1977. Published by the Chemical. Society of Japan. THE CONFIGURATION OF(+)-GLUTINOSONE1). Akio MURAI, Hirofumi. TAKETSURU, Fujio. YAGIHASHI,.
CHEMISTRY
LETTERS,
pp.
663-664,
1977.
Published
THE CONFIGURATION
Akio
MURAI,
Hirofumi
of
Chemistry,
Fujio
The
configuration
Science,
transformation
in
the
presence
of
Glutinosone, isolated
an
from
was
assiqned
all
asymmetric
pletely
leaves
of
centers
and
benzene
We
3-monoacetates
(room
with
at
C2
and
the
(1.2
oil,in
5
h)
reagent
in
in
46%
and
have
not
comis
cor-
the
at
methanol
C3).The
temp,
the
1Ba
R=Ac
and
23%
25
min) to
and
yields,
qlycol(2)(5
at
and
C3)and4.72(3H,br,3H
J=6.5,8.5,and
of
8.5
ether
1H,ABq of
corresponding
R=H
34
2-
Hz, H
at
and
water
(room
temp,
compound,2-oxo-3-acetate(3),oil,in
hydrolysis with
in
the
3-monoacetate(2b),when oxidized
2.95(each
C3).Treatment
(room
afforded
107-107.5℃,
mixture
2-dehydr。 and
pyridine
chromatography
the unreacted
heterogeneous
δ2.71
yield,
group
of
anhydride(2.3equiv)in by
t
bond with concomitant a
virus,
configuration
that(+)-qlutinosone
Hz,H
at a
into
J=9Hz, H equiv)
and
mosaic
the
evidence
followed
J=8.5Hz,H
converted
tobacco
isopropenyl
2,3-diacetate3)(2c)and
yield:[α]D±59.4°;
4.84(1H,d
double
describe
３.31(1H,tJ=8.5
Jones
basis
as "phytoalexin"
with
an
C12):2b,[α]D-38.9°;δ3.62(1H,do
21h),was 61%
now
60.5-62.5℃
the
4.60(1H,t
with
of
acetic
temp,
35%):2a,4)[α]D-33.6° δ
C2)and
the
NMR spectrum
formula 1B.
(2a)and 2b),mp
respectively,
on the
qualified infected
(-)-rishitin3)(2)with (1:20)
and
coworkers.2)However,
disposition
yet. by
Treatment of and
glutinosa
by Burden
determined
represented
KATSUI,
reagent.
Nicotiana
the
Japan
University,
determined
(-)-rishitin
norsesquiterpene
and
Nobukatsu
Hokkaido
was
from
shift
antifungal
formula 1A
been
rectly
the
of
060
of(+)-glutinosone
chemical
Society
MASAMUNE of
Sapporo
the
Chemical
YAGIHASHI,
Tadashi
Faculty
of
the
OF(+)-GLUTINOSONE1)
TAKETSURU, and
Department
by
J=19
compound 3 resulted
a Hz,2H
with in
at
potassium
migration
of
give△1(10)-3-hydroxy-2-ketone(1B), 3-acetate(1Ba),oil,(41%):1B;[α]D
2
R1=α-OH,β-H,R2=α-H,β-OH 2aR1=α-OAc,β-H,R2=α-H,β-OH
2bR1=α-OH,β-H,R2=α-H,β-OAc 2c R1=α-OAc,β-H,R2=α-H,β-OAc 3 R1=O,R2=α-H,β-OAc
C1)and hydroxide the
5(10)-
4
664
Chemistry
+57.2°;m/e
220(M+),192,191,162,147,134,121,
and
(ε14,500);vmax(CHCl3)3470,1676,1645,1620,and
d
J = 6 Hz,
H at
14-CH3),
C3),
4.72
C1)= 1Ba,
(2H,
CH3)
and
5.11
identical at
C4
Hydride
in
(CDCl3)
1.11 (1H,
d
of
the
NMR signals
0.6
to
the
respective
collapsed
a
C4
=
10
that
C5 the
be
(ε
to
the
glutinosone
of
(1H,
(CDCl3)
the
1.12
spectra
the
(1B)
(NaBH4 in
C2H5OH)
do
d J
(1H,
br
s WH = 5 Hz,
question
and
A ring shift
shown
J
=
6
Hz,
H at
Hz,
14-
were
exists
in
and
a half-chair
reagent
Eu(dpm)3
protons
on
in
= 10
formula 4.
8 Hz,
(4),
H at
H at
C3),
C1).
The
conformation.2)
effected
the
glycol2) 3400cm-1;δ
Ad-
complete
A ring,
which
Irradiation
separation
were
at
correlated
δ 3.89
(14-CH3)
6.80 tricou-
protons
It
12
configura-
gave and
(1H,
the two
d
absolute
5.28
δ
J =
compound 1B
3.18
the
d
s WH = 4 Hz,
(3H,
of
establishing
(1H,
br
14-CH3),
broad
at
follows at
ring
and
C5
is
hence,(+)-
correctly
Part
XV of
represented
"Studies
Kitahara, 50,
F. 1217
2)
R.
S.
3)
N.
Katsui,
J.
Chem.
A.
Matsunaga,
Soc.
1201
All
compounds
UV and
the
N.
The
M.
and
T.
G.
Takasugi,
Commun.,
G. M.
1968,
N.
described good
XIV,
Masamune,
Vincent,
N. and
Katsui, N.
A.
Sato,
Matsunaga,
Bull.
Phytochemistry,
Imaizumi,
43;
Sato,
herein
accord
with
were
spectra
Chem.
Soc.
and
T. K.
T.
Masamune, Tomiyama,
14,
Masamune, A.
and
Murai,
Bull.
221
K.
M.
Chem.
(1975).
Tomiyama,
Takasugi,
Soc.
Jpn.,
gave the
measured
otherwise denote
elementary
assigned in
analyses
structures.
ethanol,
stated.
ethanol
Abbreviations
"singlet,
doublet,
and The and
IR,
d,
and
NMR
rotations,
carbon
"s,
triplet,
MS,
optical
tetrachloride, t,
q,
quartet,
br,
and
broad,
do"
and
respectively.
optical
rotation
unknown;
R.
We are
indebted
spectra
Part
Murai,
.
unless
double,"
A.
Katsui,
NMR spectra
NMR
FOOTNOTES
Phytoalexins;"
Bailey,
Chem.
respectively, in
A.
Murai,
(1977)
in
the
Yagihashi,
J. A.
50,
on
and
(1977).
Burden,
spectra
6)
5.90
3.79
C2),
at
in
A
is
Jpn.,
5)
δ
All
OH),
(1B)•5,6)
individual as
Hz.
nm
formula 1B.
H.
4)
s,
and
15,200);
C3).
REFERENCES 1)
(1H,
C12),
glutinosone,
the
to
10
237
axial(α-configuration)in
respect
by
H at
indicating
proton
oriented
that
between to
nm
Hz,
H at
slightly
Hz),
236
= 6 Hz,
signa15
constant and
J
multiplet a
2H at
(+)-glutinosone
8 Hz,
equiv
broad
3.72
yield:[α]D-29.6°;vmax(CHCl3)3580
due
C4)into
pling
d
mol
13-CH3),
of (+)-glutinosone
indicated
dition
(J
natural
56%
J =
of
plat
of C7 of
a
(3H,
br
NMR spectrum
at
12
reduction
mp136-138℃,
4.06
mex
and
s,
s WH = 5 Hz,
d J =
those
C3,
(3H,
λ
(1H,
with
tions
(H
br
94(base);λmax
1977
896cm-1;δ(CDCl3)1.23(3H,
1.73
[α]D±64.8°,
Letters,
of
S.
Burden to
of
glutinosone (private
Doctor
R.
or
any
communication, S.
Burden
for
of
its
derivatives
has
so
far
been
1977). providing
us
with
copies
of
the
glutinosone.
(Received
March 31, 1977)
