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Epoxidation of γ-methylene-γ-butyrolactones by dimethyldioxirane
0040-4039/89 $3.00 f .OO 4223-4226,1989 Maxwell Pergamon Macmillan plc
Tetrahedron Letters,Vo1.30,No.32,pp Printed in Great Britain
EPOXIDATION
OF
yMETIIYLENE-y-BU’I’YROLACTONES
Waldemar Adam*, Lazaros Haajiarapoglou,
BY DIMETIIYLDIOXIRANE
Volker Jiiger * and Bernhard Seidel.
Instituteof Organic Chemishy,University ofwiirzburg, AmHubIand, D-8700 Wilnburg,
Federal Republic of Germany
Abstract : Dimethyldioxirane
(as acetone solution) converts
and esters to the corresponding
epoxides
y-Methylene-y-butyrolactones chemistry
of which
in excellent
1 constitute
warrants intensive
a class of compounds
investigation.
of both the C=C and the C=O functionalities, nucleophiles.
This leads normally
/ AI=
ok
W+)
0
that only recentlyt
An intriguing
making
to 1,bdicarbonyl
isomers (Eq. 1) 2. Of particular relevance
y-methylene-y-butyrolactones
and other enol &tones
yields.
them susceptible
derivatives
have become accessible,
the
feature of these enol lactones is the presence towards
attack
or, in catalytic processes,
to the present study are preliminary
by electropliiles
to the indicated cyclic
results on the bromine
addition
E+--JyJgYi-u(‘OR) 0 Jl---J 0 0
to
(1)
1 yield highly reactive dibromo compounds
W&i and the reluctance of’ 1 towards mCPBA cpoxidation,
enol ester C=C bond much less reactive as compared we report on the successful potentially
epoxidation
to an [internal)
of enol Inctones
trialkyl-substituted
making
the
alkene 2c.Jb. Presently
I to afford the labile epoxy esters 2, which constitute
useful building blocks for organic synthesis.
SCNEME
1
A few epoxy esters related to 2 have been prepared directly from enol esters using peroxy acids 4, but in most cases the former have been postulated natural product containing
..
as transient
this epoxy lactone
intermediates,
rearranging
to keto esters 5. In one case, a
moiety has been isolated, nnrnety jolkinolide
4223
B, and subsequently
4224
its structure synthesis
elucidated
by spectroscopy,
chemical
transformation,
and X-ray crystallography
7.
An efticient epoxidizing transformations recently
corresponding
under striclly neuu-nl condition and thus avoids the acid-catalyzed
agent, which perrorms
of the epoxide products, a common difficulty
(Scheme
1) it was shown
that dioxiranes
with peroxy acids,
(as ketone
epoxide [ 1 1, aflatoxin B 111 to the corresponding
carbons t2 to arene oxides [ 3 1, and allenes 13 to spirodioxidcs should be an idea1 reagent for the epoxidation Indeed, dimethyldioxirane
transformed
solutionsj
9
epoxide
CHS,,,
to prepare
1 the
to
0
procedure
( ca. 0.07-O.li
CH3
tfrnt dimctl,yldioxirailc
lactones 2 by
spiroepoxy peroxy
0
acid
even under burfered conditions,
(2)
O 2
led to complete decomposition.
entails adding rapidly a solution of dimethyldioxirane
(l&20%
sieves ( 4A ), to a cooled
The
molar excess) in ( -20 oC ), stirred
( 1.06 mmof ) in abs. Cf~f2Cf2 ( 10 mL) under N2. The stirring was ( cf. Table 1 ) or the enol hclone
consumption
yielding the hitherto unknown,
0
-TX--J
M ), which was dried over molecular
until complete
hydro-
Rl
0
6
solution of the y-methylene-y-butyrolactone continued
tu to the
aromatic
the corresponding
spiroepoxy
,. P
1 of these exocyclic enof.lactones,
general epoxidation
enol ethers
[ 4 1. It was our contention
y-methyfene-y-buyrolactones
+
epoxidation
8 Most
R2 R3
RI
0
convert
[ 2 1, polycyclic
R2 R3
J-J
is dimethyldioxirane.
of enol factones.
lactones 2 (Eq. 2) in high yjefd (Table 1). Attempts
acetone
6, and by total
labile spiroepoxy
I ;~nd tflc solvent removed
in vacua,
factories 2 in high purity (NMR,TLC).
Table 1. Epoxidation a of the @4ethy&ene-y-butyrolmtmes I to the Spirocpoxy L~ctones 2 by Dimethyldioxirane. Methylene-lactone
R1
R2
R3
Reaction time (h)
Epoxy Iactone 2
1
Yield,(%)
Ref.”
b
a
H
H
H
2.0
96
14
b
CH3
CH3
H
3.0
96
15
C
CH3
H
H
3.5
95 cf
16
d
H
CH3
3.5
94 e
17
a In CH2Cl2/CH3COCH3 rue given in tie foolnoter
H
ant-20 OC. b Yield of isolalcd prodoc~ C Sclcclcd spcctr:d data for cnch OTthe 1.7-dioxnspiro[2.4jhcptan-6-ones
; IR
dala WCTCobtained by using a Perkin Elmer 1420 irwrumcm;
spectral were rtm on a Brukcr WM-250 spectromelcr. instmmcnL
Iii NMR ( 250 Mllz ) and 33C NMR ( 63 MHz )
referring chemical shilrr to Mc4Si; MS spectra were obraincd on a Varian MATCH
d As a ca. 60:40 mixlurc of two diastcrcomcrs. C As a ca. 6.5~35 mixtow ol IWOdiasvxcomcrs.
As an extension,
the three
endocycfic
enol lactones
2
and esters 3, 5, and 7 (cf. Table 2) were examined,
7
4226
5. !:
8:(a) (b)
McDonald, R.N. in Mechanisms of Molecular Migrations; Thyagarajan B.S. (Ed.),Vol. 3, Chapter 2; Wiley-Interscience, New York, 197 1 Uemura, D. ; Hirata, Y. Tetrahedron Left. 1972, 1387 ; 1977, 283. Katsumura, S. ; Kimura, A. ; lsoe, A. Tetrahedron, 1989, Q, 1337. Adam, W. ; Curci , R. ; Edwards, J.O. Act. Chem. Res. 1989, in press. Murray, R.W. Chem. Rev. 1989 , in press. Curci , R. in Advances in Oxygenated Processes ; Baumstark, A.L. (Ed.) ; Vol. 2, Chapter I ; JAI Press ; Greenwich , in press. Murray, R.W. ; Jeyaraman , R. J. Org. Chem. 198.5,50,2847. Adam, W. ; Ghan , Y.-Y. ; Cremer, D. ; Gauss +I. ; Scheutzow , D. ; Schindler , M. J. Org. Chem. 1987,52. ,280O. Mello, R. ; Fiorentino. M. ; Sciacovelli, 0. ; Curci , R. J. Org. Chem. 1988, 3, 3890. Troisi , L. ; Cassidei , L. ; Lopez, L. ; Mello, R. ; Curci , R. Tetrahedron Lett. 1989,jQ,257. Baertschi , SW. ; Raney , K.D. ; Stone, M.P. ; Harris , T.M. J:Am. Chem. Sot. 1988 ,110,
ici
9.b) (b)
w :::
Agarwal , S.K. ; Boyd , D.R. ; Jennings, B.W. , McGuckin, R.M. ; O’Kane, G.A. 1989, a, 123. 13. (a) Crandall , J.K. ; Batal , D.J. J. Org. Chem. 1988, z, 1338. (b) Crandall , J.K. ; Batal , D.J. Tetrahedron Leu. 198&B, 4791 12.
14.
Terrahedron
L&t.
2a; IR (CC14): 1815 cm-l (C=O).- lH NMR (250 MHz, CDCl3) : 6 = 2.32-2.43 (m, lH), 2.67-
3.01 (m, 3H). 2.97 and 3.31 (AB, JAB = 3.72 Hz, 2H).- 13C NMR (63 MHz, CDCl3): 6 = 26.0, 28.1, 50.4 and 88.3 (oxirane C) , 174.1 (C=O).- MS (70 eV): m/z (%) = 114 (M+, 8), 86 (32). 56 (100). 15.
2b; IFt (CC14): 1820 cm-l (C=O) .- lH NMR ( 250 MHz, CDC13): 6 = 1.11 (s, CHQ, 1.25 (s, Cm),
2.54 and 2.71 (AB, JAR = 17.43 Hz, 2H), 2.95 and 3.23 (CD, JCD = 3.57 Hz, 2H).-
16.
13C NMR
(63 MHz, CDCl3) : 6 = 21.7, 25.4, 37.3,42.8, 47.7 and 93.6 (oxirane C) , 173.1 (C=O).MS (70 eV) : m/z (%) = 142 (M+, 0.3), 113 (4), 70 (7), 56 (100). 2c; IR (CC14): 1810 cm-l (C=O) ; 60:40 mixture of two diastereomers by NMR. 1H NMR (250 MHz, CDCi3): 6 = 1.05 and 1.21 (2d, J = 6.87 and 7.16 Hz, 3H; CH3 of minor and major isomers), 2.35 3.12 (m, 3H), 2.93, 3.30 and 3.02, 3.20 (AB of minor and major isomers, J = 3.59 and 3.64 Hz, 2H).-
17.
13C NMR (63 MHz, CDC13), major isomer: 6 = 16.7, 33.2,36.3,48;9 and 92.3 (oxirane C), 173.5 (C=O); minor isomer: S = 13.2, 31.7, 35.7,48.2 and 90.3 (oxirane C), 173.6 (C=O).MS (70 eV) m/z (%) = 128 (M+, 0.6), 99 (6), 70 (25), 42 (100). 2d; IR (CCl4): 1815 cm-l (C=O); 65:35 mixture of two diastereomers by NMR.lH NMR (250 MHz, CDC13): 6 = 1.37 and 1.42 (2d, J = 7.21 and 7.22 Hz, 3H; CH3 of major and minor isomers), 2.103.17 (m, 3H), 2.94, 3.25 and 2.96, 3.31 (AB of minor and major isomers, J = 3.90 and 3.63 Hz, 2I-I).l3C NMR (63 MHz, CDC13), major isomer: 6 = 15.5, 33.9, 34.4,49.5 and 86.3 (oxirane C), 177.4 (C=O); minor isomer: 6 = 16.4, 34.1, 34.6, 50.9 and 86.9 (oxirane C), 176.8 ppm (C=O).MS (70 eV), m/z (% )= 128 (M+, 1), 99 (6), 70 (I 9), 42 (100).
18.
4; IR (CCl4): 1780 cm-l (C=O); 1H NMR (250 MHz, CDC13): 6 = 1.12 (s, CH3), 1.26 (s, CH3). 2.17-2.35 (m, 2H), 3.01 (dd, J = 2.55 and 1.56 Hz, 1H) , 5.23 (d, lH, J = 2.70 Hz); 13C NMR (63 MHZ, CDC13): 6 = 23.71 26.6, 31.3, 58.3 and 77.8 (oxirane C), 167.3 ppm (C=O).- MS (70 eV): m/z (%) = 142 (M+, 1), 113 (15) 57 (100).
19.
6; IR (Cc&): 1775 cm-l (C=O); IH NMR (250 MHz, CDC13): 6 = 1.30 - 2.90 (m).- 13C NMR (63 MHz, CDCl3): 6= 19.8, 20.0, 24.7, 27.4, 27.5, 27.8, 61.5 and 87.0 (oxirane C), 168.1 ppm (GO> .- MS (70eV): m/z (%) = 168 (M+, 2), 124 (30), 1I1 (100).
20.
Forth, W.; Henschler, D.; Rummel, W. (Eds.), in Pharmakologie (Received
in
Germany
2 June
1989)
und Toxikologie,
5th ed.,
Tetrahedron Letters,Vo1.30,No.32,pp Printed in Great Britain
EPOXIDATION
OF
yMETIIYLENE-y-BU’I’YROLACTONES
Waldemar Adam*, Lazaros Haajiarapoglou,
BY DIMETIIYLDIOXIRANE
Volker Jiiger * and Bernhard Seidel.
Instituteof Organic Chemishy,University ofwiirzburg, AmHubIand, D-8700 Wilnburg,
Federal Republic of Germany
Abstract : Dimethyldioxirane
(as acetone solution) converts
and esters to the corresponding
epoxides
y-Methylene-y-butyrolactones chemistry
of which
in excellent
1 constitute
warrants intensive
a class of compounds
investigation.
of both the C=C and the C=O functionalities, nucleophiles.
This leads normally
/ AI=
ok
W+)
0
that only recentlyt
An intriguing
making
to 1,bdicarbonyl
isomers (Eq. 1) 2. Of particular relevance
y-methylene-y-butyrolactones
and other enol &tones
yields.
them susceptible
derivatives
have become accessible,
the
feature of these enol lactones is the presence towards
attack
or, in catalytic processes,
to the present study are preliminary
by electropliiles
to the indicated cyclic
results on the bromine
addition
E+--JyJgYi-u(‘OR) 0 Jl---J 0 0
to
(1)
1 yield highly reactive dibromo compounds
W&i and the reluctance of’ 1 towards mCPBA cpoxidation,
enol ester C=C bond much less reactive as compared we report on the successful potentially
epoxidation
to an [internal)
of enol Inctones
trialkyl-substituted
making
the
alkene 2c.Jb. Presently
I to afford the labile epoxy esters 2, which constitute
useful building blocks for organic synthesis.
SCNEME
1
A few epoxy esters related to 2 have been prepared directly from enol esters using peroxy acids 4, but in most cases the former have been postulated natural product containing
..
as transient
this epoxy lactone
intermediates,
rearranging
to keto esters 5. In one case, a
moiety has been isolated, nnrnety jolkinolide
4223
B, and subsequently
4224
its structure synthesis
elucidated
by spectroscopy,
chemical
transformation,
and X-ray crystallography
7.
An efticient epoxidizing transformations recently
corresponding
under striclly neuu-nl condition and thus avoids the acid-catalyzed
agent, which perrorms
of the epoxide products, a common difficulty
(Scheme
1) it was shown
that dioxiranes
with peroxy acids,
(as ketone
epoxide [ 1 1, aflatoxin B 111 to the corresponding
carbons t2 to arene oxides [ 3 1, and allenes 13 to spirodioxidcs should be an idea1 reagent for the epoxidation Indeed, dimethyldioxirane
transformed
solutionsj
9
epoxide
CHS,,,
to prepare
1 the
to
0
procedure
( ca. 0.07-O.li
CH3
tfrnt dimctl,yldioxirailc
lactones 2 by
spiroepoxy peroxy
0
acid
even under burfered conditions,
(2)
O 2
led to complete decomposition.
entails adding rapidly a solution of dimethyldioxirane
(l&20%
sieves ( 4A ), to a cooled
The
molar excess) in ( -20 oC ), stirred
( 1.06 mmof ) in abs. Cf~f2Cf2 ( 10 mL) under N2. The stirring was ( cf. Table 1 ) or the enol hclone
consumption
yielding the hitherto unknown,
0
-TX--J
M ), which was dried over molecular
until complete
hydro-
Rl
0
6
solution of the y-methylene-y-butyrolactone continued
tu to the
aromatic
the corresponding
spiroepoxy
,. P
1 of these exocyclic enof.lactones,
general epoxidation
enol ethers
[ 4 1. It was our contention
y-methyfene-y-buyrolactones
+
epoxidation
8 Most
R2 R3
RI
0
convert
[ 2 1, polycyclic
R2 R3
J-J
is dimethyldioxirane.
of enol factones.
lactones 2 (Eq. 2) in high yjefd (Table 1). Attempts
acetone
6, and by total
labile spiroepoxy
I ;~nd tflc solvent removed
in vacua,
factories 2 in high purity (NMR,TLC).
Table 1. Epoxidation a of the @4ethy&ene-y-butyrolmtmes I to the Spirocpoxy L~ctones 2 by Dimethyldioxirane. Methylene-lactone
R1
R2
R3
Reaction time (h)
Epoxy Iactone 2
1
Yield,(%)
Ref.”
b
a
H
H
H
2.0
96
14
b
CH3
CH3
H
3.0
96
15
C
CH3
H
H
3.5
95 cf
16
d
H
CH3
3.5
94 e
17
a In CH2Cl2/CH3COCH3 rue given in tie foolnoter
H
ant-20 OC. b Yield of isolalcd prodoc~ C Sclcclcd spcctr:d data for cnch OTthe 1.7-dioxnspiro[2.4jhcptan-6-ones
; IR
dala WCTCobtained by using a Perkin Elmer 1420 irwrumcm;
spectral were rtm on a Brukcr WM-250 spectromelcr. instmmcnL
Iii NMR ( 250 Mllz ) and 33C NMR ( 63 MHz )
referring chemical shilrr to Mc4Si; MS spectra were obraincd on a Varian MATCH
d As a ca. 60:40 mixlurc of two diastcrcomcrs. C As a ca. 6.5~35 mixtow ol IWOdiasvxcomcrs.
As an extension,
the three
endocycfic
enol lactones
2
and esters 3, 5, and 7 (cf. Table 2) were examined,
7
4226
5. !:
8:(a) (b)
McDonald, R.N. in Mechanisms of Molecular Migrations; Thyagarajan B.S. (Ed.),Vol. 3, Chapter 2; Wiley-Interscience, New York, 197 1 Uemura, D. ; Hirata, Y. Tetrahedron Left. 1972, 1387 ; 1977, 283. Katsumura, S. ; Kimura, A. ; lsoe, A. Tetrahedron, 1989, Q, 1337. Adam, W. ; Curci , R. ; Edwards, J.O. Act. Chem. Res. 1989, in press. Murray, R.W. Chem. Rev. 1989 , in press. Curci , R. in Advances in Oxygenated Processes ; Baumstark, A.L. (Ed.) ; Vol. 2, Chapter I ; JAI Press ; Greenwich , in press. Murray, R.W. ; Jeyaraman , R. J. Org. Chem. 198.5,50,2847. Adam, W. ; Ghan , Y.-Y. ; Cremer, D. ; Gauss +I. ; Scheutzow , D. ; Schindler , M. J. Org. Chem. 1987,52. ,280O. Mello, R. ; Fiorentino. M. ; Sciacovelli, 0. ; Curci , R. J. Org. Chem. 1988, 3, 3890. Troisi , L. ; Cassidei , L. ; Lopez, L. ; Mello, R. ; Curci , R. Tetrahedron Lett. 1989,jQ,257. Baertschi , SW. ; Raney , K.D. ; Stone, M.P. ; Harris , T.M. J:Am. Chem. Sot. 1988 ,110,
ici
9.b) (b)
w :::
Agarwal , S.K. ; Boyd , D.R. ; Jennings, B.W. , McGuckin, R.M. ; O’Kane, G.A. 1989, a, 123. 13. (a) Crandall , J.K. ; Batal , D.J. J. Org. Chem. 1988, z, 1338. (b) Crandall , J.K. ; Batal , D.J. Tetrahedron Leu. 198&B, 4791 12.
14.
Terrahedron
L&t.
2a; IR (CC14): 1815 cm-l (C=O).- lH NMR (250 MHz, CDCl3) : 6 = 2.32-2.43 (m, lH), 2.67-
3.01 (m, 3H). 2.97 and 3.31 (AB, JAB = 3.72 Hz, 2H).- 13C NMR (63 MHz, CDCl3): 6 = 26.0, 28.1, 50.4 and 88.3 (oxirane C) , 174.1 (C=O).- MS (70 eV): m/z (%) = 114 (M+, 8), 86 (32). 56 (100). 15.
2b; IFt (CC14): 1820 cm-l (C=O) .- lH NMR ( 250 MHz, CDC13): 6 = 1.11 (s, CHQ, 1.25 (s, Cm),
2.54 and 2.71 (AB, JAR = 17.43 Hz, 2H), 2.95 and 3.23 (CD, JCD = 3.57 Hz, 2H).-
16.
13C NMR
(63 MHz, CDCl3) : 6 = 21.7, 25.4, 37.3,42.8, 47.7 and 93.6 (oxirane C) , 173.1 (C=O).MS (70 eV) : m/z (%) = 142 (M+, 0.3), 113 (4), 70 (7), 56 (100). 2c; IR (CC14): 1810 cm-l (C=O) ; 60:40 mixture of two diastereomers by NMR. 1H NMR (250 MHz, CDCi3): 6 = 1.05 and 1.21 (2d, J = 6.87 and 7.16 Hz, 3H; CH3 of minor and major isomers), 2.35 3.12 (m, 3H), 2.93, 3.30 and 3.02, 3.20 (AB of minor and major isomers, J = 3.59 and 3.64 Hz, 2H).-
17.
13C NMR (63 MHz, CDC13), major isomer: 6 = 16.7, 33.2,36.3,48;9 and 92.3 (oxirane C), 173.5 (C=O); minor isomer: S = 13.2, 31.7, 35.7,48.2 and 90.3 (oxirane C), 173.6 (C=O).MS (70 eV) m/z (%) = 128 (M+, 0.6), 99 (6), 70 (25), 42 (100). 2d; IR (CCl4): 1815 cm-l (C=O); 65:35 mixture of two diastereomers by NMR.lH NMR (250 MHz, CDC13): 6 = 1.37 and 1.42 (2d, J = 7.21 and 7.22 Hz, 3H; CH3 of major and minor isomers), 2.103.17 (m, 3H), 2.94, 3.25 and 2.96, 3.31 (AB of minor and major isomers, J = 3.90 and 3.63 Hz, 2I-I).l3C NMR (63 MHz, CDC13), major isomer: 6 = 15.5, 33.9, 34.4,49.5 and 86.3 (oxirane C), 177.4 (C=O); minor isomer: 6 = 16.4, 34.1, 34.6, 50.9 and 86.9 (oxirane C), 176.8 ppm (C=O).MS (70 eV), m/z (% )= 128 (M+, 1), 99 (6), 70 (I 9), 42 (100).
18.
4; IR (CCl4): 1780 cm-l (C=O); 1H NMR (250 MHz, CDC13): 6 = 1.12 (s, CH3), 1.26 (s, CH3). 2.17-2.35 (m, 2H), 3.01 (dd, J = 2.55 and 1.56 Hz, 1H) , 5.23 (d, lH, J = 2.70 Hz); 13C NMR (63 MHZ, CDC13): 6 = 23.71 26.6, 31.3, 58.3 and 77.8 (oxirane C), 167.3 ppm (C=O).- MS (70 eV): m/z (%) = 142 (M+, 1), 113 (15) 57 (100).
19.
6; IR (Cc&): 1775 cm-l (C=O); IH NMR (250 MHz, CDC13): 6 = 1.30 - 2.90 (m).- 13C NMR (63 MHz, CDCl3): 6= 19.8, 20.0, 24.7, 27.4, 27.5, 27.8, 61.5 and 87.0 (oxirane C), 168.1 ppm (GO> .- MS (70eV): m/z (%) = 168 (M+, 2), 124 (30), 1I1 (100).
20.
Forth, W.; Henschler, D.; Rummel, W. (Eds.), in Pharmakologie (Received
in
Germany
2 June
1989)
und Toxikologie,
5th ed.,