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Lythraceae alkaloids. Structure and stereochemistry of the biphenyl ether alkaloids of decodon verticillatus
Tetrahedron Letters No.42, printed in Great Britain.
pp, 5125-5128,
1966.
Pergmn
press
Ltd.
LY THRACEAE ALKALOIDS. STRUCTURE AND STEREOCHEMISTRY OF THE BIPHENYL ETHER ALKALOIDS OF DECODON VERTICILLATUS (1) James P. Ferris, R. C. Briner. C. B. Boyce and M. J. Wolf Department of Chemistry, Florida State University, Tallahassee, Florida The Salk Institute for Biological Studies, Ia Jolla, California (Received
17 July 19661 in revised
In our previous alkaloids
verticillatus,
our attention decaline
because
revealed
the presence
were
from
of interest
and vertaline.
could be detected
in the infrared
groups
spectra
bases
(2)
Decodon
alkaloids
were
extracts
decaline
a chemically
or n. m. r.
was
plant family. from
of in-
of Decodon
of two new alkaloids,
as no direct
and the observation
of these
of the major
which on methylation
each contained
to be an ether,
n. m. r.
amounts
Structurally
that was assumed
two methoxyl
These
of the basic
of appreciable
because
alkaloids
(3)
investigation
15 Angust 1966)
the Lythraceae
and desmethylvertaline,
to decaline
forr
the structures
to two minor
and vertaline.
further
methyldecaline verted
we reported
that have been isolated
We then turned
ter&t
paper
inert
oxygen
link
for its presence The presence
of six aromatic
compatible
con-
and vertaline
evidence
spectra.
des-
were
protons
with abiphenyl
of
in the
ether
function. At this point an x-ray of vertaline
was undertaken
munication
by Dr.
We were
u. v.
and Dr.
tern of the biphenyl in the stereochemistry
ether
L.
structure
The i. r.,
of decaline
are identical.
of the structure
and this resulted
Hamilton
structure.
spectra
spectra
J.
then able to assign
of the vertaline and mass
analysis
This
establishes
is the same
in structure
Steinrauf)
I (private
for vertaline.
IV to decaline
n. m. r.
and vertaline
of the hydrobromide
optical
at the quinolizidine
5123
dispersion
idqntical
that the methoxylation
in each and the bases ring.
(4)
with the aid
rotatory
are virtually
com-
differ
and the patonly
5126
No.12
bCH,
NH8
III
IV
G$:
OCH,
a v 0.
cl.J:
R=H,R':H
VI 0. R=H,R'=H
b.
R:CHs, R':H
b. R=CH,, R':H
c.
R:R'= CH,CO
c. R:R'=CH,CO
No.13
5127
When decaline resonance
of H-3”
observed
and vertaline shifts
previously
N-oxide
oxygen
from
with the biphenyl
coming
in close
This peak, is a singlet
in decaline in I.
pattern
The deshielding
of H-3”
Models
reveals
It was possible
of the -cis or trans
nature
consistent
are clearly
Furthermore, and 7. 05 t former
and a trans-fusion
onance
of the methiodide (6.41
decaline
the basis
Emde
only in cleavage
is consistent
in the latter.
ether series
(6)
ring fusion.
with a trans-fusion
in the
field
resthan
in decaline.
(7)
II or IV.
degradation
assign
the structure
IV to decaline
of the methiodides
with sodium
of decaline
in liquid ammonia
amine to yield
(2) but also
series.
not of
and Va in
Compounds
Vb and VIb and acetylated
on
and
results
in cleavage
3-phenylpropanol
and Via in the vertaline to yield
is at higher
(5)
series
the N-methyl
) consistent
(8) and lactone
methylated
and
with a cis-fusion -
Finally 7)
in
“Bohlmann
the vertaline
(6.79
of the quarternary
the biphenyl
(6. 68 yin
bands”
of decaline
of decaline
reduction
the decaline Via were
series)
to uniquely
of the Emde
vertaline.
t
spectra
with a trans-quinolizidine shift of H-4
is either
It was possible
ring juncture.
However,
consistent
this re-
III as a possibility
of the quinolizidine
in the infrared
with the
fulfill
with the -cis ring fusion.
in the decaline
Therefore,
analysis II-IV
structure
by the
that the oxygen
“Bohlmann
the chemical
that of vertaline
requires
do not exhibit
observable
desmethyldecaline
ring at H-3”.
as predicted
Stereochemical
to eliminate
and desmethylvertaline
the infrared bands”
and vertaline,
that only structures
on the basis
the n. m. r. shift was
(2) and is due to the
to the phenyl
in the N-oxides
quirement.
Vertaline
alkaloids
group be next to H-3”.
aid of Dreiding
to N-oxides A similar
proximity
methoxylarion
of the N-oxide
are converted
2. 8 2 to2.1Z.
to yield
Va and Vc and
VIC. It was not possible line form
although
to obtain the derivatives
in some
obtained
on the amorphous
confirm
the assigned
285 rnp
6 5890)
instances
structures.
and mass
satisfactory
preparations.
spectra
of V and VI in crystalanalytical
The spectral
The u. V. spectra (e.g.
VIc,
Mt 407,
data were
data in Table
(e.g.
Via,
Xmax
N-methylpiperi-
I
5128
No.42
deine ion 98) provides
further
support
for these
TABLE N-CH3= -
OCH3= ~
Va Vb VC
7.70 7.68 7. 80
Via VIb VIC
7.60 7.60 7.75
The optical
structure
CH3COb
6.21 (6 protons) 6. 25, 6. 20, 6. 16 6.20, 6. 15
7. 62,
8. 00
1770,
1740
6.20 6.21, 6.23,
7.70,
8.00
1770,
1740
Address
J. P. Ferris, Kirkpatrick, J.
n.m.
rotation
of decaline.
(2) (3)
(6 protons) 6. 19, 6. 14 6. 18
P.
(IX-I-~)
and that of VIb is -35’
to J. P. F.
C. B. Boyce, J. A. Weisbach,
Therefore
which
IV is the
J. Org.
Chem.
27,
(4)
F.
(6)
F. Bohlmann, 2705 (1965)
(7)
T. M. Moynehan, K. Schofield, Katritzky, J. Chem. Sot. 2637
(8)
P. A. (1937)
Sartoretto and R. H.
2985
B. Douglas, J. L. Letters. in press (1966)
(1962)
communication.
Chem. D.
at The Salk Institute.
R. C. Brines, Tetrahedron
(5)
(9)
i. r.
are diasteriomers.
See accompanying Bohlmann,
b.
(9)
correspondence
Ferris,
(z)
r.
of Vb is t60°
that Vb and Vb
(1)
I CH3COa
a.
establishes
structures.
Ber.
Schumann
&l,
2157
(1958)
and C. Arndt, R. A. (1962)
Y.
Tetrahedron Jones
and A.
Letters. R.
and F. J. Sowa, J. Am. Chem. Sot. 2. 503 F. Manske, 55 (1950) -ibid. z, Another biphenyl ether alkaloid, lagerine, oxygenated at the 5” and 6’ positions and with the lactone side chain at the 3’ position has been isolated from Lagerstroemia indica.
pp, 5125-5128,
1966.
Pergmn
press
Ltd.
LY THRACEAE ALKALOIDS. STRUCTURE AND STEREOCHEMISTRY OF THE BIPHENYL ETHER ALKALOIDS OF DECODON VERTICILLATUS (1) James P. Ferris, R. C. Briner. C. B. Boyce and M. J. Wolf Department of Chemistry, Florida State University, Tallahassee, Florida The Salk Institute for Biological Studies, Ia Jolla, California (Received
17 July 19661 in revised
In our previous alkaloids
verticillatus,
our attention decaline
because
revealed
the presence
were
from
of interest
and vertaline.
could be detected
in the infrared
groups
spectra
bases
(2)
Decodon
alkaloids
were
extracts
decaline
a chemically
or n. m. r.
was
plant family. from
of in-
of Decodon
of two new alkaloids,
as no direct
and the observation
of these
of the major
which on methylation
each contained
to be an ether,
n. m. r.
amounts
Structurally
that was assumed
two methoxyl
These
of the basic
of appreciable
because
alkaloids
(3)
investigation
15 Angust 1966)
the Lythraceae
and desmethylvertaline,
to decaline
forr
the structures
to two minor
and vertaline.
further
methyldecaline verted
we reported
that have been isolated
We then turned
ter&t
paper
inert
oxygen
link
for its presence The presence
of six aromatic
compatible
con-
and vertaline
evidence
spectra.
des-
were
protons
with abiphenyl
of
in the
ether
function. At this point an x-ray of vertaline
was undertaken
munication
by Dr.
We were
u. v.
and Dr.
tern of the biphenyl in the stereochemistry
ether
L.
structure
The i. r.,
of decaline
are identical.
of the structure
and this resulted
Hamilton
structure.
spectra
spectra
J.
then able to assign
of the vertaline and mass
analysis
This
establishes
is the same
in structure
Steinrauf)
I (private
for vertaline.
IV to decaline
n. m. r.
and vertaline
of the hydrobromide
optical
at the quinolizidine
5123
dispersion
idqntical
that the methoxylation
in each and the bases ring.
(4)
with the aid
rotatory
are virtually
com-
differ
and the patonly
5126
No.12
bCH,
NH8
III
IV
G$:
OCH,
a v 0.
cl.J:
R=H,R':H
VI 0. R=H,R'=H
b.
R:CHs, R':H
b. R=CH,, R':H
c.
R:R'= CH,CO
c. R:R'=CH,CO
No.13
5127
When decaline resonance
of H-3”
observed
and vertaline shifts
previously
N-oxide
oxygen
from
with the biphenyl
coming
in close
This peak, is a singlet
in decaline in I.
pattern
The deshielding
of H-3”
Models
reveals
It was possible
of the -cis or trans
nature
consistent
are clearly
Furthermore, and 7. 05 t former
and a trans-fusion
onance
of the methiodide (6.41
decaline
the basis
Emde
only in cleavage
is consistent
in the latter.
ether series
(6)
ring fusion.
with a trans-fusion
in the
field
resthan
in decaline.
(7)
II or IV.
degradation
assign
the structure
IV to decaline
of the methiodides
with sodium
of decaline
in liquid ammonia
amine to yield
(2) but also
series.
not of
and Va in
Compounds
Vb and VIb and acetylated
on
and
results
in cleavage
3-phenylpropanol
and Via in the vertaline to yield
is at higher
(5)
series
the N-methyl
) consistent
(8) and lactone
methylated
and
with a cis-fusion -
Finally 7)
in
“Bohlmann
the vertaline
(6.79
of the quarternary
the biphenyl
(6. 68 yin
bands”
of decaline
of decaline
reduction
the decaline Via were
series)
to uniquely
of the Emde
vertaline.
t
spectra
with a trans-quinolizidine shift of H-4
is either
It was possible
ring juncture.
However,
consistent
this re-
III as a possibility
of the quinolizidine
in the infrared
with the
fulfill
with the -cis ring fusion.
in the decaline
Therefore,
analysis II-IV
structure
by the
that the oxygen
“Bohlmann
the chemical
that of vertaline
requires
do not exhibit
observable
desmethyldecaline
ring at H-3”.
as predicted
Stereochemical
to eliminate
and desmethylvertaline
the infrared bands”
and vertaline,
that only structures
on the basis
the n. m. r. shift was
(2) and is due to the
to the phenyl
in the N-oxides
quirement.
Vertaline
alkaloids
group be next to H-3”.
aid of Dreiding
to N-oxides A similar
proximity
methoxylarion
of the N-oxide
are converted
2. 8 2 to2.1Z.
to yield
Va and Vc and
VIC. It was not possible line form
although
to obtain the derivatives
in some
obtained
on the amorphous
confirm
the assigned
285 rnp
6 5890)
instances
structures.
and mass
satisfactory
preparations.
spectra
of V and VI in crystalanalytical
The spectral
The u. V. spectra (e.g.
VIc,
Mt 407,
data were
data in Table
(e.g.
Via,
Xmax
N-methylpiperi-
I
5128
No.42
deine ion 98) provides
further
support
for these
TABLE N-CH3= -
OCH3= ~
Va Vb VC
7.70 7.68 7. 80
Via VIb VIC
7.60 7.60 7.75
The optical
structure
CH3COb
6.21 (6 protons) 6. 25, 6. 20, 6. 16 6.20, 6. 15
7. 62,
8. 00
1770,
1740
6.20 6.21, 6.23,
7.70,
8.00
1770,
1740
Address
J. P. Ferris, Kirkpatrick, J.
n.m.
rotation
of decaline.
(2) (3)
(6 protons) 6. 19, 6. 14 6. 18
P.
(IX-I-~)
and that of VIb is -35’
to J. P. F.
C. B. Boyce, J. A. Weisbach,
Therefore
which
IV is the
J. Org.
Chem.
27,
(4)
F.
(6)
F. Bohlmann, 2705 (1965)
(7)
T. M. Moynehan, K. Schofield, Katritzky, J. Chem. Sot. 2637
(8)
P. A. (1937)
Sartoretto and R. H.
2985
B. Douglas, J. L. Letters. in press (1966)
(1962)
communication.
Chem. D.
at The Salk Institute.
R. C. Brines, Tetrahedron
(5)
(9)
i. r.
are diasteriomers.
See accompanying Bohlmann,
b.
(9)
correspondence
Ferris,
(z)
r.
of Vb is t60°
that Vb and Vb
(1)
I CH3COa
a.
establishes
structures.
Ber.
Schumann
&l,
2157
(1958)
and C. Arndt, R. A. (1962)
Y.
Tetrahedron Jones
and A.
Letters. R.
and F. J. Sowa, J. Am. Chem. Sot. 2. 503 F. Manske, 55 (1950) -ibid. z, Another biphenyl ether alkaloid, lagerine, oxygenated at the 5” and 6’ positions and with the lactone side chain at the 3’ position has been isolated from Lagerstroemia indica.