Synthesis of 1,2-oxygenated 6-arylfurofuran lignan: stereoselective synthesis of (1S,2S,5R,6S)-1-hydroxysamin.

Article abstract of DOI:10.1271/bbb.66.1495

(1S,2S,5R,6S)-6-(3,4-Methylenedioxyphenyl)-3,7-dioxabicyclo[3.3.0]octan-1,2-diol ((+)-1-hydroxysamin 1) was synthesized, starting from olefin 8. Stereoselective alpha-hydroxylation was achieved after converting 8 to aldehyde 13. Resulting unstable alpha-hydroxy aldehyde 14 was then transformed to (+)-1-hydroxysamin (1). This is a new efficient synthetic route to 1,2-oxygenated 6-arylfurofuran lignans.

Full text of DOI:10.1271/bbb.66.1495

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Synthesis of 1,2-Oxygenated 6-arylfurofuran Lignan:
Stereoselective Synthesis of (1S,2S,5R,6S)-1-
hydroxysamin
Satoshi YAMAUCHIa, Satoshi BANDOa & Yoshiro KINOSHITAa
a College of Agriculture, Ehime University Tarumi 3-5-7, Matsuyama, Ehime 790-8566,
Japan
Published online: 22 May 2014.
To cite this article: Satoshi YAMAUCHI, Satoshi BANDO & Yoshiro KINOSHITA (2002) Synthesis of 1,2-Oxygenated 6-
arylfurofuran Lignan: Stereoselective Synthesis of (1S,2S,5R,6S)-1-hydroxysamin, Bioscience, Biotechnology, and
Biochemistry, 66:7, 1495-1499, DOI: 10.1271/bbb.66.1495
To link to this article: http://dx.doi.org/10.1271/bbb.66.1495
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Biosci. Biotechnol. Biochem., 66 (7), 1495–1499, 2002
Synthesis of 1,2-Oxygenated 6-arylfurofuran Lignan: Stereoselective
Synthesis of (1S,2S,5R,6S)-1-hydroxysamin
Satoshi YAMAUCHI,† Satoshi BANDO, and Yoshiro KINOSHITA
College of Agriculture, Ehime University, Tarumi 3-5-7, Matsuyama, Ehime 790-8566, Japan
Received January 9, 2002; Accepted March 5, 2002
(1
dioxabicyclo[3.3.0]octan-1,2-diol ((
1) was synthesized, starting from oleˆn 8. Stereoselec-
tive -hydroxylation was achieved after converting 8 to
S
,2
S
,5
R
,6
S
)-6-(3,4-Methylenedioxyphenyl)-3,7-
sis of the 6-aryl-2-aryloxy-1-hydroxy-3,7-dioxabicy-
clo[3.3.0]octane type of lignan 24),5) (Fig.).
＋
)-1-hydroxysamin
Although some synthetic methods for optically
active samin are known,6),7),8) only one stereoselective
synthetic route to optically active 1-hydroxysamin (1)
has been reported.3) However, the long pathway for
this synthetic method inhibits the production of
many synthetic analogues of 1,2-oxygenated 6-aryl-
furofuran lignan. The many processes for protecting
and deprotecting the hydroxy groups result in a
lengthy procedure for the synthesis of oxidized lig-
nan. To develop more e‹cient synthetic method,
direct stereoselective introduction of the tertiary
hydroxy group by an oxidant was planned. Thus,
enol ether or enolate 3 was adopted as a substrate for
this oxidation reaction (Fig.). This oxidant would at-
tack from the opposite side of the substituent at the 3
position, and the resulting product could then be
converted to 1-hydroxysamin 1.
a
aldehyde 13. Resulting unstable
a
-hydroxy aldehyde 14
＋
was then transformed to ( )-1-hydroxysamin (1). This
is a new e‹cient synthetic route to 1,2-oxygenated 6-
arylfurofuran lignans.
Key words: lignan; furofuran lignan
Furofuran lignan, which is one of the largest
groups of lignans, has interesting biological charac-
teristics1) such as antioxidative activity, antitumour
activity, cytotoxic activity, and an inhibitor of cAMP
phosphodiesterase. The synthetic study of this
furofuran lignan is important for further research
into its biological activity, and many synthetic routes
has been developed.2) Our synthetic study has been
focused on the 1,2-oxygenated 6-arylfurofuran lig-
nans,3) 1 and 2, because only a few synthetic route to
this type of lignan have been reported.4),5) This study
is expected to contribute to biological research into
the structure-activity relationship of furofuran lignan
and to discover new biological activities of 1,2-oxyg-
enated 6-arylfurofuran lignan. The method used to
stereoselectively introduce the three substituents on
to a furofuran ring is also important. This present
report describes the stereoselective synthesis of
It was assumed that the substrate for this oxidation
could be obtained from oleˆn 7.9) Scheme 1 shows
the retrosynthetic analysis of 1-hydroxysamin (1). 1-
Hydroxysamin (1) could be obtained from
a-hydroxy-
aldehyde 4 by deprotection. Aldehyde 5 could be
converted to a-hydroxyaldehyde 4 by stereoselective
oxidation to an enol ether or enolate from 5. Alde-
hyde 5 would be obtained from lactone 6 by carbon-
carbon bond formation at the
a position, reduction,
intramolecular cyclization, and subsequent oxida-
tion. Oleˆn 7 could be transformed to lactone 6
by successive oxidation. This oleˆn 7 could be
(1S,2S,5R,6S)-1-hydroxysamin (1) in fewer steps
than previously described.3) This 1-hydroxysamin
type of lignan is a useful compound for biological
testing and an important intermediate for the synthe-
stereoselectively prepared from
(S)-4-benzyl-2-
oxazolidinone and 4-pentenoic acid by Mailoli's
Fig.
To whom correspondence should be addressed. Fax: +81-89-977-4364; E-mail: syamauch
†
＠
agr.ehime-u.ac.jp

1496
S. YAMAUCHI et al.
Scheme 1. Retrosynthetic Analysis of (1S,2S,5R,6S)-1-Hydroxysamin (1).
method.9)
lation to aldehyde 13, which is the key reaction for
the synthesis of 1-hydroxysamin. Direct -hydroxyla-
tion of aldehyde 13, using 2-sulfonyloxaziridine10)
and MoOPH11) with a base, did not give
-hydroxyal-
a
Results and discussion
a
Oleˆn 8, which was stereoselectively prepared
dehyde 14 and resulted in recovery of the aldehyde.
Oxidation via an acetyl enol ether also resulted in
recovery of aldehyde. The conversion of 13 to 14 was
achieved via triisopropylsilyl enol ether, which was
prepared by treating 13 with triisopropylsilyl
tri‰uoromethanesulfonate, 1,8-diazabicyclo[5.4.0]
from (
S)-4-benzyl-2-oxazolidinone and 4-pentenoic
acid in 4 steps9) in 56
z
overall yield, was selected as
the starting material. Successive oxidation of 8 by os-
mium tetroxide, sodium periodate, and silver car-
bonate-celite gave lactone 9 in 92
z yield.
Although the aldol condensation of 9 with formal-
undec-7-ene, and 4-dimethylaminopyridine in a
dehyde did not proceed, the reaction with methyl
quantitative yield. After the unstable silyl enol ether
had been subjected to osmium oxidation, the crude
chloroformate gave 10 in 90
z conversion yield.
Stereoselectivity in this condensation reaction was
not necessary, because product 2 -10 was obtained
as a single isomer. The observation of NOE between
4-H and the methylene protons of a silyloxymethyl
group showed the 3
relation between 2-H and 4-H conˆrmed the conˆgu-
ration at the 2 position to be . At this stage, the
product was treated with
mine followed by silica gel column chromatography
to convert the dimers of -hydroxyaldehyde 14 to a
monomer.12) It is well known that a hydroxy aldehyde
N,N?-dimethylethylenedia-
R
a
R
, 4
S
conˆguration. Another cor-
is easily dimerized. Resulting unstable a-hydroxyal-
dehyde 14 was therefore immediately treated with
R
tetrabutylammonium ‰uoride to cleave the silyl
carbon-carbon formation required for the synthesis
of 1-hydroxysamin was achieved. Lithium aluminum
hydride reduction of lactone 10 aŠorded desired triol
ether, giving (1
S
,2
S
,5
R
,6
S
)-1-hydroxysamin 1 as a
20
single isomer in 78
z
yield: [
a
]
+74.5, c 0.51 in
D
CHCl3; lit.3) [
a
]
20 +74.8,
c
0.21 in CHCl3. The NMR
D
11 (63
hemiacetal was transformed to triol 11 by sodium
borohydride reduction (57 ). The total yield of triol
11 from lactone 10 was 76 . Cyclization of triol 11
to tetrahydrofuran ring 12 was achieved by S 1 in-
z
) and corresponding hemiacetal (22
z
). This
data agreed with previously described data.3)
This new stereoselective synthetic method for
z
z
(1
from (
acid to provide 12
e‹cient synthetic method than that previously de-
scribed (25 steps, 0.3
overall yield).3) Since the
S,2S,5R,S)-1-hydroxysamin (1) involved 14 steps
S
)-4-benzyl-2-oxazolidinone and 4-pentenoic
overall yield. This is a more
N
z
tramolecular etheriˆcation, using a catalytic amount
of 10-camphorsulfonic acid. This cyclization gave
z
desired 2
S
-12 as a diastereomeric mixture of 4R S
transformation of the hemiacetal portion in the 1-
hydroxysamin type of lignan to an acetal is possible,5)
this method also provides a new synthetic route to the
optically active 6-aryl-2-aryloxy-1-hydroxy-3,7-diox-
abicyclo[3.3.0]octane 2 type of lignan.
W
(1 1) in 83
z
yield. No undesired 2
parent. Pyridinium chlorochromate oxidation of 12
furnished aldehyde 13 as a 2 3 diastereomeric mix-
R isomer was ap-
W
W
ture in 72
z yield. Since this aldehyde could be con-
verted to an enolate or enol ether, it was used for the
next step without separation of the 4R S diastereom-
Experimental
W
ers.
The next stage involved stereoselective
a
-hydroxy-
All melting point (mp) data are uncorrected. NMR

Synthesis of Optically Active 1-Hydroxysamin
1497
Scheme 2. Synthesis of (1
Reagents and conditions (yield): (a) (1) OsO4, NMO, acetone, tert-BuOH, H2O, r.t., 24 h; (2) NaIO4, MeOH, r.t., 3 h; (3) Ag2CO3-
Celite, toluene, re‰ux, 1 h (92 , 3 steps); (b) LHMDS, ClCO2CH3, THF, „75 C, 2 h (90 conversion yield); (c) (1) LiAlH4, THF,
r.t., 3 h; (2) NaBH4, EtOH, 3 h (76 , 2 steps); (d) CSA, CH2Cl2, r.t., 24 h (83 ); (e) PCC, MS 4A, CH2Cl2, r.t., 5 h (72 ); (f) (1) TIP-
SOTf, DBU, DMAP, CH2Cl2, r.t., 2 h (100 ); (2) OsO4, NMO, acetone, tert-BuOH, H2O, r.t., 24 h, and then (CH3NHCH2)2, ben-
zene, re‰ux, 0.5 h, SiO2 (71 ); (g) -Bu4NF, THF, r.t., 1 h (78 ).
S,2S,5R,6S)-1-Hydroxysamin (1).
z
9
z
z
z
z
z
z
n
z
data were measured by a JNM-EX400 spectrometer,
while IR spectra were determined with a Shimadzu
FTIR-8100 spectrometer. EIMS and FABMS data
were measured with Hitachi M-80B and JEOL
HX-110 spectrometers, respectively, and optical
rotation was evaluated with HORIBA SEPA-200
1:5) to give a hemiacetal (5.24 g). A reaction mixture
of this hemiacetal (5.24 g, 0.011 mol) and Ag2CO3-
Celite (12.1 g, 1 mmol g, 0.012 mol) in toluene
W
(30 ml) was heated under re‰ux for 1 h before ˆltra-
tion. The ˆltrate was concentrated, and the resulting
residue was applied to silica gel column chro-
equipment. [
a
]Dvalues are in units of 10„1 deg
matography (EtOAc-hexane 3:1) to give lactone 9
cm2g„1. The silica gel used was Wakogel C-300
(Wako, 200–300 mesh).
(5.22 g, 92
+9.7 (
z from oleˆn 8) as a colorless oil. [a]
20
D
c
1.03, CHCl3). IR nmax (CHCl3) cm„1: 2987,
1777, 1507, 1449, 1113, 1042. NMR
d
H(CDCl3): 1.08
(3R,4S)-3-(tert-Butyldiphenylsilyloxy)methyl-4-
(9H, s, C(C
H
3)3), 2.54 (1H, m, 3-
H
), 2.64 (1H, dd,
＝
＝
17.6,
(3,4-methylenedioxyphenyl)-4-butanolide (9).
A
J
17.6, 8.3 Hz, 2-C
H
H), 2.70 (1H, dd,
J
＝
＝
reaction solution of oleˆn 8 (5.51 g, 0.012 mol), 4-
methylmorpholine -oxide (1.63 g, 0.014 mol), and
OsO4 (2 H2O solution, 1 ml) in acetone (20 ml),
9.3 Hz, 2-CH
H
), 3.68 (1H, dd,
J
10.7, 4.4 Hz,
10.7, 4.9 Hz,
N
C
H
HOTBDPS), 3.73 (1H, dd,
J
＝
＝
z
CH
(2H, s, OC
(1H, s, Ar
7.37–7.46 (6H, m, Ar
NMR
H
OTBDPS), 5.29 (1H, d,
2O), 6.62 (1H, d,
), 6.73 (1H, d,
), 7.61–7.62 (4H, m, Ar
J
6.8 Hz, 4-H), 5.95
7.8 Hz, Ar ), 6.69
tert-butyl alcohol (5 ml), and H2O (5 ml) was stirred
at room temperature for 24 h before addition of
NaHSO3. After the mixture was ˆltered, the ˆltrate
was concentrated. The resulting residue was dis-
solved in H2O and EtOAc. The organic solution was
separated, washed with brine, and dried (Na2SO4).
Evaporation gave a crude glycol. A reaction mixture
of this crude glycol and NaIO4 (2.73 g, 0.013 mol) in
MeOH (10 ml) was stirred at room temperature for
3 h. After the mixture was concentrated, the residue
was dissolved in H2O and EtOAc. The organic solu-
tion was separated, washed with brine, and dried
(Na2SO4). After evaporation, the residue was applied
to silica gel column chromatography (EtOAc-hexane
H
H
J
H
＝
J
7.8 Hz, Ar
H
H
),
).
H
d
C(CDCl3): 19.3, 26.9, 31.2, 46.4, 62.1, 82.8,
101.3, 106.2, 108.2, 119.6, 127.9, 130.0, 132.4,
132.8, 135.5, 135.6, 147.8, 148.1, 176.1. MS m z (EI,
W
20 eV): 417 (M+-C(CH3)3, 32), 387 (100), 199 (42).
Anal. Found: C, 70.87; H, 6.61
C28H30O5Si: C, 70.86; H, 6.37
z. Calcd. for
z
.
(2R,3R,4S)-3-(tert-Butyldiphenylsilyloxy)methyl-
2-methoxycarbonyl-4-(3,4-methylenedioxyphenyl)-4-
butanolide (10). To a solution of LHMDS (1
M
in
THF; 17.6 ml, 0.018 mol) in THF (150 ml) was

1498
S. YAMAUCHI et al.
added a solution of lactone 9 (5.60 g, 0.012 mol) in
THF (50 ml) at „75 C. After the solution was
stirred at „75 C for 30 min, a solution of methyl
plied to silica gel column chromatography (EtOAc-
9
hexane 1:1) to give triol 11 (61 mg) as a colorless oil.
20
9
The total yield of 11 was 76
CHCl3). IR
1445, 1429, 1113, 1042. NMR
s, C(C 3)3), 2.05–2.15 (2H, m, 2-
), 3.15–3.38 (1H, br., O
z
. [
a
]
„20.2 (
c
0.69,
D
chloroformate (1.36 ml, 0.018 mol) in THF (20 ml)
was added. The reaction solution was stirred at
n
max(CHCl3) cm„1: 3386, 2947, 1505,
H(CDCl3): 1.05 (9H,
d
„75
9C for 2 h before additions of sat. aq. NH4Cl
H
H
H
, 3-
H ), 2.77 (1H,
solution and EtOAc. The organic solution was sepa-
rated, washed with brine, dried (Na2SO4), and
evaporated. The residue was applied to silica gel
column chromatography (EtOAc-hexane 1:1) to give
br. s, OH
), 3.38–3.57 (1H,
＝
br., O
H
), 3.62–3.75 (5H, m), 3.77 (1H, dd,
J
11.2,
＝
5.9 Hz), 4.80 (1H, d,
J
5.9 Hz, 1-
), 6.76 (1H, s, Ar
H ), 7.55–7.60 (4H, m, Ar
H ), 5.92 (2H, s,
OC
H
2O), 6.69 (2H, s, Ar
H
H
H
),
).
10 (3.04 g) and recovered lactone 9 (2.71 g). The con-
7.34–7.44 (6H, m, Ar
NMR
20
version yield was 90
IR
1159, 1113, 1042. NMR
C(C 3)3), 2.96 (1H, m, 3-
3.7 Hz, C HOTBDPS), 3.74 (1H, dd,
3.4 Hz, CH OTBDPS), 3.81 (3H, s, C
z
. [
a
]
+1.8 (
c
1.09, CHCl3).
d
C(CDCl3): 19.1, 26.9, 41.3, 48.5, 63.1, 63.5,
D
n
max(CHCl3) cm„1: 2984, 1782, 1742, 1507, 1462,
64.4, 73.4, 101.0, 106.6, 108.0, 119.6, 127.7, 127.8,
129.9, 132.7, 132.8, 135.6, 137.1, 146.8, 147.8. MS
d
H(CDCl3): 1.08 (9H, s,
), 3.65 (1H, dd,
H
H
J
J
＝
＝
11.2,
11.2,
m z (FAB): 531 (M+Na+, 100), 173 (71), 135 (57).
W
H
Found (HRMS): M++Na, 531.2185. Calcd. for
C29H36O6SiNa: 531.2179.
H
H
J
3O), 3.98
＝
9.8 Hz,
＝
(1H, d,
4- ), 5.96 (2H, s, OC
1.5 Hz, Ar
J
11.2 Hz, 2-
H
), 5.21 (1H, d,
2O), 6.61 (1H, dd,
8.1 Hz, Ar
), 7.36–7.48 (6H, m, Ar
). NMR C(CDCl3): 19.3,
＝
H
H
J
8.1,
), 6.73
),
(2S,3R,4R S)-3-(tert-Butyldiphenylsilyloxy)-
W
H
), 6.72 (1H, d,
J
＝
H
methyl-4-hydroxymethyl-2-(3,4-methylenedioxy-
phenyl)tetrahydrofuran (12). A reaction solution
of triol 11 (0.55 g, 1.08 mmol) and CSA (10 mg,
0.043 mmol) in CH2Cl2 (10 ml) was stirred at room
temperature for 24 h before addition of a few drops
of Et3N. After concentration, the residue was applied
to silica gel column chromatography (EtOAc-hexane
1:5) to give hydroxymethyltetrahydrofuran 12
＝
(1H, d,
J
1.5 Hz, Ar
H
H
7.58–7.63 (4H, m, Ar
H
d
26.9, 49.1, 50.6, 53.0, 59.5, 77.2, 81.3, 101.4, 106.7,
108.2, 120.7, 127.9, 128.0, 130.1, 130.5, 132.4,
132.5, 135.5, 135.6, 148.2, 148.3, 167.7, 170.7. MS
m z (EI, 70 eV): 475 (M+-CO2CH3, 82), 150 (84),
W
135 (91), 105 (100). Anal. Found: C, 67.87; H,
6.29
z
. Calcd. for C30H32O7Si: C, 67.65; H, 6.06
z
.
(0.44 g, 83
colorless oil. IR
1445, 1429, 1113, 1042. NMR
(4.5H, s), 1.06 (4.5H, s), 1.97 (0.5H, m), 2.34 (0.5H,
z
) in a 1 1 diastereomeric mixture as a
W
n
max(CHCl3) cm„1: 3424, 2934, 1505,
H(CDCl3): 1.04
(1S,2R)-2-(tert-Butyldiphenylsilyloxy)methyl-3-
hydroxymethyl-1-(3,4-methylenedioxyphenyl)-1,4-
butanediol (11). To an ice-cooled suspension of
LiAlH4 (0.07 g, 1.84 mmol) in THF (10 ml) was
added a solution of lactone 10 (0.50 g, 0.94 mmol) in
THF (10 ml). The reaction mixture was stirred at
room temperature for 3 h before addition of sat. aq.
MgSO4 solution and K2CO3. After the mixture was
ˆltered, the ˆltrate was concentrated. The residue
was puriˆed by silica gel column chromatography
(EtOAc-hexane 1:1) to give triol 11 (0.3 g) and the
corresponding hemiacetal (0.11 g). Hemiacetal:
d
＝
m), 2.51 (0.5H, m), 2.64 (0.5H, dd,
2.74 (0.5H, m), 3.13 (0.5H, dd,
J
J
7.8, 3.4 Hz),
＝
7.8, 3.9 Hz),
3.59–3.75 (3.5H, m), 3.83–3.96 (1.5H, m), 4.03
(0.5H, dd, 8.8, 8.3 Hz), 4.21 (0.5H, dd, 8.8,
7.8 Hz), 4.43 (1H, d, 8.3 Hz), 5.92–5.94 (2H, m),
8.3, 1.5 Hz), 6.59 (0.5H, dd,
J
＝
J
＝
＝
J
＝
J
6.49 (0.5H, dd,
J
J
＝
＝
8.3, 1.5 Hz), 6.62–6.68 (1.5H, m), 6.74 (0.5H, d,
1.5 Hz), 7.30–7.47 (6H, m), 7.55–7.65 (4H, m).
NMR dC(CDCl3) 19.1, 26.7, 26.8, 43.8, 47.1, 51.7,
54.7, 61.3, 61.9, 63.9, 64.6, 70.3, 70.5, 82.2, 83.3,
100.9, 106.2, 106.5, 107.9, 108.0, 119.2, 119.8,
127.7, 127.8, 127.9, 129.8, 129.9, 130.0, 132.5,
NMR dH(CDCl3): 1.05 (9H, m), 1.96 (0.5H, m), 2.25
(0.5H, m), 2.37–2.44 (1H, m), 2.48–2.52 (0.5H, m),
2.98 (0.5H, m), 3.60–3.76 (4.5H, m), 3.86 (0.5H, m),
132.6, 132.8, 135.1, 135.5, 135.9, 147.8. MS m z (EI,
W
4.76 (0.5H, d,
J
＝
9.3 Hz), 4.89 (0.5H, d,
J
＝
8.8 Hz),
20 eV): 490 (M+, 3), 234 (97), 199 (65), 161 (100).
＝
＝
5.42 (0.5H, dd,
5.57 (0.5H, dd,
J
J
5.6, 2.2 Hz, anomeric proton),
4.6, 3.2 Hz, anomeric proton),
Anal. Found: C, 70.75; H, 7.08
C29H34O5Si: C, 70.99; H, 6.98
z
. Calcd. for
z.
5.92–5.93 (2H, m), 6.60–6.69 (2H, m), 6.74 (0.5H, d,
＝
＝
1.5 Hz), 7.30–7.47
J
1.5 Hz), 6.88 (0.5H, d,
J
(2S,3R,4R S)-4-(tert-Butyldiphenylsilyloxy)-
W
(6H, m), 7.55–7.65 (4H, m). A reaction mixture of
this hemiacetal (0.11 g, 0.21 mmol) and NaBH4
(8 mg, 0.21 mmol) in EtOH (10 ml) was stirred at
methyl-5-(3,4-methylenedioxyphenyl)-3-tetrahydro-
furancarbaldehyde (13). A reaction mixture of alco-
hol 12 (0.40 g, 0.82 mmol), PCC (0.20 g, 0.93 mmol)
and MS 4A (1 g) in CH2Cl2 (20 ml) was stirred at
room temperature for 5 h. After the mixture was
ˆltered, the ˆltrate was concentrated. The residue
was applied to silica gel column chromatography
(EtOAc-hexane 1:5) to give aldehyde 13 (0.29 g,
room temperature for 3 h before addition of 1
M
aq.
HCl solution. After neutralization with sat. aq.
NaHCO3 solution, the mixture was concentrated.
The residue was dissolved in H2O and EtOAc. The
organic solution was separated, washed with brine,
dried (Na2SO4), and evaporated. The residue was ap-
72
z
) in a 2 3 diastereomeric mixture as a colorless
W

Synthesis of Optically Active 1-Hydroxysamin
1499
20
D
oil. IR
1429, 1113, 1042. NMR
2.49 (0.6H, m), 2.55 (0.4H, m), 3.20 (0.6H, m), 3.26
n
max(CHCl3) cm„1: 2948, 1725, 1505, 1447,
H(CDCl3): 1.06 (9H, s),
78
lit.3) [
z
) as a colorless oil. [
a
]
+74.5 (
c
0.51, CHCl3),
20
d
a] +74.8, (c 0.21, CHCl3).
D
＝
J
(0.4H, m), 3.68–3.73 (1H, m), 3.80 (0.6H, dd,
10.7, 4.4 Hz), 3.86 (0.4H, dd, 10.7, 4.1 Hz), 4.02
Acknowledgments
J
＝
＝
＝
(0.6H, dd,
J
9.3, 8.3 Hz), 4.24 (0.4H, dd,
J
9.3,
We thank the staŠ of Advanced Instrumentation
Center For Chemical Analysis Ehime University for
400 MHz NMR and EIMS measurements, and the
staŠ of NMR and MS Operation Center in Faculty
of Pharmaceutical Science at Fukuoka University
for FABMS measurements. We are grateful to
Marutomo Co. for ˆnancial support.
＝
7.3 Hz), 4.29 (0.4H, dd,
J
9.3, 6.8 Hz), 4.39 (0.6H,
＝
＝
dd,
(0.4H, d,
6.45 (0.4H, d,
6.67–6.72 (1.2 H, m), 7.35–7.47 (6H, m), 7.58–7.65
J
9.3, 4.4 Hz), 4.60 (0.6H, d,
J
8.3 Hz), 4.68
7.3 Hz), 5.91 (0.8 H, s), 5.92 (1.2H, s),
8.3 Hz), 6.58–6.64 (1.4H, m),
＝
J
J
＝
＝
(4H, m), 9.70 (0.6H, d,
J
2.0 Hz, CHO), 10.0
＝
(0.4H, d,
J
2.5 Hz, CHO). NMR C(CDCl3) 19.1,
d
19.2, 26.8, 26.9, 51.2, 53.5, 55.1, 60.4, 62.4, 67.2,
67.4, 81.9, 83.1, 101.0, 106.2, 106.7, 108.0, 119.4,
119.9, 127.8, 127.9, 129.9, 130.0, 132.6, 132.9,
133.0, 134.0, 134.7, 135.6, 135.7, 147.1, 147.3,
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