(CH3COϫ5), 23.73 (C7), 28.27, 29.47 (gem-CH3), 37.36 (C8), 37.46 (C1),
38.19 (C4), 44.25 (C2), 62.20 (C6Ј), 68.72 (C3, C4Ј), 71.62, 71.64 (C2Ј,
C5Ј), 73.00 (C3Ј), 76.20 (C9), 99.17 (C1Ј), 123.70 (C5), 137.13 (C6),
169.23, 169.44, 170.37, 170.63 170.82 (COϫ5). IR (CHCl3) cmϪ1: 1755
(OCO). SIMS m/z: 607.2748 [Calcd for C29H44O12Na (MϩϩNa) 607.2728].
[a]D26 Ϫ41.0° (cϭ0.93, MeOH).
1
11a: Colorless foams; H-NMR (500 MHz, CD3OD) d: 1.05, 1.07 (each
3H, s, gem-Me), 1.17 (3H, d, Jϭ6 Hz, 9-Me), 1.45 (1H, m, 8-H), 1.49 (1H, t,
Jϭ12 Hz, 2ax-H), 1.53 (1H, m, 8-H), 1.64 (3H, s, 5-Me), 1.83 (1H, ddd,
Jϭ12, 3.5, 2 Hz, 2eq-H), 2.01 (1H, br dd, Jϭ16.5, 9 Hz, 4ax-H), ca. 2.02
(1H, m, 7-H), 2.12 (1H, br td, Jϭ12.5, 5 Hz, 7-H), 2.34 (1H, br dd, Jϭ16.5,
5 Hz, 4eq-H), 3.15 (1H, dd, Jϭ9, 8 Hz, 2Ј-H), 3.29 (2H, m, 4Ј-H, 5Ј-H), 3.35
(1H, t, Jϭ9 Hz, 3Ј-H), 3.67 (1H, dd, Jϭ12, 5 Hz, 6Ј-H), 3.70 (1H, sext,
Jϭ6 Hz, 9-H), 3.86 (1H, dd, Jϭ12, 2 Hz, 6Ј-H), 4.05 (1H, m, 3-H), 4.42
(1H, d, Jϭ8 Hz, 1Ј-H). 13C-NMR (125 MHz, CD3OD) d: 20.02 (5-CH3),
23.24 (9-CH3), 25.54 (C7), 28.81, 30.27 (gem-CH3), 38.78 (C1), 39.78 (C4),
40.67 (C8), 47.50 (C2), 62.75 (C6Ј), 69.17 (C9), 71.67 (C4Ј), 73.27 (C3),
75.18 (C2Ј), 77.87 (C5Ј), 78.13 (C3Ј), 102.33 (C1Ј), 125.09 (C5), 138.54
12a: Colorless foams; 1H-NMR (500 MHz, CDCl3) d: 1.01, 1.04 (each
3H, s, gem-Me), 1.23 (3H, d, Jϭ6 Hz, 9-Me), 1.49 (1H, t, Jϭ12 Hz, 2ax-H),
1.54 (1H, m, 8-H), 1.60 (3H, s, 5-Me), 1.64 (1H, m, 8-H), 1.79 (1H, ddd,
Jϭ12, 3.5, 2 Hz, 2eq-H), 1.94 (1H, br dd, Jϭ16.5, 9 Hz, 4ax-H), 1.98 (2H,

882
Vol. 51, No. 7
m, 7-H2), 2.01 (3H), 2.03 (3H), 2.04 (6H), 2.08 (3H) (each s, OAcϫ5), 2.18
Me), 1.08 (3H, d, Jϭ6 Hz, 9-Me), 1.52 (2H, m, 8-H2), 1.56 (3H, s, 5-Me),
(1H, br dd, Jϭ16.5, 5.5 Hz, 4eq-H), 3.70 (1H, ddd, Jϭ9.5, 5, 2.5 Hz, 5Ј-H), 1.61 (1H, t, Jϭ12 Hz, 2ax-H), 1.81 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-H), ca.
3.91 (1H, m, 3-H), 4.13 (1H, dd, Jϭ12, 2.5 Hz, 6Ј-H), 4.25 (1H, dd, Jϭ12, 1.88 (1H, m, 7-H), 2.13 (1H, br dd, Jϭ16.5, 10 Hz, 4ax-H), ca. 2.25 (1H, m,
5 Hz, 6Ј-H), 4.63 (1H, d, Jϭ8 Hz, 1Ј-H), 4.88 (1H, sext, Jϭ6 Hz, 9-H), 4.96 7-H), 2.36 (1H, br dd, Jϭ16.5, 6 Hz, 4eq-H), 3.85 (1H, sext, Jϭ6 Hz, 9-H),
(1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.07 (1H, t, Jϭ9.5 Hz, 4Ј-H), 5.21 (1H, t, 4.15 (1H, ddd, Jϭ10, 5.5, 3.5 Hz, 5Ј-H), 4.49 (1H, dd, Jϭ12, 5.5 Hz, 6Ј-H),
Jϭ9.5 Hz, 3Ј-H). 13C-NMR (125 MHz, CDCl3) d: 19.69, 19.76 (5-CH3, 9-
CH3), 20.61 20.64, 20.69, 20.75, 21.34 (CH3COϫ5), 23.91 (C7), 28.49,
4.65 (1H, dd, Jϭ12, 3.5 Hz, 6Ј-H), 4.92 (1H, d, Jϭ8 Hz, 1Ј-H), 5.21 (1H, m,
3-H), 5.50 (1H, dd, Jϭ10, 8 Hz, 2Ј-H), 5.68 (1H, t, Jϭ10 Hz, 4Ј-H), 5.91
29.53 (gem-CH3), 36.28 (C8), 37.60 (C1), 38.72 (C4), 45.89 (C2), 62.32 (1H, t, Jϭ10 Hz, 3Ј-H), 7.25—7.58 (15H, m, ArH), 7.82—8.06 (10H, m,
(C6Ј), 68.70 (C4Ј), 71.34 (C9), 71.57 (C2Ј), 71.76 (C5Ј), 72.94 (C3Ј), 73.47
(C3), 99.43 (C1Ј), 123.65 (C5), 137.11 (C6), 169.26, 169.44, 170.37,
ArH). SIMS m/z: 917.3511 [Calcd for C54H54O12Na (MϩϩNa) 917.3510].
13a: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 0.92, 0.98 (each
170.68, 170.82 (COϫ5). IR (CHCl3) cmϪ1: 1755 (OCO). SIMS m/z: 3H, s, gem-Me), 1.33 (3H, d, Jϭ6 Hz, 9-Me), 1.48 (3H, s, 5-Me), 1.49 (1H,
607.2726 [Calcd for C29H44O12Na (MϩϩNa) 607.2728]. [a]D26 Ϫ43.7° t, Jϭ12 Hz, 2ax-H), 1.56—1.77 (2H, m, 8-H2), 1.80 (1H, ddd, Jϭ12, 3.5,
(cϭ0.94, MeOH).
2 Hz, 2eq-H), 1.87 (1H, br dd, Jϭ16.5, 9.5 Hz, 4ax-H), 2.01 (2H, br t,
12b: Colorless foams; 1H-NMR (500 MHz, CDCl3) d: 1.01, 1.02 (each Jϭ8.5 Hz, 7-H2), 2.13 (1H, br dd, Jϭ16.5, 5 Hz, 4eq-H), 3.98 (1H, m, 3-H),
3H, s, gem-Me), 1.23 (3H, d, Jϭ6 Hz, 9-Me), 1.49 (1H, t, Jϭ12 Hz, 2ax-H), 4.19 (1H, ddd, Jϭ9.5, 6, 3.5 Hz, 5Ј-H), 4.51 (1H, dd, Jϭ12, 6 Hz, 6Ј-H),
1.56 (2H, m, 8-H2), 1.61 (3H, s, 5-Me), 1.79 (1H, ddd, Jϭ12, 3.5, 2 Hz, 2eq-
4.63 (1H, dd, Jϭ12, 3.5 Hz, 6Ј-H), 4.98 (1H, d, Jϭ8 Hz, 1Ј-H), 5.11 (1H,
H), 1.89 (1H, br td, Jϭ13, 5 Hz, 7-H), 1.94 (1H, br dd, Jϭ16, 9.5 Hz, 4ax- sext, Jϭ6 Hz, 9-H), 5.50 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.62 (1H, t, Jϭ9.5 Hz,
H), 2.01 (3H), 2.03 (3H), 2.04 (6H), 2.08 (3H) (each s, OAcϫ5), 2.06 (1H,
m, 7-H), 2.18 (1H, br dd, Jϭ16, 5.5 Hz, 4eq-H), 3.70 (1H, ddd, Jϭ9.5, 5,
4Ј-H), 5.91 (1H, t, Jϭ9.5 Hz, 3Ј-H), 7.04—7.58 (15H, m, ArH), 7.82—8.06
(10H, m, ArH). SIMS m/z: 917.3521 [Calcd for C54H54O12Na (MϩϩNa)
2.5 Hz, 5Ј-H), 3.91 (1H, m, 3-H), 4.13 (1H, dd, Jϭ12, 2.5 Hz, 6Ј-H), 4.25 917.3510].
(1H, dd, Jϭ12, 5 Hz, 6Ј-H), 4.63 (1H, d, Jϭ8 Hz, 1Ј-H), 4.88 (1H, sext,
13b: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 0.94, 0.95 (each
Jϭ6 Hz, 9-H), 4.96 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.07 (1H, t, Jϭ9.5 Hz, 4Ј- 3H, s, gem-Me), 1.33 (3H, d, Jϭ6 Hz, 9-Me), 1.49 (3H, s, 5-Me), 1.49 (1H,
H), 5.21 (1H, t, Jϭ9.5 Hz, 3Ј-H). 13C-NMR (125 MHz, CDCl3) d: 19.63 (5- t, Jϭ12 Hz, 2ax-H), 1.66 (2H, m, 8-H2), 1.81 (1H, ddd, Jϭ12, 3.5, 2 Hz,
CH3), 19.79 (9-CH3), 20.61, 20.64, 20.69, 20.75, 21.34 (CH3COϫ5), 23.96 2eq-H), 1.87 (1H, br dd, Jϭ16.5, 10 Hz, 4ax-H), ca. 1.90 (1H, m, 7-H), ca.
(C7), 28.46, 29.51 (gem-CH3), 36.34 (C8), 37.59 (C1), 38.72 (C4), 45.87 2.08 (1H, m, 7-H), 2.12 (1H, br dd, Jϭ16.5, 5.5 Hz, 4eq-H), 3.98 (1H, m, 3-
(C2), 62.32 (C6Ј), 68.70 (C4Ј), 71.32 (C9), 71.57 (C2Ј), 71.77 (C5Ј), 72.94
(C3Ј), 73.47 (C3), 99.43 (C1Ј), 123.65 (C5), 137.07 (C6), 169.25, 169.43,
170.35, 170.66, 170.80 (COϫ5). IR (CHCl3) cmϪ1: 1755 (OCO). SIMS m/z:
607.2750 [Calcd for C29H44O12Na (MϩϩNa) 607.2728]. [a]D25 Ϫ28.3°
(cϭ0.88, MeOH).
H), 4.19 (1H, ddd, Jϭ9, 6, 3.5 Hz, 5Ј-H), 4.52 (1H, dd, Jϭ12, 6 Hz, 6Ј-H),
4.63 (1H, dd, Jϭ12, 3.5 Hz, 6Ј-H), 4.98 (1H, d, Jϭ8 Hz, 1Ј-H), 5.11 (1H,
sext, Jϭ6 Hz, 3-H), 5.50 (1H, dd, Jϭ9.5, 8 Hz, 2Ј-H), 5.62 (1H, t, Jϭ9.5 Hz,
4Ј-H), 5.91 (1H, t, Jϭ9.5 Hz, 3Ј-H), 7.24—7.58 (15H, m, ArH), 7.82—8.06
(10H, m, ArH). SIMS m/z: 917.3522 [Calcd for C54H54O12Na (MϩϩNa)
Benzoylation of Pentaols 6a, b and 11a, b To a solution of the pentaol 917.3510].
6a (18.4 mg, 0.049 mmol) in pyridine (1.0 ml) was added benzoyl chloride
(0.20 ml) and the mixture was stirred under an argon atmosphere at rt for
20 h, poured into ice-water and extracted with AcOEt. The extracts were
References
washed successively with aq. 5% HCl, saturated aq. NaHCO3, and brine.
Evaporation of the dried extracts gave a residue, which was purified by
short-CC (AcOEt–hexane, 15 : 85) to yield the pentabenzoate 8a (39.4 mg,
90%). The compounds 8b (51%), 13a (88%) and 13b (77%) were prepared
in the same manner as described above.
1) Straubinger M., Knapp H., Oka N., Watanabe N., Winterhalter P., J.
Agric. Food Chem., 45, 4053—4056 (1997).
2) Sefton M. A., Skouroumounis G. K., Massy-Westropp R. A., Williams
P. J., Aust. J. Chem., 42, 2071—2084 (1989).
3) Yamano Y., Watanabe Y., Watanabe N., Ito M., Chem. Pharm. Bull.,
48, 2017—2018 (2000).
4) Yamano Y., Watanabe Y., Watanabe N., Ito M., J. Chem. Soc., Perkin
Trans. 1, 2002, 2833—2844 (2002).
5) Matsumura K., Hashiguchi S., Ikariya T., Noyori R., J. Am. Chem.
Soc., 119, 8738—8739 (1997).
6) Kunz H., Harreus A., Liebigs Ann. Chem., 1982, 41—48 (1982).
7) Otsuka H., Phytochemistry, 37, 461—465 (1994).
8) Kasai R., Suzuo M., Asakawa J., Tanaka O., Tetrahedron Lett., 1977,
175—178 (1977).
8a: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 0.78, 0.83 (each 3H,
s, gem-Me), 1.29 (3H, d, Jϭ6 Hz, 9-Me), ca. 1.37 (1H, m, 8-H), 1.53 (1H, t,
Jϭ12 Hz, 2ax-H), 1.42 (3H, s, 5-Me), ca. 1.54 (1H, m, 8-H), 1.73 (1H, ddd,
Jϭ12, 3.5, 2 Hz, 2eq-H), 1.76 (1H, m, 7-H), 1.95 (1H, br td, Jϭ13, 4.5 Hz,
7-H), 2.07 (1H, br dd, Jϭ16.5, 10 Hz, 4ax-H), 2.30 (1H, br dd, Jϭ16.5,
5.5 Hz, 4eq-H), 3.73 (1H, m, 9-H), 4.18 (1H, ddd, Jϭ10, 6, 3.5 Hz, 5Ј-H),
4.51 (1H, dd, Jϭ12, 6 Hz, 6Ј-H), 4.65 (1H, dd, Jϭ12, 3.5 Hz, 6Ј-H), 4.92
(1H, d, Jϭ8 Hz, 1Ј-H), 5.13 (1H, m, 3-H), 5.57 (1H, dd, Jϭ10, 8 Hz, 2Ј-H),
5.64 (1H, t, Jϭ10 Hz, 4Ј-H), 5.92 (1H, t, Jϭ10 Hz, 3Ј-H), 7.25—7.58 (15H,
m, ArH), 7.82—8.06 (10H, m, ArH). SIMS m/z: 917.3497 [Calcd for
C54H54O12Na (MϩϩNa) 917.3510].
9) Kasai R., Okihara M., Asakawa J., Mizutani K., Tanaka O., Tetrahe-
dron, 35, 1427—1432 (1979).
8b: Colorless foams; 1H-NMR (300 MHz, CDCl3) d: 1.03 (6H, s, gem-