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Crystal structure and absolute configuration of fumitremorgin B, a tremorgenic toxin from Aspergillus fumigatus fres.
CRYS!I’AL
STRUCTURE
A TREMORGENIC
AND ABSOLUTE
TOXIN FROM ASPERGILLUS Mlkio Ysmazskl*
Research
CONFIGURATION
Institute
FUMIGATUS
Faculty
of Pharmaceutxal
Hongo,
Bunkyo-ku,
.
Chlba Urnverslty
, Japan
\ Toshlyukl
FRES
B,
and Haruhiro FuJunoto
for Chemoblcdynamlcs,
Izumicho , Narashlno , Cbba
OF FUMITREMORGIN
and Akiyama,
Usho
Sciences,
Tokyo,
Sankawa and Yolchl
Unlverslty
Iltska
of Tokyo
Japan
(Roeeired IB Japmm26 Ootobor19741roooimd in UK for pblioatioa26 Ilo~a~bor 1974)
In regard
to tremorgenlc
from Asperrtlllus proposed
cribes
fumiaatus Fres.
a structure
the basis
of spectral
studies
was determined
determlned
growrng
(I ) wlthout dlscusslon
the stereostructure
structure
and neurotropic
on FTB
by the X-ray
on the stereochemistry
configuration
analysis
of FTB
P of Hauptman, R-value
l
2 Y 394)
(Karle)
by difference
--I
Me
The relative
on des-
stereochemical configuration
was
of FTB
recrystallized
from MeOH
molecules
in a unit cell
b=24.925,
c=7.321
(A).
of dunenslons
a=1 4.771
A total of 201 I
observed
) independent
collected
mth a Rigaku 4 circle radiation.
mth 4
structure
( 1699
factors
were
diffractometer
The structure
was solved
by means of the MDKS and tmple product formulae
and appllcatlon
revealed
Fourier
This communication
orthorhomblc , space group P2,2,2,
using CuKa
28
B (FTB)
of FTB.
Crystals
8
.
2)
and its absolute
obtalned by the hydrolysis
are
for fumltremorp
of FTB. Itself,
were Isolated
We have previously
derivatives
H n
A 23
1J)
on home niade l*mlsoll.
and its hydrogenated
and the absolute
based on that of prollne
metabolltes , four fumitremorpns
of the tangent formula.
the whole skeletal
syntheses
atoms.
gate the location
The E-map of the solution
Refinement of the missing
27
by least squares atoms including
grving the lowest
techniques the water
followed of crysta-
28
No.
llieatron.
The
anrsotropic
structure
thermal
has been refined
parameters
by block-matnx
least squares
to an R factor
of 0
i
I I with
for C, 0 and N atoms.
C8
As previously purified
by preparative
The optical
2)
reported
rotatory
proline
was obtained by the hydrolysis
paper chromatography
dispersion
of proline
usrng a solvent
with that of the authentic sample of L-(-)
absolute
conflguratlon
1)
a)M
Yamaaakl,
J. Fd.
Hyg.
Pharm.
2)
M.Yamaeakl,
Sot
Bull.
calculation
S.Suzukl,
(Tokyo),
12, 2,
(T.A.)
of the formulae.
proline
system of n-BuOH-AcOH-H20
(S-configuration).
Therefore,
( 4:1 :
which 1s the
H FuJimoto,
Y Maebayashl,
(b)M.Yamazakl,
K.Miyaki, S.Suzukl,
S.Hatakeysma, K.Mlyakr,
Chem.
1739 (1971)
Structure is grateful
and
as shown rn the figure.
370 (l971),
K.Mlyakr,
“Crystal
One of the authors
is establlshed
Japan,
K.Sasago,
3) H A. Hauptman, 4)
Y Hone,
with 6N-HCl
obtalned as above showed a menus plain curve
ldenttcal
of FTB
of FTB
Chem. Commun. Determrnatlonvv to Dr.
408
(I 974).
Plenum Press,
J. V. Sllverton
of N.I.H.
N.Y.
(I 972).
m U.S.A.
for the
I ).
STRUCTURE
A TREMORGENIC
AND ABSOLUTE
TOXIN FROM ASPERGILLUS Mlkio Ysmazskl*
Research
CONFIGURATION
Institute
FUMIGATUS
Faculty
of Pharmaceutxal
Hongo,
Bunkyo-ku,
.
Chlba Urnverslty
, Japan
\ Toshlyukl
FRES
B,
and Haruhiro FuJunoto
for Chemoblcdynamlcs,
Izumicho , Narashlno , Cbba
OF FUMITREMORGIN
and Akiyama,
Usho
Sciences,
Tokyo,
Sankawa and Yolchl
Unlverslty
Iltska
of Tokyo
Japan
(Roeeired IB Japmm26 Ootobor19741roooimd in UK for pblioatioa26 Ilo~a~bor 1974)
In regard
to tremorgenlc
from Asperrtlllus proposed
cribes
fumiaatus Fres.
a structure
the basis
of spectral
studies
was determined
determlned
growrng
(I ) wlthout dlscusslon
the stereostructure
structure
and neurotropic
on FTB
by the X-ray
on the stereochemistry
configuration
analysis
of FTB
P of Hauptman, R-value
l
2 Y 394)
(Karle)
by difference
--I
Me
The relative
on des-
stereochemical configuration
was
of FTB
recrystallized
from MeOH
molecules
in a unit cell
b=24.925,
c=7.321
(A).
of dunenslons
a=1 4.771
A total of 201 I
observed
) independent
collected
mth a Rigaku 4 circle radiation.
mth 4
structure
( 1699
factors
were
diffractometer
The structure
was solved
by means of the MDKS and tmple product formulae
and appllcatlon
revealed
Fourier
This communication
orthorhomblc , space group P2,2,2,
using CuKa
28
B (FTB)
of FTB.
Crystals
8
.
2)
and its absolute
obtalned by the hydrolysis
are
for fumltremorp
of FTB. Itself,
were Isolated
We have previously
derivatives
H n
A 23
1J)
on home niade l*mlsoll.
and its hydrogenated
and the absolute
based on that of prollne
metabolltes , four fumitremorpns
of the tangent formula.
the whole skeletal
syntheses
atoms.
gate the location
The E-map of the solution
Refinement of the missing
27
by least squares atoms including
grving the lowest
techniques the water
followed of crysta-
28
No.
llieatron.
The
anrsotropic
structure
thermal
has been refined
parameters
by block-matnx
least squares
to an R factor
of 0
i
I I with
for C, 0 and N atoms.
C8
As previously purified
by preparative
The optical
2)
reported
rotatory
proline
was obtained by the hydrolysis
paper chromatography
dispersion
of proline
usrng a solvent
with that of the authentic sample of L-(-)
absolute
conflguratlon
1)
a)M
Yamaaakl,
J. Fd.
Hyg.
Pharm.
2)
M.Yamaeakl,
Sot
Bull.
calculation
S.Suzukl,
(Tokyo),
12, 2,
(T.A.)
of the formulae.
proline
system of n-BuOH-AcOH-H20
(S-configuration).
Therefore,
( 4:1 :
which 1s the
H FuJimoto,
Y Maebayashl,
(b)M.Yamazakl,
K.Miyaki, S.Suzukl,
S.Hatakeysma, K.Mlyakr,
Chem.
1739 (1971)
Structure is grateful
and
as shown rn the figure.
370 (l971),
K.Mlyakr,
“Crystal
One of the authors
is establlshed
Japan,
K.Sasago,
3) H A. Hauptman, 4)
Y Hone,
with 6N-HCl
obtalned as above showed a menus plain curve
ldenttcal
of FTB
of FTB
Chem. Commun. Determrnatlonvv to Dr.
408
(I 974).
Plenum Press,
J. V. Sllverton
of N.I.H.
N.Y.
(I 972).
m U.S.A.
for the
I ).