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On stereochemistry of osmium tetroxide oxidation of allylic alcohol systems: examples
Tetrahedron Letters,Vo1.24,No.37,pp Printed in Great Britain
ON STEREOCHEMISTRY
OF OSMIUM
0040-4039/83 $3.00 + .OO 01983 Pergamon Press Ltd.
3947-3950,1983
TETROXIDE
OXIDATION
OF ALLYLIC
ALCOHOL
SYSTEMS:
EXAMPLES
W. J. Christ, Department
of Chemistry,
Forty-two
Abstract:
examples
formulation
In the outcome mulation known
preceding
of osmium
in the
compounds fied
and
into
at only
or alkoxyl compound
(b) conjugated
end
cases
group
the
at both
ratio
of
examples
from
examples
are
ends
due
of the and
this
are
their
02138,
USA
of
the empirical
of the
stereochemical
divided
nonconjuqated
to a hydroxyl cases
where
olefinic minor
as well
in the Table
further
The
for-
classification
into
(a) nonconjugated
compounds group
center
ratio
are
of
classi-
is present
due
to a hydroxyl
indicated
predicted
stereoisomers,
This
as examples
with
or alkoxyl a chiral
bond.
1,2
derivatives.
laboratory
Finally,
(2) the
the major
and
listed
systems
center and
formulation
alcohols
compounds.
bond,
the consistency
an empirical
Acyclic
a chiral
olefinic
is present
represents
selected
Massachusetts
paper.
of allylic
carbonyl
where
of the
presented
systems.
and Y. Kishi* Cambridge,
to demonstrate
preceding
unpublished
Some
(B) cyclic
(1) the
one
in the
oxidation
with
J. K. Cha, University,
presented
we have
paper,
tetroxide
literature. and
are
proposed
is consistent
(A) acyclic
Harvard
by
for
this
each
empirical
formulation. Seventeen
examples
fact
that,
tive
osmylation
alkoxyl seem
group
SV20.21, This
exceptions
are
Related stereochemical Preliminary paper
have
product
obtained
Acknowledgment National his
(examples
that
appreciation
Financial
for
to these
35 and --
assistance
poor
a chiral
bond
(examples
each
in compounds
also
other for
conjugated
must
except
due
under one
22,
A-a-2),
the
their
or
effects
in compounds
24 and --
Is,
26.
compounds
carefully,
out
stereoselec-
to a hydroxyl
another
carbonyl
be made
to point
in directing
center
complement
systems
for
since
(examples at
least
two
osmylation,
oxidation of
it would
of allylic of
the
the major
be
alcohols
olefins
interesting and
their
described
product
corresponds
Science
Foundation
to examine
the
derivatives.
in the to that
preceding of
the major
oxidation.5
from
(NS 12108)
a postdoctoral
where
are
two groups
oxidation
stereochemistry
of Health
cases
explanation
groups
36).314
formulation
tetroxide
further
acyl
olefinic
of
counteract
on permanganate the
by osmium
Institutes
of the
effects
of permanganate
experiments
the
to be applicable
empirical
outcome
shown
they
application
known
to the
while
ends
the
require paper,
For
and -17).
is,
seems
However,
do not
preceding
at both
that
formulation
A-b).
2
is present
-23 and 25,
A-a-l
in the
(examples
to be additive;
under
under
as mentioned
the National is gratefully
fellowship
from
3947
acknowledged.
Merck,
Sharp
and
One
(CHE of us
Dohme.
78-06296) (WJC)
and
the
expresses
3948
Table
A. Acyclic
System3
a. Nonconjugated
Compounds
- 1
G8 :
Fatlo
= 1:o
R=X2=H. X1=CH*OMe g8 :
Patio
= *:1
R = cFyMe,
2 = x2 =
acetonL%
14 lo
10
11
:
Ratio = 1:O x = SLm)2w-B”l,
:
Ratio
R =
=
7:l
(CH2) 202X (Ph)
z(t-N
15
11
:
Rat10
x = Si(Ph)*M3U),
a. Nonconjugated
Compounds
- 2
R
=
B-O”
= 4:l R =
B-oaz1
3949
Table A. a. Nonconjugated
A. Acyclic
- 2 (Continued)
Systems
b. Conjugated
B. Cyclic
Compounds
Carbonyl
Systems
Compounds
(Continued)
3950
References 1.
J. K. Cha, W. J. Christ,
2.
For a review on osmium
3.
H. Fujioka,
7367
K.
J.
Tetrahedron
oxidation,
to the differences and isolated
carbonyl
may take the preferred
rule.
(1959).
In the organic
Gilbert
stork at Columbia esters.
the one expected The experiment interesting
fashion, dicted
colloquium
compounds. somewhat
R. H. Cornforth,
conformation
Namely,
resembling
University
discussed
0~04 oxidation
outcome
by Iwai and Tomita
Potassium
Assuming
permanganate
for osmium
tetroxide
oxidation
oxidation
outcome
for the
J. Chem. Sot., 112 Professor
was also opposite
to
Bull. Japan, 2, 976 (1961)l is
of diene -43 yielded
arabinose,
takes place on the diene system
of permanganate
oxidation
was opposite
but
in a stepwise
to that pre-
oxidation.
Adv. Carbohydr.
This ratio is based on the amount of product(s) W. J. Christ,
9.
S. S. Ko, M. Yonaga,
J. K. Cha, and Y. Kishi, and Y. Kishi,
S. S. Ko, J. M. Finan, M. Yonaga,
:
arabinose
2, 107 (1946).
Chem.,
8.
104,
carbonyl
of trisubstituted
of his example
[Chem. Pharm.
permanganate
7.
10.
J. Am.
the dipole model
on March 14, 1983, at Harvard University,
The stereochemical
the stereochemical
R. Lespieau,
(1980).
between
unsaturated
and K. K. Mathew,
-45 6.
187
and Y. Hirata,
from this formulation.
reported
to add.
not ribose.
in the preferred
olefinic
conformation
See, J. W. Cornforth,
a,&unsaturated
Chem. Rev., _, 80
see M. Schroder,
(1982).
a,@unsaturated compounds
Lett., 24, 0000 (1983).
Cha, J. Leder, Y. Kishi, D. Uemura,
This might be attributed
Cram's
5.
tetroxide
W. J. Christ,
Chem. Sot., 104, 4.
and Y. Kishi,
and Footnotes
isolated
unpublished
unpublished
by crystallization.
results.
results.
Y. Kishi, D. Uemura,
and Y. Hirata,
J. Am. Chem. Sot.,
7364 (1982).
11.
S. H. Kang, W. W. McWhorter,
12.
J. A. Secrist,
13.
T. Katsuki,
and Y. Kishi, unpublished
III and K. D. Barnes,
A. W. M. Lee, P. Ma, V. S. Martin,
and F. J. Walker,
J. Org. Chem.,
47, 1373
14.
N.
15.
R. Behrend
and G. Heyer, Justus Liebigs
16.
H. Fujioka
and Y. Kishi,
K. Kochetkov
and B. A. Dmitriev,
unpublished
Th. Posternak
and H. Friedli,
Wolczunowicx,
Bars, Cocu, and Posternak
Chim. Acta,
K. B. Sharpless,
z,
803 (1965).
Ann. Chem., 418,
Helv. Chim. Acta, 6,
the stereochemistry
pointed
294
(1919).
251 (1953).
out the importance
of 0s04 oxidation
R. M. Srivastava
20.
D. M. Vyas and G. W. Hay, Can. J. Chem., 53,
and R. K. Brown, Can. J. Chem., 49,
1339
1362 (1975).
of homoallylic
hydroxyl
of polyhydroxycyclopentenes
53, 2288 (1970) and references cited therein].
19.
(Received in USA 24 May 1983)
D. Tuddenham,
results.
18.
in directing
4526 (1980).
S. Masamune,
(1982).
Tetrahedron,
17.
groups
results,
J. Org. Chem., 45,
(1971).
[Helv.
ON STEREOCHEMISTRY
OF OSMIUM
0040-4039/83 $3.00 + .OO 01983 Pergamon Press Ltd.
3947-3950,1983
TETROXIDE
OXIDATION
OF ALLYLIC
ALCOHOL
SYSTEMS:
EXAMPLES
W. J. Christ, Department
of Chemistry,
Forty-two
Abstract:
examples
formulation
In the outcome mulation known
preceding
of osmium
in the
compounds fied
and
into
at only
or alkoxyl compound
(b) conjugated
end
cases
group
the
at both
ratio
of
examples
from
examples
are
ends
due
of the and
this
are
their
02138,
USA
of
the empirical
of the
stereochemical
divided
nonconjuqated
to a hydroxyl cases
where
olefinic minor
as well
in the Table
further
The
for-
classification
into
(a) nonconjugated
compounds group
center
ratio
are
of
classi-
is present
due
to a hydroxyl
indicated
predicted
stereoisomers,
This
as examples
with
or alkoxyl a chiral
bond.
1,2
derivatives.
laboratory
Finally,
(2) the
the major
and
listed
systems
center and
formulation
alcohols
compounds.
bond,
the consistency
an empirical
Acyclic
a chiral
olefinic
is present
represents
selected
Massachusetts
paper.
of allylic
carbonyl
where
of the
presented
systems.
and Y. Kishi* Cambridge,
to demonstrate
preceding
unpublished
Some
(B) cyclic
(1) the
one
in the
oxidation
with
J. K. Cha, University,
presented
we have
paper,
tetroxide
literature. and
are
proposed
is consistent
(A) acyclic
Harvard
by
for
this
each
empirical
formulation. Seventeen
examples
fact
that,
tive
osmylation
alkoxyl seem
group
SV20.21, This
exceptions
are
Related stereochemical Preliminary paper
have
product
obtained
Acknowledgment National his
(examples
that
appreciation
Financial
for
to these
35 and --
assistance
poor
a chiral
bond
(examples
each
in compounds
also
other for
conjugated
must
except
due
under one
22,
A-a-2),
the
their
or
effects
in compounds
24 and --
Is,
26.
compounds
carefully,
out
stereoselec-
to a hydroxyl
another
carbonyl
be made
to point
in directing
center
complement
systems
for
since
(examples at
least
two
osmylation,
oxidation of
it would
of allylic of
the
the major
be
alcohols
olefins
interesting and
their
described
product
corresponds
Science
Foundation
to examine
the
derivatives.
in the to that
preceding of
the major
oxidation.5
from
(NS 12108)
a postdoctoral
where
are
two groups
oxidation
stereochemistry
of Health
cases
explanation
groups
36).314
formulation
tetroxide
further
acyl
olefinic
of
counteract
on permanganate the
by osmium
Institutes
of the
effects
of permanganate
experiments
the
to be applicable
empirical
outcome
shown
they
application
known
to the
while
ends
the
require paper,
For
and -17).
is,
seems
However,
do not
preceding
at both
that
formulation
A-b).
2
is present
-23 and 25,
A-a-l
in the
(examples
to be additive;
under
under
as mentioned
the National is gratefully
fellowship
from
3947
acknowledged.
Merck,
Sharp
and
One
(CHE of us
Dohme.
78-06296) (WJC)
and
the
expresses
3948
Table
A. Acyclic
System3
a. Nonconjugated
Compounds
- 1
G8 :
Fatlo
= 1:o
R=X2=H. X1=CH*OMe g8 :
Patio
= *:1
R = cFyMe,
2 = x2 =
acetonL%
14 lo
10
11
:
Ratio = 1:O x = SLm)2w-B”l,
:
Ratio
R =
=
7:l
(CH2) 202X (Ph)
z(t-N
15
11
:
Rat10
x = Si(Ph)*M3U),
a. Nonconjugated
Compounds
- 2
R
=
B-O”
= 4:l R =
B-oaz1
3949
Table A. a. Nonconjugated
A. Acyclic
- 2 (Continued)
Systems
b. Conjugated
B. Cyclic
Compounds
Carbonyl
Systems
Compounds
(Continued)
3950
References 1.
J. K. Cha, W. J. Christ,
2.
For a review on osmium
3.
H. Fujioka,
7367
K.
J.
Tetrahedron
oxidation,
to the differences and isolated
carbonyl
may take the preferred
rule.
(1959).
In the organic
Gilbert
stork at Columbia esters.
the one expected The experiment interesting
fashion, dicted
colloquium
compounds. somewhat
R. H. Cornforth,
conformation
Namely,
resembling
University
discussed
0~04 oxidation
outcome
by Iwai and Tomita
Potassium
Assuming
permanganate
for osmium
tetroxide
oxidation
oxidation
outcome
for the
J. Chem. Sot., 112 Professor
was also opposite
to
Bull. Japan, 2, 976 (1961)l is
of diene -43 yielded
arabinose,
takes place on the diene system
of permanganate
oxidation
was opposite
but
in a stepwise
to that pre-
oxidation.
Adv. Carbohydr.
This ratio is based on the amount of product(s) W. J. Christ,
9.
S. S. Ko, M. Yonaga,
J. K. Cha, and Y. Kishi, and Y. Kishi,
S. S. Ko, J. M. Finan, M. Yonaga,
:
arabinose
2, 107 (1946).
Chem.,
8.
104,
carbonyl
of trisubstituted
of his example
[Chem. Pharm.
permanganate
7.
10.
J. Am.
the dipole model
on March 14, 1983, at Harvard University,
The stereochemical
the stereochemical
R. Lespieau,
(1980).
between
unsaturated
and K. K. Mathew,
-45 6.
187
and Y. Hirata,
from this formulation.
reported
to add.
not ribose.
in the preferred
olefinic
conformation
See, J. W. Cornforth,
a,&unsaturated
Chem. Rev., _, 80
see M. Schroder,
(1982).
a,@unsaturated compounds
Lett., 24, 0000 (1983).
Cha, J. Leder, Y. Kishi, D. Uemura,
This might be attributed
Cram's
5.
tetroxide
W. J. Christ,
Chem. Sot., 104, 4.
and Y. Kishi,
and Footnotes
isolated
unpublished
unpublished
by crystallization.
results.
results.
Y. Kishi, D. Uemura,
and Y. Hirata,
J. Am. Chem. Sot.,
7364 (1982).
11.
S. H. Kang, W. W. McWhorter,
12.
J. A. Secrist,
13.
T. Katsuki,
and Y. Kishi, unpublished
III and K. D. Barnes,
A. W. M. Lee, P. Ma, V. S. Martin,
and F. J. Walker,
J. Org. Chem.,
47, 1373
14.
N.
15.
R. Behrend
and G. Heyer, Justus Liebigs
16.
H. Fujioka
and Y. Kishi,
K. Kochetkov
and B. A. Dmitriev,
unpublished
Th. Posternak
and H. Friedli,
Wolczunowicx,
Bars, Cocu, and Posternak
Chim. Acta,
K. B. Sharpless,
z,
803 (1965).
Ann. Chem., 418,
Helv. Chim. Acta, 6,
the stereochemistry
pointed
294
(1919).
251 (1953).
out the importance
of 0s04 oxidation
R. M. Srivastava
20.
D. M. Vyas and G. W. Hay, Can. J. Chem., 53,
and R. K. Brown, Can. J. Chem., 49,
1339
1362 (1975).
of homoallylic
hydroxyl
of polyhydroxycyclopentenes
53, 2288 (1970) and references cited therein].
19.
(Received in USA 24 May 1983)
D. Tuddenham,
results.
18.
in directing
4526 (1980).
S. Masamune,
(1982).
Tetrahedron,
17.
groups
results,
J. Org. Chem., 45,
(1971).
[Helv.