- Email: [email protected]
Tin(II) chloride catalyzed addition of diazo sulfones, diazo phosphine oxides, and diazo phosphonates to aldehydes.
Tenahdron
Letters, Vol.
33. No. 9. pp. 1131.1134.1992
0040.4039b2
Printed in Great Britain
Pergamon
s3.00 + .oo Press plc
TIN(H) CHLORIDE CATALYZED ADDITION OF DIAZO SULFONES, DIAZO PHOSPHINE OXIDES, AND DIAZO PHOSPHONATES TO ALDEHYDES.
Christopher
Department
R. Holmquist,
Eric J. Roskamp*
of Chemistry, Northwestern University, Evanston, Illinois 60208-3 113
Key Words: Tin(I1) chloride, catalyst, P-keto phosphine oxides, and P-keto
Abstract: aldehydes sulfones, with
primary
encumbered
The
aldehydes 42-56%.
prepared
substrates,
in
give
only
Several
studied.3 and
ketones5
5-36%
reaction
with
ethyl
than which
Reactions
those are
of
secondary
more
sterically
yields.
and
has
phosphorous
been
example,
reaction conditions
of
extensively
analogs,
and a-diazophosphine basic
add to p- keto
respectively.
53-79%,
aldehydes,
compounds
sulfur
under
phosphonates,
yields,
tertiary
carbonyl
For
of amines, reported
P-keto
higher
with
of a-diazo
in the presence We previously by
proceed
and
a-diazophosphonates,2b and
nldehydes”
oxides,
Reactions
chemists.1
sulfonesza,
esters
phosphine
chemistry
organic
run
Diazo sulfones, diazo phosphine oxides, and diazo phosphonates in the presence of a catalytic amounts of tin(I1) chloride to yield P-keto
aldehydes,
P-keto sulfones, phosphonates.
diazomethyl
yields
chloride.7 We now report the extension and P-keto sulfones, P-k&o phosphonates,
in
the
as
If this converted
presence
of
by
a-diazo-
have
also
been
phosphonates
alkynes.
enamines are produced.6 that aldehydes are efficiently diazoacetate
such
oxides,2c
studied
with
reaction to
catalytic
is
P-keto tin(II)
of this methodology for the preparation of P-keto phosphine oxides (eq 1,2). Our new
method allows the preparation of these synthetically useful available starting materials under mild, non-basic conditions. 1131
compounds from P-Keto sulfones,
readily P-keto
1132
Table 1: Tin(I1) Catalyzed Insertion Diazo Compound and Aldehyde
+
+
of Diazo
Compounds.
Product:
0-r >r 1;
O
H
Eq.
Time
SnCl2 -
-
h
0.1
2
50
0.1
3
36
0.1
>4b
75
0.2
2.5
56
0.2
3
<5c
0.2
>4d
53
0.2
8
42
0.2
8
: 1oc
0.2
>8d
0
H
0 Ph\l’-P--i, Ph’ N
H
2
+
0-r >r 1;
O
H
0
+
H
Isolated yields unless otherwise not rom the IH NMR spectrum. d Reaction
Reaction run incomplete after
. b
overnig 18 hours.
CY
Id
nated
1133
phosphonates,
and
excess
or phosphonate
sulfone
j3-keto
phosphine
9%,o S
Tol’
are
generally
prepared
by
addition
of
to an ester.8
SnCl2 (0.1 eq), RCHO
N2
*
rt, CH2C12
2 R’R?
oxides
carbanion
SnCl2 (0.2 eq), RCHO
PL__32
(2)
rt, CH2C12
R’ = Ph, OEt Tosyl van
diazomethane,
Leusen.za
catalytic gradually highly
When
amount of consumed. dependent
on the
phosphine
diazo works
oxides,
The of
(4.00
ethyl
(4.40
until
reaction remaining petroleum
in
1.0
period,
oil
was
method
of an aldehyde
mL
of
ether/ethyl
and
was
of
diazo
g of tin(I1)
a solution chloride was
by
and
then
flash
with
phosphorus
and the
(GM42732)
for support
p-
these
both
tosyl
compounds
give
mmol)
tosyl
reaction
nitrogen
g
(0.40
g of
removed
After had in
on silica
(79%)
of
Chemical
of this research.
Society,
of The Petroleum
and the National
g of in 5.0
diazomethane
was
evolution
chromatography10 0.954
of 0.590
temperature.
The
volatiles
mixture
chloride
0.784
at room
column to
of
observed.
We wish to thank the Donors
by the American
diazo-
however,
observed
To a stirred
was consumed
acetate”)
administered
is is
and
a brief
followed
by
ceased.
The
vacua.
4-phenyl-l-tosyl-2-
Research
Institute
The
gel 60 (12:l
butanone.
Acknowledgement:
of
and a
and
phosphonates
to diazosulfones, As
reaction
0.075
methylene
filtered
purified9
to P-keto
1. Relative slowly.
the
added
evolution
compound
was
diazomethylphosphonate2b
are converted
is representative:
was
nitrogen
the diazo mixture
to a solution
by the
aldehydes.
mmol)
chloride
diethyl
more
diazoacetate,
experimental
mmol)
prepared
aldehyde.
in Table
react
following methylene
is readily
is added
of the
as shown
unencumbered
induction TLC
nature
with
hydrocinnamaldehyde mL
diazomethane
compounds
and
best
solid,
reaction conditions, phosphine oxide*c
phosphorus
diazomethane
tosyl
yellow
tin(H) chloride, nitrogen is evolved and the diazo compound As shown in Table 1, the yield of the resulting j3-keto sulfone
Under similar methyl-P,P-diphenyl keto
a stable
Fund,
of Health
1134
REFERENCES
AND NOTES
For a review of the preparation see: Regitz, M.; Maas, G. Diaza Press, Orlando, 1986.
and chemistry of aliphatic diazo compounds Compounds: Properties and Synthesis, Academic
(a) van Leusen, A.M.; Strating, J. Noland, W.E. Ed,; John Wiley & Marmor, R.S.; Hilbert, P. J. Org. phosphonate was also prepared methyl)carbamate in 72% yield alumina for 48 hours. (c) Regitz,
Organic Synthesis Collective Volume VI; Sons, New York, 1988, 981. (b) Seyferth, D.; Chem. 1971, 36, 1379. Diethyl diazomethylfrom ethyl N-nitroso-N-(diethyl phosphonoby stirring its ethereal solution over basic M. Liebigs Ann. Chem. 1971, 748, 207.
(a) Regitz, M.; Boehshar, M.; Arenz, S.; Heydt, H. Chem. Ber. 1989, 122, 565. (b) Lewis, R.T.; Motherwell, W.B. Tetrahedron Lett. 1988,29, 5033. (c) Bartnik, R.; Wawrynko, K. J. Chem. Sot., Perkin Trans. I 1987, 715. (d) Gilbert, J.C.; Blackburn, B.K. J. Org. Chem. 1986,51, 4087. (e) Regitz, M.; Schoder, W. Synthesis 1985, 178. (f) Kuo, Y.C.; Aoyama, T.; Shioiri, T. Chem. Pharm. Bull. 1982,30, 526. (g) Hovius, K.; Engberts, J.B. Tetrahedron Lett. 1972, 2477. (h) Middelbos, W.; Zwanenburg, B.; Strating, J. Reel. Trav. Chim. Pays-Bas 1971, 90, 435. 4.
Gilbert,
J.C.; Weerasooriya,
5.
Colvin,
E.W.;
Hamill,
6.
Gilbert,
J.C.;
Senaratne,
7.
(a) Holmquist, C.R.; Roskamp, E.J. J. Org. Chem. 1989,54, Hornbuckle, S.F.; Zhang, Z.; Zhi, 1,. J. Org. Chem. 1990,55,
8.
(a) Levin, D.; Warren, S. Tetrahedron Lett. 1985,26, 505. (b) Aboujaoude, E.E.; Colligon, N.; Teulade, M.P.; Savignac, P. Phosphorous and Sulphur 1985, 25, 57. (c) Becker, H.D.; Russell, G.A. J. Org. Chem. 1963,28, 1896. (d) House, H.O.; Larson J.K. J. Org. Chem. 1968,33, 61.
9.
The only significant side product observed in these reactions is a chloromethyl compound, presumably formed from reaction of the diazo compound with tin(H) chloride or hydrogen chloride.
10.
Still, W. C.; Kahn,
11.
Dichloromethane/acetone (15:l) polar P-keto phosphonates and
U. J. Org.
Chem. 1982,47,
1837.
B.J. J. Chem. Sot. Perkin Trans. I 1977, 8, 869. K.P.
Tetrahedron
Lett. 1984,
M.; Mitra, A. J. Org. Chem. 1978,43,
(Received in USA 4 November 199 1j
25,
2303. 3258. 5297.
(b) Padwa,
A.;
2923.
was used as the solvent oxides. B-keto phosphine
system
for
the
more
Letters, Vol.
33. No. 9. pp. 1131.1134.1992
0040.4039b2
Printed in Great Britain
Pergamon
s3.00 + .oo Press plc
TIN(H) CHLORIDE CATALYZED ADDITION OF DIAZO SULFONES, DIAZO PHOSPHINE OXIDES, AND DIAZO PHOSPHONATES TO ALDEHYDES.
Christopher
Department
R. Holmquist,
Eric J. Roskamp*
of Chemistry, Northwestern University, Evanston, Illinois 60208-3 113
Key Words: Tin(I1) chloride, catalyst, P-keto phosphine oxides, and P-keto
Abstract: aldehydes sulfones, with
primary
encumbered
The
aldehydes 42-56%.
prepared
substrates,
in
give
only
Several
studied.3 and
ketones5
5-36%
reaction
with
ethyl
than which
Reactions
those are
of
secondary
more
sterically
yields.
and
has
phosphorous
been
example,
reaction conditions
of
extensively
analogs,
and a-diazophosphine basic
add to p- keto
respectively.
53-79%,
aldehydes,
compounds
sulfur
under
phosphonates,
yields,
tertiary
carbonyl
For
of amines, reported
P-keto
higher
with
of a-diazo
in the presence We previously by
proceed
and
a-diazophosphonates,2b and
nldehydes”
oxides,
Reactions
chemists.1
sulfonesza,
esters
phosphine
chemistry
organic
run
Diazo sulfones, diazo phosphine oxides, and diazo phosphonates in the presence of a catalytic amounts of tin(I1) chloride to yield P-keto
aldehydes,
P-keto sulfones, phosphonates.
diazomethyl
yields
chloride.7 We now report the extension and P-keto sulfones, P-k&o phosphonates,
in
the
as
If this converted
presence
of
by
a-diazo-
have
also
been
phosphonates
alkynes.
enamines are produced.6 that aldehydes are efficiently diazoacetate
such
oxides,2c
studied
with
reaction to
catalytic
is
P-keto tin(II)
of this methodology for the preparation of P-keto phosphine oxides (eq 1,2). Our new
method allows the preparation of these synthetically useful available starting materials under mild, non-basic conditions. 1131
compounds from P-Keto sulfones,
readily P-keto
1132
Table 1: Tin(I1) Catalyzed Insertion Diazo Compound and Aldehyde
+
+
of Diazo
Compounds.
Product:
0-r >r 1;
O
H
Eq.
Time
SnCl2 -
-
h
0.1
2
50
0.1
3
36
0.1
>4b
75
0.2
2.5
56
0.2
3
<5c
0.2
>4d
53
0.2
8
42
0.2
8
: 1oc
0.2
>8d
0
H
0 Ph\l’-P--i, Ph’ N
H
2
+
0-r >r 1;
O
H
0
+
H
Isolated yields unless otherwise not rom the IH NMR spectrum. d Reaction
Reaction run incomplete after
. b
overnig 18 hours.
CY
Id
nated
1133
phosphonates,
and
excess
or phosphonate
sulfone
j3-keto
phosphine
9%,o S
Tol’
are
generally
prepared
by
addition
of
to an ester.8
SnCl2 (0.1 eq), RCHO
N2
*
rt, CH2C12
2 R’R?
oxides
carbanion
SnCl2 (0.2 eq), RCHO
PL__32
(2)
rt, CH2C12
R’ = Ph, OEt Tosyl van
diazomethane,
Leusen.za
catalytic gradually highly
When
amount of consumed. dependent
on the
phosphine
diazo works
oxides,
The of
(4.00
ethyl
(4.40
until
reaction remaining petroleum
in
1.0
period,
oil
was
method
of an aldehyde
mL
of
ether/ethyl
and
was
of
diazo
g of tin(I1)
a solution chloride was
by
and
then
flash
with
phosphorus
and the
(GM42732)
for support
p-
these
both
tosyl
compounds
give
mmol)
tosyl
reaction
nitrogen
g
(0.40
g of
removed
After had in
on silica
(79%)
of
Chemical
of this research.
Society,
of The Petroleum
and the National
g of in 5.0
diazomethane
was
evolution
chromatography10 0.954
of 0.590
temperature.
The
volatiles
mixture
chloride
0.784
at room
column to
of
observed.
We wish to thank the Donors
by the American
diazo-
however,
observed
To a stirred
was consumed
acetate”)
administered
is is
and
a brief
followed
by
ceased.
The
vacua.
4-phenyl-l-tosyl-2-
Research
Institute
The
gel 60 (12:l
butanone.
Acknowledgement:
of
and a
and
phosphonates
to diazosulfones, As
reaction
0.075
methylene
filtered
purified9
to P-keto
1. Relative slowly.
the
added
evolution
compound
was
diazomethylphosphonate2b
are converted
is representative:
was
nitrogen
the diazo mixture
to a solution
by the
aldehydes.
mmol)
chloride
diethyl
more
diazoacetate,
experimental
mmol)
prepared
aldehyde.
in Table
react
following methylene
is readily
is added
of the
as shown
unencumbered
induction TLC
nature
with
hydrocinnamaldehyde mL
diazomethane
compounds
and
best
solid,
reaction conditions, phosphine oxide*c
phosphorus
diazomethane
tosyl
yellow
tin(H) chloride, nitrogen is evolved and the diazo compound As shown in Table 1, the yield of the resulting j3-keto sulfone
Under similar methyl-P,P-diphenyl keto
a stable
Fund,
of Health
1134
REFERENCES
AND NOTES
For a review of the preparation see: Regitz, M.; Maas, G. Diaza Press, Orlando, 1986.
and chemistry of aliphatic diazo compounds Compounds: Properties and Synthesis, Academic
(a) van Leusen, A.M.; Strating, J. Noland, W.E. Ed,; John Wiley & Marmor, R.S.; Hilbert, P. J. Org. phosphonate was also prepared methyl)carbamate in 72% yield alumina for 48 hours. (c) Regitz,
Organic Synthesis Collective Volume VI; Sons, New York, 1988, 981. (b) Seyferth, D.; Chem. 1971, 36, 1379. Diethyl diazomethylfrom ethyl N-nitroso-N-(diethyl phosphonoby stirring its ethereal solution over basic M. Liebigs Ann. Chem. 1971, 748, 207.
(a) Regitz, M.; Boehshar, M.; Arenz, S.; Heydt, H. Chem. Ber. 1989, 122, 565. (b) Lewis, R.T.; Motherwell, W.B. Tetrahedron Lett. 1988,29, 5033. (c) Bartnik, R.; Wawrynko, K. J. Chem. Sot., Perkin Trans. I 1987, 715. (d) Gilbert, J.C.; Blackburn, B.K. J. Org. Chem. 1986,51, 4087. (e) Regitz, M.; Schoder, W. Synthesis 1985, 178. (f) Kuo, Y.C.; Aoyama, T.; Shioiri, T. Chem. Pharm. Bull. 1982,30, 526. (g) Hovius, K.; Engberts, J.B. Tetrahedron Lett. 1972, 2477. (h) Middelbos, W.; Zwanenburg, B.; Strating, J. Reel. Trav. Chim. Pays-Bas 1971, 90, 435. 4.
Gilbert,
J.C.; Weerasooriya,
5.
Colvin,
E.W.;
Hamill,
6.
Gilbert,
J.C.;
Senaratne,
7.
(a) Holmquist, C.R.; Roskamp, E.J. J. Org. Chem. 1989,54, Hornbuckle, S.F.; Zhang, Z.; Zhi, 1,. J. Org. Chem. 1990,55,
8.
(a) Levin, D.; Warren, S. Tetrahedron Lett. 1985,26, 505. (b) Aboujaoude, E.E.; Colligon, N.; Teulade, M.P.; Savignac, P. Phosphorous and Sulphur 1985, 25, 57. (c) Becker, H.D.; Russell, G.A. J. Org. Chem. 1963,28, 1896. (d) House, H.O.; Larson J.K. J. Org. Chem. 1968,33, 61.
9.
The only significant side product observed in these reactions is a chloromethyl compound, presumably formed from reaction of the diazo compound with tin(H) chloride or hydrogen chloride.
10.
Still, W. C.; Kahn,
11.
Dichloromethane/acetone (15:l) polar P-keto phosphonates and
U. J. Org.
Chem. 1982,47,
1837.
B.J. J. Chem. Sot. Perkin Trans. I 1977, 8, 869. K.P.
Tetrahedron
Lett. 1984,
M.; Mitra, A. J. Org. Chem. 1978,43,
(Received in USA 4 November 199 1j
25,
2303. 3258. 5297.
(b) Padwa,
A.;
2923.
was used as the solvent oxides. B-keto phosphine
system
for
the
more