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Regioselective hydration of alkynones by palladium catalysis
Tetrahedron Printed in
Letters,Vo1.28,No.27,pp Great Britain
REGIOSELECTIVE HYDRATION
Katsuharu Department
Abstract: tions
Diketones
are
by
palladium
dikektones
whereas
ester Methyl cury
of Industrial
afford
are
ternal
has
bearing
catalysts
alkynones
in
BY PALLADIUM CATALYSIS
and Kiitiro
University,
prepared
5-heptyn-2-one
conveniently
prepared
in acidic of
Utimoto*
Yoshida,
from and
Kyoto,
alkynyl
606, Japan
ketones
under
mild
2-(2-nonynyl)cyclohexanone
condi-
give
and 5,6_didehydroprostaglandin
from
easily
Other
media.l
controlled
sensitive
by
accessible
ketones,
neighboring
afforded oxypalladation 728
regioselective
for
hydration
of
neutral
conditions
by palladium
This
alkynones.
the
group
has
groups
terminal
however,
Although
low regioselectivity.2
been
acid
intramolecular
ladium
Imai,
Kyoto
regioselectively
catalysis;
because
acetylenes
reported
Imi, Kumiko Chemistry,
2-(2-heptynylhzyclopentanone
hydration
acetylenes
acetylenes
OF ALKYNONES
+ .OO Ltd.
1,4-
E2 methyl
1,5-diketones.
ketones
catalyzed
internal
oo40-4039/87 $3.00 Pergamon Journals
3127-3130,1987
less
seldom
orientation
participation,
prepared
results.
us the
describes
by merfrom
of hydration of in1,3-6 application to
satisfactory
prompted
paper
are
acetylenes
Recently
possible
use
regioselective
of
pal-
hydration
of
catalysis.’ H20
R’mR* 0
-
0 3
H20
,-C@(,(II)
R$&R* 0
t
+
5
4 Hydration mL)
solution
0.05
mmol,
at
room
ethereal
of 3-alkynyl of
was
added The
was
solution acetonitrile
treatment
with
intramolecular
over
Na2S04
180 mg,
96%
above
described
to cyclopentanone
the
ultrasonic
derivative,
was
diluted and
0.96
water
and
exclusively.’
palladium 5-Decyne
was
2-(2-nonynyl)cyclohexanone 3127
give
’
Treatment did
(9a) gave
for ether.
of
not
the
of acetylenes. a 1,5-diketone,
2-(3-
1-octyne
give
any after
10 h The
1,4-diketone,
recovered
indicated hydration
a
(13 mg,
wave” with
to
also
(10~1, 2.2
PdCl2(MeCN)2
extracted
catalysis
observations
palladium-catalyzed
mmol),
by ultrasonic
concentrated
yield)
These for
To an acetonitrile-water
irradiated
with
irradiation.
catalyst.
of ketone
first.
170 mg,
mixture
(74
palladium
assistance
(64
the
dried
under
prolonged
and
was
oxoheptyl)cyclopentanone after
examined
mixture
temperature.
aqueous
1 was
2-(2-heptynyl)cyclopentanone
5 mol%)
product
ketones
with
hydrated analogous
importance
of
In contrast 2-(2-oxononyl)-
3128
Table
I.
Diketones
from
Alkynones
Hydration
Diketone
Al kynone
6a
(R = Bu)
6b
(Me)
6c (HI
a0 % 0
by Regioselective
,R
9a
(R = Hex)
9b
(Me)
0
7a
0
CL OO
ion
Yield
Time
(h)
(%)
10 [5.5
R
Gf
React
2
92
8
19.5
81a
12
67]g
40
84
3.5
1oc
(H)
lla
(R = Me)
llb
(Ph)
R 12b
0
l4
98b 99lh
24
99
11
921
1.5
12a
%
91lf
7b
121 9c
96
55c
[50
271i
24
79d
2
67e
: Ketoaldehyde 7 (R = H) could not be detected. Less than 1% of the corresponding delta-diketone was detected by GLC. z Containing 5% of the corresponding delta-diketone. Containing 4% of the corresponding delta-diketone. T Enone 17 was obtained in 17% yield. Results obtained by Au catalysis are shown in brackets. i Containing 3% the corresponding ketoaldehyde 7 (R = H). Containing 10% of delta-diketone. i Obtained a mixture containing 27% of 124 21% of 2,6-heptanedione, and 53% of unchanged starting material 1 la
3129
( 1Oa) ’ ’ as a sole
cyclohexanone (1 la),
an example
of acyclic
heptanedione
(12a)
hexanedione
(12b).
and
any
of
diketone
The
acetylenic
summarized
of
from
terminal
of the
selective
0.137
acetylene
temperature
of
and gave
the
irradiation
above
the
same
the
followed
alkynones
of 5-heptyn-2-one
acetonitrile
(1 lb)
spatial
gave
distance
by hydrolysis
gives
6-phenyl-2,5-
between
through
2,5-
oxygen
2 gives
a 1,5-
5.
under
above
the
formation
6a,
described
a 1,4-diketone
of more
intermediate
conditions
are
stable
(1 mg,
3 mol%)
El
product
methyl
20
R = tBuMe2Si
intermediate
E2 methyl
irradiation
in 0.5
of
mL of
selectively 4 takes
Removal of the
ester
a
(18)
formed
precedence
mixture
illustrates
of
acetonitrile-H20
ester l2 (19, 40.6
19 in good yield.
by NMR measurement
R=H
8 was
2.
Ultrasonic
reaction.
18
as the
from
5,6_didehydroprostaglandin
was clarified
mg,
18
(50.0
(25:l)
at
77 % yield).
of the reaction
the mg, room
Protected
protective
group
during
mixture.
19
7-decyn-2-one
was obtained
of
5-oxo-prostaglandin
ultrasonic
of
controlled
PdC12(MeCN)2
20 gave
by
a 1,4-diketone
formation
namely,
hydration
derivative
When
6c,
of sterically
utility
mmol)
oxypalladation
4 provides
1,5-diketone
Regioselective synthetic
in aqueous
6-phenyl-5-hexyn-2-one
is determined
hydration
Treatment
yield.
catalyst
1.
to
formation
i.e.
though
isolated
palladium
Analogously
regioselectivity
carbon,
in Table
In contrast
in 84% with
alkynone,
exclusively.
3 and reactions Examples
product
(21)
major
was
product
IT+-
subjected with
to
the
contamination
above
hydration,
benzene
of two possible
diketones.
derivative
22L3
-
03%
21
8 C&C(CH2)4
ywdLfr7rf 0
CH3CH2 (CH2)4GCHS
22
0 :
20 Recently amine
reported
to acetylene
hydration
action
prompted
the
of
sodium
probable
64 aurate
to
application
the
intramolecular
the
catalyst
of
addition
for
of
regioselective
alkynones.14
Although condition,
16
catalytic
moiety
:
lower
sodium
aurate
regioselectivity
(NaAuC14) is observed
is effective for
the
for
hydration
hydration
of
acetylene
of alkynones.
under
Typical
neutral
procedures:
3130
a mixture
of 6a (180 mg,
MeOH-HZ0
(1O:l)
was
up gave-7a
in 91% yield.”
Exceptionally complex
CL
&
are
diketone
was obtained
NaAuC14’2H20
by ultrasound
Results
23 gave
mixture
o
1.01 mmol),
irradiated
at
added
(14 mg,
room
in Table
24 (85% yield)
by Pd(lI) catalyzed
0.03
mmol,
temperature
selectively
85%
24 The authors
wish
for Developmental
and
H. G. Viehe,
Ed; 1977; 4 Ed., F. Hudrlik
S. Patai G. Stork
4.
J. Hooz
5.
Reference
6.
Although the
to thank
John
N. Yanagihara, 1986, 108,
Commercial
Appl.
Chem.,
Chemie
of
the
1, Chapter
1964, s
Chem,
(Houben-Weyl),
E. Muller
Carbon-Carbon
Triple
Bond;
7.
935, 936.
1970, a
1105.
as Pd(I1) and Ru(III), applications
1983, a
K. Iritani,
transformation
ultrasonic
have
have
been
little
reported
as catalysts
for
reported.
1845. K. Utimoto,
2.08 (IH,
2.60
(2H, dt,
(PH,
m),
(IH,
214.6,
25.2, ‘H
quint.
J = 7.5 Hz),
31.19,
29.98,
14.
Y. Fukuda,
15.
Both
29.50,
7.3
dd,
209.6,
31.7,
m),
and H. Nozaki,
L
Am. ----,
Chem.
Sot.
J
2.16
terminal in
Japan
Hz),
2.73
J
137.3, 21.9,
(IH,
= 7.0,
131.2,
18.8,
(CDC13), 22.33,
J
oxypalladation
has
as MS.
7.0
= 7.5,
5.69 72.9,
Hz),
J = 6.4 Hz),
1.89 (2H,
dt,
1.20-1.50
J = 7.1,
7.1
18.3 Hz),
(IH,
dd,
71.7,
55.1,
3.67
J = 6.7, 53.0,
(3H,
s), 3.95-4.20
15.3 Hz); 51.6,
45.8,
13C NMR 41.5,
39.7,
14.0.
1.16 (9H,
t,
(18H,
15.73; MS m/z
acetylenes
28 March
dd,
15.3 Hz),
and H. Nozaki,
and internal
via
was used.
13C NMR as well
(9H, s), 2.4-2.6
24.75,
K. Utimoto,
furans
’ H NMR (CDC13), 0.89 (3H, br-t,
= 8.2,
22.6,
into
(2H, m), 2.33 (2H, t, J = 7.2 Hz), 2.46 (2H, t, J = 7.3 Hz),
173.6,
NMR
ketones
to be published.
Bl200J-I)
1.76 (2H, dt,
2.15-2.40
J = 3.8,
5.55
33.0,
(2H,
m),
1712 cm-‘;
(Branson
by ‘H NMR,
1738 (C=O) cm-‘;
1.50-1.70
of 2-alkynyl
and K. Utimoto,
cleaner
was determined
Hz),
(Received
such
H. Shiragami,
m),
IR
Chemistry
Sot,
synthetic
C. Lambert,
IR 3372 (OH),
37.3,
and Cul-
2753.
(8H,
(CDC13),
13.
Pure
observed;
Structure
Organischen
1978; Part
Chem.
Can. J.
VIII metals,
Palladium-catalyzed
IO.
Am.
of acetylenes,
K. Utimoto,
11.
Science,
2, p. 241. group
hydration
been
of Education,
(61850153).
and Notes der
In The
& Sons Inc., J.
and R. B. Layton,
7.
12.
Wiley
Ministry
Research
1>
:
p.726.
A. M. Hudrlik,
and R. Borch,
the
Scientific
In Methoden
Vol. V/2a, and
Ed.;
8.
9.
a
hydration.
References V. Jager
3.
although
0
for Grant-in-Aid
P.
work-
CCJ
OH
Acknowledgement
2.
Aqueous
by Au(Il1) catalysis,
>99
1.
in 4 Ml of
I.
23
ture
3 mol%)
for 5.5 h.
J = 7.5 Hz), m);
1987)
1.4-1.6
(6H,
208.8,
137.9,
m),
ketones
1987, & in good yields
I.73
136.2,
456 (M+).
Heterocycles, gave
13C NMR,
297. by Au catalysis.
(6H, 43.44,
Letters,Vo1.28,No.27,pp Great Britain
REGIOSELECTIVE HYDRATION
Katsuharu Department
Abstract: tions
Diketones
are
by
palladium
dikektones
whereas
ester Methyl cury
of Industrial
afford
are
ternal
has
bearing
catalysts
alkynones
in
BY PALLADIUM CATALYSIS
and Kiitiro
University,
prepared
5-heptyn-2-one
conveniently
prepared
in acidic of
Utimoto*
Yoshida,
from and
Kyoto,
alkynyl
606, Japan
ketones
under
mild
2-(2-nonynyl)cyclohexanone
condi-
give
and 5,6_didehydroprostaglandin
from
easily
Other
media.l
controlled
sensitive
by
accessible
ketones,
neighboring
afforded oxypalladation 728
regioselective
for
hydration
of
neutral
conditions
by palladium
This
alkynones.
the
group
has
groups
terminal
however,
Although
low regioselectivity.2
been
acid
intramolecular
ladium
Imai,
Kyoto
regioselectively
catalysis;
because
acetylenes
reported
Imi, Kumiko Chemistry,
2-(2-heptynylhzyclopentanone
hydration
acetylenes
acetylenes
OF ALKYNONES
+ .OO Ltd.
1,4-
E2 methyl
1,5-diketones.
ketones
catalyzed
internal
oo40-4039/87 $3.00 Pergamon Journals
3127-3130,1987
less
seldom
orientation
participation,
prepared
results.
us the
describes
by merfrom
of hydration of in1,3-6 application to
satisfactory
prompted
paper
are
acetylenes
Recently
possible
use
regioselective
of
pal-
hydration
of
catalysis.’ H20
R’mR* 0
-
0 3
H20
,-C@(,(II)
R$&R* 0
t
+
5
4 Hydration mL)
solution
0.05
mmol,
at
room
ethereal
of 3-alkynyl of
was
added The
was
solution acetonitrile
treatment
with
intramolecular
over
Na2S04
180 mg,
96%
above
described
to cyclopentanone
the
ultrasonic
derivative,
was
diluted and
0.96
water
and
exclusively.’
palladium 5-Decyne
was
2-(2-nonynyl)cyclohexanone 3127
give
’
Treatment did
(9a) gave
for ether.
of
not
the
of acetylenes. a 1,5-diketone,
2-(3-
1-octyne
give
any after
10 h The
1,4-diketone,
recovered
indicated hydration
a
(13 mg,
wave” with
to
also
(10~1, 2.2
PdCl2(MeCN)2
extracted
catalysis
observations
palladium-catalyzed
mmol),
by ultrasonic
concentrated
yield)
These for
To an acetonitrile-water
irradiated
with
irradiation.
catalyst.
of ketone
first.
170 mg,
mixture
(74
palladium
assistance
(64
the
dried
under
prolonged
and
was
oxoheptyl)cyclopentanone after
examined
mixture
temperature.
aqueous
1 was
2-(2-heptynyl)cyclopentanone
5 mol%)
product
ketones
with
hydrated analogous
importance
of
In contrast 2-(2-oxononyl)-
3128
Table
I.
Diketones
from
Alkynones
Hydration
Diketone
Al kynone
6a
(R = Bu)
6b
(Me)
6c (HI
a0 % 0
by Regioselective
,R
9a
(R = Hex)
9b
(Me)
0
7a
0
CL OO
ion
Yield
Time
(h)
(%)
10 [5.5
R
Gf
React
2
92
8
19.5
81a
12
67]g
40
84
3.5
1oc
(H)
lla
(R = Me)
llb
(Ph)
R 12b
0
l4
98b 99lh
24
99
11
921
1.5
12a
%
91lf
7b
121 9c
96
55c
[50
271i
24
79d
2
67e
: Ketoaldehyde 7 (R = H) could not be detected. Less than 1% of the corresponding delta-diketone was detected by GLC. z Containing 5% of the corresponding delta-diketone. Containing 4% of the corresponding delta-diketone. T Enone 17 was obtained in 17% yield. Results obtained by Au catalysis are shown in brackets. i Containing 3% the corresponding ketoaldehyde 7 (R = H). Containing 10% of delta-diketone. i Obtained a mixture containing 27% of 124 21% of 2,6-heptanedione, and 53% of unchanged starting material 1 la
3129
( 1Oa) ’ ’ as a sole
cyclohexanone (1 la),
an example
of acyclic
heptanedione
(12a)
hexanedione
(12b).
and
any
of
diketone
The
acetylenic
summarized
of
from
terminal
of the
selective
0.137
acetylene
temperature
of
and gave
the
irradiation
above
the
same
the
followed
alkynones
of 5-heptyn-2-one
acetonitrile
(1 lb)
spatial
gave
distance
by hydrolysis
gives
6-phenyl-2,5-
between
through
2,5-
oxygen
2 gives
a 1,5-
5.
under
above
the
formation
6a,
described
a 1,4-diketone
of more
intermediate
conditions
are
stable
(1 mg,
3 mol%)
El
product
methyl
20
R = tBuMe2Si
intermediate
E2 methyl
irradiation
in 0.5
of
mL of
selectively 4 takes
Removal of the
ester
a
(18)
formed
precedence
mixture
illustrates
of
acetonitrile-H20
ester l2 (19, 40.6
19 in good yield.
by NMR measurement
R=H
8 was
2.
Ultrasonic
reaction.
18
as the
from
5,6_didehydroprostaglandin
was clarified
mg,
18
(50.0
(25:l)
at
77 % yield).
of the reaction
the mg, room
Protected
protective
group
during
mixture.
19
7-decyn-2-one
was obtained
of
5-oxo-prostaglandin
ultrasonic
of
controlled
PdC12(MeCN)2
20 gave
by
a 1,4-diketone
formation
namely,
hydration
derivative
When
6c,
of sterically
utility
mmol)
oxypalladation
4 provides
1,5-diketone
Regioselective synthetic
in aqueous
6-phenyl-5-hexyn-2-one
is determined
hydration
Treatment
yield.
catalyst
1.
to
formation
i.e.
though
isolated
palladium
Analogously
regioselectivity
carbon,
in Table
In contrast
in 84% with
alkynone,
exclusively.
3 and reactions Examples
product
(21)
major
was
product
IT+-
subjected with
to
the
contamination
above
hydration,
benzene
of two possible
diketones.
derivative
22L3
-
03%
21
8 C&C(CH2)4
ywdLfr7rf 0
CH3CH2 (CH2)4GCHS
22
0 :
20 Recently amine
reported
to acetylene
hydration
action
prompted
the
of
sodium
probable
64 aurate
to
application
the
intramolecular
the
catalyst
of
addition
for
of
regioselective
alkynones.14
Although condition,
16
catalytic
moiety
:
lower
sodium
aurate
regioselectivity
(NaAuC14) is observed
is effective for
the
for
hydration
hydration
of
acetylene
of alkynones.
under
Typical
neutral
procedures:
3130
a mixture
of 6a (180 mg,
MeOH-HZ0
(1O:l)
was
up gave-7a
in 91% yield.”
Exceptionally complex
CL
&
are
diketone
was obtained
NaAuC14’2H20
by ultrasound
Results
23 gave
mixture
o
1.01 mmol),
irradiated
at
added
(14 mg,
room
in Table
24 (85% yield)
by Pd(lI) catalyzed
0.03
mmol,
temperature
selectively
85%
24 The authors
wish
for Developmental
and
H. G. Viehe,
Ed; 1977; 4 Ed., F. Hudrlik
S. Patai G. Stork
4.
J. Hooz
5.
Reference
6.
Although the
to thank
John
N. Yanagihara, 1986, 108,
Commercial
Appl.
Chem.,
Chemie
of
the
1, Chapter
1964, s
Chem,
(Houben-Weyl),
E. Muller
Carbon-Carbon
Triple
Bond;
7.
935, 936.
1970, a
1105.
as Pd(I1) and Ru(III), applications
1983, a
K. Iritani,
transformation
ultrasonic
have
have
been
little
reported
as catalysts
for
reported.
1845. K. Utimoto,
2.08 (IH,
2.60
(2H, dt,
(PH,
m),
(IH,
214.6,
25.2, ‘H
quint.
J = 7.5 Hz),
31.19,
29.98,
14.
Y. Fukuda,
15.
Both
29.50,
7.3
dd,
209.6,
31.7,
m),
and H. Nozaki,
L
Am. ----,
Chem.
Sot.
J
2.16
terminal in
Japan
Hz),
2.73
J
137.3, 21.9,
(IH,
= 7.0,
131.2,
18.8,
(CDC13), 22.33,
J
oxypalladation
has
as MS.
7.0
= 7.5,
5.69 72.9,
Hz),
J = 6.4 Hz),
1.89 (2H,
dt,
1.20-1.50
J = 7.1,
7.1
18.3 Hz),
(IH,
dd,
71.7,
55.1,
3.67
J = 6.7, 53.0,
(3H,
s), 3.95-4.20
15.3 Hz); 51.6,
45.8,
13C NMR 41.5,
39.7,
14.0.
1.16 (9H,
t,
(18H,
15.73; MS m/z
acetylenes
28 March
dd,
15.3 Hz),
and H. Nozaki,
and internal
via
was used.
13C NMR as well
(9H, s), 2.4-2.6
24.75,
K. Utimoto,
furans
’ H NMR (CDC13), 0.89 (3H, br-t,
= 8.2,
22.6,
into
(2H, m), 2.33 (2H, t, J = 7.2 Hz), 2.46 (2H, t, J = 7.3 Hz),
173.6,
NMR
ketones
to be published.
Bl200J-I)
1.76 (2H, dt,
2.15-2.40
J = 3.8,
5.55
33.0,
(2H,
m),
1712 cm-‘;
(Branson
by ‘H NMR,
1738 (C=O) cm-‘;
1.50-1.70
of 2-alkynyl
and K. Utimoto,
cleaner
was determined
Hz),
(Received
such
H. Shiragami,
m),
IR
Chemistry
Sot,
synthetic
C. Lambert,
IR 3372 (OH),
37.3,
and Cul-
2753.
(8H,
(CDC13),
13.
Pure
observed;
Structure
Organischen
1978; Part
Chem.
Can. J.
VIII metals,
Palladium-catalyzed
IO.
Am.
of acetylenes,
K. Utimoto,
11.
Science,
2, p. 241. group
hydration
been
of Education,
(61850153).
and Notes der
In The
& Sons Inc., J.
and R. B. Layton,
7.
12.
Wiley
Ministry
Research
1>
:
p.726.
A. M. Hudrlik,
and R. Borch,
the
Scientific
In Methoden
Vol. V/2a, and
Ed.;
8.
9.
a
hydration.
References V. Jager
3.
although
0
for Grant-in-Aid
P.
work-
CCJ
OH
Acknowledgement
2.
Aqueous
by Au(Il1) catalysis,
>99
1.
in 4 Ml of
I.
23
ture
3 mol%)
for 5.5 h.
J = 7.5 Hz), m);
1987)
1.4-1.6
(6H,
208.8,
137.9,
m),
ketones
1987, & in good yields
I.73
136.2,
456 (M+).
Heterocycles, gave
13C NMR,
297. by Au catalysis.
(6H, 43.44,