- Email: [email protected]
Geniposidic acid, an iridoid glucoside from Genipa americana
Tetrahedron Lsttcrs
no. 50,
GENIPOSIDIC By R.
pp 5125 -
ACID,
51~
AN IRIDOID
1972;
GLUGOSIDE
at its C -1 carbonl.
cyclopentanoid
P”
I
scent of the nepetalactones4
tallized
to constant
from
was administered specific
R=tl, R’=CH)
24 dpm/ymole;
onine-methyl-14C
also afforded
As a prelude
R’=CHs R=B-D-4eeliebiosr, R’=CH4 R= 8- 0 -glucose, R’ = H
to further
tracer
in fruit of Genipa americana
geniposide insect
(2) or from
(21, 24,
non-glucosidic
monoterpenes5).
to Genipa cuttings
activity
recrystallization,
’
II=@-D-glucose,
and related
28 dpm/pmole,
studies
genipin (27,
28.
constituents.
5125
precursors
genipin (1) isolated
genipin in mother A parallel
28 dpm/pmole;
we set out to examine
(Rubiaceae)
In an -in viva tracer
and labeled
0. 012% total incorporation). labeled
and its 1-P-D-gentiobioside3,
COOR
(ll
of this type and its presence
question whether it is derived
hy-
O
(2)
(8) (4)
a hemiacetal
OR :
Q ”
13 November 1972)
Genipin (1) is one of the few
(Rubiaceae).
/’
mevalonate-2-14C
in Great Britain.
AMERICANA
possessing
geniposide2(2)
jasminoides
CH) ‘I’
aglucones
GENIPA
monoterpene
Both its 1-p-D-glucoside.
occur in the higher plant Gardenia
stable
FROM
reoeived In UK for publication
Genipin (1) is a highly oxygenated
(3),
printed
Pergamon press.
Guarnaccia, K. hi. Madyastha, E. Tegtmeyer and C. J. Coscia (Dept. of Biochemistry, St. Louis University School of Medicine, St. Louis, Missouri 63104)
(Received in USA 3 October
droxyl
1972.
liquors
experiment
led us to (reminiexperiment and recrysfrom
last
with methi-
0. 01% total incorporation).
Genipa americana
for other iridoid
A methanol
extract
of Genipa americana
graphy on Dowex 1-formate
form6.
ester
possessing
nmr
3 7.60
G-10-H),
spectral
(d, C-3-H.
exhibited
J3, 5 - 1 Hz, (s OCH3)r
1.9 +
Upon subjecting specific
glucose
which exhibited
spectral
3 7.62
spectral
(m,
to anion exchange
properties 5.8
properties,
(d, C-3-H.
(m,
C-7-H).
4.75
Am,235
nm
afforded
a methyl [n.,
+9”,
Jl 9= 7 He), .
ester
4. 34 (m
pentaacetate2
m. p. 135”
uv Xmax 235 nm (log g 4. 0); nmr
(m C-l&H),
4.2
(dd, CH20Ac
(4)
4. 34 (m G-10-H)
m. p. 165’,
5. 3 (d, C-l-H,
The methyl
uv:
chromato-
component
J3 5= 0. 5 Hz), ,
of geniposide2(2),
properties,
G-7-H).
acid a major
of this acid with diazomethane
3. 5 (dd, CH2 of glucose).
5.90
2.10
nmr,
J3, 5 = 0. 5 He),
consistent
C-3-H),
glucoside
Treatment
and physical
3. 88 (s 0CH3),
likewise
iridoid
shift in base,
and 3. 5 (dd, CH2 of glucose).
was subjected
Upon elution with 0.1 N formic
was obtained haying characteristic (log E 3. 87) hypsochromic
leaves
7. 47 (d,
of glucose),
3.75
(5 CH3CO). the methyl ester
oxidase
assay7.
8-Glucosidase
the characteristic
with (1) was established
pentaacetate
blue color
by spectral,
to acid hydrolysis treatment
of geniposide
of genipin (1) in the presence
chromatographic
ing points with authentic genipin (l),
glucose
m. p. 118-120”
as well as physical [aID
+136’,
isolated
was detected
(2) afforded
an aglucone
of proteinl. means from
by a
Identity
Mixture
nrelt-
Genipa americana
showed no depression. The pentaacetate ganin tetraacetate to samples
These
Geniposidic
from
was hydrogenated
properties
tetraacetate
data establish
act.
in the presence
obtained by similar
70,
leaves
exhibited
geniposidic
acid (4) and S-adenosyl-L-methionine-methyl-
appearance
of the characteristic
blue color
resulting
of asperuloside8
and
acid as (4).
were incubated with cell-free described9.
was observed.
$-glucosidase
and nmr spectra,
of geniposidic
by chromatography
0.1% methylation
giving 7-deoxylo-
infrared
treatment
and configuration
as previously
of its pentaacetate
84 dpm/nmole),
older Genipa americana
leaves
of Pt02
superimposable
acid (4) and S-adenosyl-L-methionine-methyl-14G
(2) and purification 84,
, including
the structure
from young Genipa americana
geniposide (spec.
with identical
of ‘I-deoxyloganin
gardenoside2.
extracts
methyl ester
actidty 14C.
By addition of carrier
and recrystallisation Cell-free
preparations
during incubation
This was evidenced
upon interaction
with
by gradual
of genipin (1) or the aglu-
5127
100. 50
cone of geniposidic vitro
system These
acid (4) with protein..
from
older leaves
results
suggest
ation and deglucosylation
If loganic
the mixture
acid9 was utilized
remained
acid (4) in the biosynthesis
of iridoid
10
Inouye’s glucosides
with the -in
colorless.
genipin (1) may be readily and supports
as substrate
formed
from
postulation
possessing
geniposidic
acid (4) by methyl-
of the intermediacy a hydroxylated
of geniposidic
C-10 group
Acknowledgements Genipa americana Panama
by Prof.
&.
branches
John Dwyer.
Support from the National
containing
leaves
We thank Prof.
Science
Foundation
in Darien,
and fruit were collected
J. M.
Bobbitt for a generous
GB 17957 and the National
gift of asperuloside.
Institutes
of Health
are acknowledged.
References 1.
C.
Djerassi,
2. Org.
Nakano.
Chem,,z, -
H. Inouye. T.
T.
S
1192 (1961),
Saito.
Endo and A.
F. E.
Regnier.
M.
C. J. Coscia,
7.
J. B.
Field.
a.
L.H.
Briggs,
9.
K.M.
Madyastha,
H. Inouye,
4
W. I.
Dekker,
6.
10.
Chem. ---
G. R. Wailer,
R.
L.
H. Zalkow,
and references
H. Taguchi.
Taguchi,
G. W. K. Cavils, p. 203,
A. N. James,
and T. Pharm.
Endo,
Tetrahedron
Bull.
(Japan),
and A. R.
and J.N.
Shoolery,
cited therein.
E. J. Eisenbraun
Taylor
E. J. Eisenbraun.
g, -
Letters.2347 1066,,(1970).
and H.’ Auda,
Battersby
(1969)..
Phytocbem.,
‘Gyclopentanoid
1,
221 (1968).
Terpene
Derivatives’,
New York (1969).
Guarnaccia,
I. Paston, B.F.
P.
Cain,
and L.
Johnson, P. W.
R. Guarnaccia
S. Ueda,
and Y.
Botta,
Biochemistry,:,
and B. Herring,
LeGuesne.
J. Biol. ---
and J. N. Shoolery,
and C. J. Coscia,
Takada,
5036 (1969).
Tetrahedron
FEBS --_ Letters,
Chem..
235, =
J. Chem. ---
Letters,lrl, 3351 (1970).
1863 (1960). Sot.,
175 (1971).
2595 (1965).
no. 50,
GENIPOSIDIC By R.
pp 5125 -
ACID,
51~
AN IRIDOID
1972;
GLUGOSIDE
at its C -1 carbonl.
cyclopentanoid
P”
I
scent of the nepetalactones4
tallized
to constant
from
was administered specific
R=tl, R’=CH)
24 dpm/ymole;
onine-methyl-14C
also afforded
As a prelude
R’=CHs R=B-D-4eeliebiosr, R’=CH4 R= 8- 0 -glucose, R’ = H
to further
tracer
in fruit of Genipa americana
geniposide insect
(2) or from
(21, 24,
non-glucosidic
monoterpenes5).
to Genipa cuttings
activity
recrystallization,
’
II=@-D-glucose,
and related
28 dpm/pmole,
studies
genipin (27,
28.
constituents.
5125
precursors
genipin (1) isolated
genipin in mother A parallel
28 dpm/pmole;
we set out to examine
(Rubiaceae)
In an -in viva tracer
and labeled
0. 012% total incorporation). labeled
and its 1-P-D-gentiobioside3,
COOR
(ll
of this type and its presence
question whether it is derived
hy-
O
(2)
(8) (4)
a hemiacetal
OR :
Q ”
13 November 1972)
Genipin (1) is one of the few
(Rubiaceae).
/’
mevalonate-2-14C
in Great Britain.
AMERICANA
possessing
geniposide2(2)
jasminoides
CH) ‘I’
aglucones
GENIPA
monoterpene
Both its 1-p-D-glucoside.
occur in the higher plant Gardenia
stable
FROM
reoeived In UK for publication
Genipin (1) is a highly oxygenated
(3),
printed
Pergamon press.
Guarnaccia, K. hi. Madyastha, E. Tegtmeyer and C. J. Coscia (Dept. of Biochemistry, St. Louis University School of Medicine, St. Louis, Missouri 63104)
(Received in USA 3 October
droxyl
1972.
liquors
experiment
led us to (reminiexperiment and recrysfrom
last
with methi-
0. 01% total incorporation).
Genipa americana
for other iridoid
A methanol
extract
of Genipa americana
graphy on Dowex 1-formate
form6.
ester
possessing
nmr
3 7.60
G-10-H),
spectral
(d, C-3-H.
exhibited
J3, 5 - 1 Hz, (s OCH3)r
1.9 +
Upon subjecting specific
glucose
which exhibited
spectral
3 7.62
spectral
(m,
to anion exchange
properties 5.8
properties,
(d, C-3-H.
(m,
C-7-H).
4.75
Am,235
nm
afforded
a methyl [n.,
+9”,
Jl 9= 7 He), .
ester
4. 34 (m
pentaacetate2
m. p. 135”
uv Xmax 235 nm (log g 4. 0); nmr
(m C-l&H),
4.2
(dd, CH20Ac
(4)
4. 34 (m G-10-H)
m. p. 165’,
5. 3 (d, C-l-H,
The methyl
uv:
chromato-
component
J3 5= 0. 5 Hz), ,
of geniposide2(2),
properties,
G-7-H).
acid a major
of this acid with diazomethane
3. 5 (dd, CH2 of glucose).
5.90
2.10
nmr,
J3, 5 = 0. 5 He),
consistent
C-3-H),
glucoside
Treatment
and physical
3. 88 (s 0CH3),
likewise
iridoid
shift in base,
and 3. 5 (dd, CH2 of glucose).
was subjected
Upon elution with 0.1 N formic
was obtained haying characteristic (log E 3. 87) hypsochromic
leaves
7. 47 (d,
of glucose),
3.75
(5 CH3CO). the methyl ester
oxidase
assay7.
8-Glucosidase
the characteristic
with (1) was established
pentaacetate
blue color
by spectral,
to acid hydrolysis treatment
of geniposide
of genipin (1) in the presence
chromatographic
ing points with authentic genipin (l),
glucose
m. p. 118-120”
as well as physical [aID
+136’,
isolated
was detected
(2) afforded
an aglucone
of proteinl. means from
by a
Identity
Mixture
nrelt-
Genipa americana
showed no depression. The pentaacetate ganin tetraacetate to samples
These
Geniposidic
from
was hydrogenated
properties
tetraacetate
data establish
act.
in the presence
obtained by similar
70,
leaves
exhibited
geniposidic
acid (4) and S-adenosyl-L-methionine-methyl-
appearance
of the characteristic
blue color
resulting
of asperuloside8
and
acid as (4).
were incubated with cell-free described9.
was observed.
$-glucosidase
and nmr spectra,
of geniposidic
by chromatography
0.1% methylation
giving 7-deoxylo-
infrared
treatment
and configuration
as previously
of its pentaacetate
84 dpm/nmole),
older Genipa americana
leaves
of Pt02
superimposable
acid (4) and S-adenosyl-L-methionine-methyl-14G
(2) and purification 84,
, including
the structure
from young Genipa americana
geniposide (spec.
with identical
of ‘I-deoxyloganin
gardenoside2.
extracts
methyl ester
actidty 14C.
By addition of carrier
and recrystallisation Cell-free
preparations
during incubation
This was evidenced
upon interaction
with
by gradual
of genipin (1) or the aglu-
5127
100. 50
cone of geniposidic vitro
system These
acid (4) with protein..
from
older leaves
results
suggest
ation and deglucosylation
If loganic
the mixture
acid9 was utilized
remained
acid (4) in the biosynthesis
of iridoid
10
Inouye’s glucosides
with the -in
colorless.
genipin (1) may be readily and supports
as substrate
formed
from
postulation
possessing
geniposidic
acid (4) by methyl-
of the intermediacy a hydroxylated
of geniposidic
C-10 group
Acknowledgements Genipa americana Panama
by Prof.
&.
branches
John Dwyer.
Support from the National
containing
leaves
We thank Prof.
Science
Foundation
in Darien,
and fruit were collected
J. M.
Bobbitt for a generous
GB 17957 and the National
gift of asperuloside.
Institutes
of Health
are acknowledged.
References 1.
C.
Djerassi,
2. Org.
Nakano.
Chem,,z, -
H. Inouye. T.
T.
S
1192 (1961),
Saito.
Endo and A.
F. E.
Regnier.
M.
C. J. Coscia,
7.
J. B.
Field.
a.
L.H.
Briggs,
9.
K.M.
Madyastha,
H. Inouye,
4
W. I.
Dekker,
6.
10.
Chem. ---
G. R. Wailer,
R.
L.
H. Zalkow,
and references
H. Taguchi.
Taguchi,
G. W. K. Cavils, p. 203,
A. N. James,
and T. Pharm.
Endo,
Tetrahedron
Bull.
(Japan),
and A. R.
and J.N.
Shoolery,
cited therein.
E. J. Eisenbraun
Taylor
E. J. Eisenbraun.
g, -
Letters.2347 1066,,(1970).
and H.’ Auda,
Battersby
(1969)..
Phytocbem.,
‘Gyclopentanoid
1,
221 (1968).
Terpene
Derivatives’,
New York (1969).
Guarnaccia,
I. Paston, B.F.
P.
Cain,
and L.
Johnson, P. W.
R. Guarnaccia
S. Ueda,
and Y.
Botta,
Biochemistry,:,
and B. Herring,
LeGuesne.
J. Biol. ---
and J. N. Shoolery,
and C. J. Coscia,
Takada,
5036 (1969).
Tetrahedron
FEBS --_ Letters,
Chem..
235, =
J. Chem. ---
Letters,lrl, 3351 (1970).
1863 (1960). Sot.,
175 (1971).
2595 (1965).