epoxidation.bicarbonate-activated.h2o2, biotransformation
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3220
J. Am. Chem. Soc.
2000,
122,
3220-3221
Epoxidation of Alkenes with Bicarbonate-Activated
Hydrogen Peroxide
Huirong Yao and David E. Richardson*
Center for Catalysis, Department of Chemistry
Uni
V
ersity of Florida, Gaines
V
ille, Florida 32611-7200
Recei
Table 1.
Oxidation of Water-Soluble Alkenes by Hydrogen
Peroxide in Sodium Bicarbonate (1 M) Solutions in D
2
O (25
°
C)
a
V
ed No
V
ember 8, 1999
We describe here the discovery of the bicarbonate-catalyzed
epoxidation of alkenes with aqueous hydrogen peroxide at near-
neutral pH. For some substrates, the procedure is comparable in
apparent synthetic utility to the best methods now available for
H
2
O
2
-based alkene expoxidations that avoid extensive hydrolytic
formation of diol (e.g., ligand-accelerated methyltrioxorhenium/
H
2
O
2
1
). The new process features a stable
main group
catalyst/
activator of unexpected simplicity (bicarbonate ion) and can be
applied readily in water or mixed aqueous solutions under
homogeneous conditions.
Hydrogen peroxide is a high oxygen content, environmentally
friendly oxidant for which water is the sole byproduct in
heterolytic oxidations,
2
but it is a slow oxidant in the absence of
activation
3
due to the poor leaving tendency of the hydroxide
ion.
4
Transition metal salts or complexes have been used as
catalysts for alkene epoxidations with aqueous H
2
O
2
.
5,6
Other
methods for activation of H
2
O
2
include forming reactive peroxy-
acids from carboxylic acids,
7
forming peroxycarboximidic acid
from acetonitrile (Payne oxidation),
8
generation of peroxy-
isourea,
9
or using sodium perborate or sodium percarbonate (Na
2
-
CO
3
â1.5H
2
O
2
) in strongly basic solution.
10
Such systems can have
one or more disadvantages, such as toxic or rapidly decomposed
metal catalysts, oxidative decomposition of organic ligands,
organic byproducts, or strongly acidic or basic reaction conditions
that decompose the desired epoxide product.
A method for activating hydrogen peroxide with bicarbonate
ion was described by Drago and co-workers
11
and Richardson et
al.
12
in their studies of sulfide oxidations in alcohol/water solvents.
In the bicarbonate-activated peroxide (BAP) system,
13
the active
a
Product analysis by
1
H NMR. All reactions without bicarbonate
gave no detectable epoxide products after 24 h. Dibasic ammonium
phosphate was employed to maintain similar ionic strength and pH of
reaction media in the control reactions.
oxidant peroxymonocarbonate ion, HCO
4
-
, is formed with
t
1/2
5 min (eq 1), presumably via the perhydration of CO
2
HCO
3
-
h H
2
O
HCO
4
-
H
2
O
2
+
+
(1)
Peroxymonocarbonate is an anionic peracid with structure
HOOCO
2
-
.
14
Kinetic and thermodynamic investigations of eq 1
give a value of
E
0
(HCO
4
-
/ HCO
3
-
). 1.8 V (vs NHE), and HCO
4
-
is therefore a potent oxidant in aqueous solution. The maximum
catalytic efficiency for oxidation of organic sulfides is observed
in the pH range from 7 to 9, and the oxidation reactions are
accelerated by increasing solvent water content.
15
The reactivity
of HCO
4
-
toward sulfides suggested to us that it may also be
useful in the preparation of epoxides in water and mixed solvents,
and this was confirmed in the work described below.
The oxidation of water-soluble alkenes was carried out in D
2
O
in an NMR tube with a stoichiometric excess of H
2
O
2
(1.5-6.0
equiv). For example, 1 mL of 0.1 M 4-vinylbenzenesulfonate with
1 M NaHCO
3
was prepared in D
2
O, and 30% H
2
O
2
was added
(final [H
2
O
2
]
* To whom correspondence should be addressed. Telephone: (352) 392-
6736. Fax: (352) 392-3255. E-mail:der@chem.ufl.edu.
(1) (a) Rudolph, J.; Reddy, K. L.; Chiang, J. P.; Sharpless, K. B.
J. Am.
Chem. Soc.
1997
,
119
, 6189. (b) Herrmann, W. A.; Ding, H.; Kratzer, R. M.;
K ¨ hn, F. E.; Haider, J. J.; Fischer, R. W.
J. Organomet. Chem
.
1997
,
549
,
319.
(2) Sheldon, R. A.
Top. Curr. Chem.
1993
,
164
,21
0.15 M, pH 8).
1
H NMR studies gave a
t
1/2
value
of 1.5 h for the initial disappearance of alkene, and after 15 h,
the starting material was converted to epoxide (90%), diol (5%),
and other byproducts (5%). The same procedure was applied to
several other water-soluble alkenes (Table 1). In all cases,
reactions without added bicarbonate salt are negligible after 24 h
under similar conditions (as a control, replacement of NaHCO
3
by (NH
4
)
2
HPO
4
provided comparable ionic strength and pH). The
water-soluble alkenes in Table 1 are mostly terminal alkenes with
nearby electron-withdrawing groups. The low electron density
of these alkenes usually reduces their nucleophilicity toward
electrophilic oxygen of peroxyacids.
16
The last two entries in Table
1 show that under the aqueous conditions of these reactions,
readily hydrolyzed epoxides are partially converted to diols. This
hydrolysis can be suppressed by using solvents with lower water
content.
17
We found that the BAP system can be applied to a variety of
homogeneous alkene oxidations (including epoxidation of terminal
)
34.
(3) (a) Strukul, G.
Catalytic Oxidation with Hydrogen Peroxide as Oxidant
;
Kluwer: Dordrecht, 1992. (b) MÅ‚ochowski, J.; Said, S. B.
Pol. J. Chem
.
1997
,
71
, 149.
(4) Edwards, J. O. In
Peroxide Reaction Mechanisms
; Edwards, J. O., Ed.;
Interscience: New York, 1962; pp 67-106.
(5) Jacobson, E. N. In
Comprehensi
-
e Organometallic Chemistry II
; Abel,
E. W., Stone, F. G., Wilkinson, E., Eds.; Pergamon: New York, 1995; Vol.
12, p 1097.
(6) (a) Tetzlaff, H. R.; Espenson, J. H.
Inorg. Chem.
1999
,
38
, 881. (b)
Venturello, C.; Alneri, E.; Ricci, M.
J. Org. Chem.
1983
,
48
, 3831. (c) De
Vos, D. E.; Sels, B. F.; Reynaers, M.; Rao, Y. V. S.; Jacobs, P. A.
Tetrahedron
Lett.
1998
,
39
, 3221.
(7) (a) Swern, D. In
Organic Peroxides
; Swern, D., Ed.; Wiley-Inter-
science: New York, 1971; Vol. 2, p 355. (b) Lewis, S. H. In
Oxidation
;
Augustine, R. L., Ed.; Marcel-Dekker: New York, 1969; Vol. 1, p 213.
(8) Payne, G. B.; Deming, P. H.; Williams, P. H.
J. Org. Chem.
1961
,
26
,
659.
(9) Majetich, G.; Hicks, R.
Synlett
1996
, 649.
(10) McKillop, A.; Sanderson, W. R.
Tetrahedron
1995
,
51
, 6145.
(11) Drago, R. S.; Frank, K. M.; Yang, Y.-C.; Wagner, G. W.
Proceedings
of 1997 ERDEC Scientific Conference on Chemical and Biological Defense
Research
; ERDEC, 1998.
(12) Richardson, D. E.; Yao, H.; Xu, C.; Drago, R. S.; Frank, K. M.;
Wagner, G. W.; Yang, Y.-C.
Proceedings of 1998 ERDEC Scientific
Conference on Chemical and Biological Defense Research
; ECBC, 1999.
(13) Richardson, D. E.; Yao, H.; Frank, K. M.; Bennett, D.
J. Am. Chem.
Soc.
2000
,
122
, in press.
(14) (a) Flanagan, J.; Jones, D. P.; Griffith, W. P.; Skapski, A. C.; West,
A. P.
J. Chem. Soc., Chem. Commun.
1986
,20
V
(15) Although used in large concentrations, bicarbonate is a catalyst so
the oxidations described here are low
E
factor reactions, in contrast to
stoichiometric activators where a leaving group becomes a byproduct. See
Sheldon, R. A.
J. Chem. Technol. Biotechnol
.
1997
,
68
, 381.
(16) (a) Prat, D.; Lett, R.
Tetrahedron Lett.
1986
,
27
, 707. (b) Prat, D.;
Delpech, B. Lett, R.
Tetrahedron Lett.
1986
,
27
, 711. (c) Stevens, H. C.;
Kamen, A. J.
J. Am. Chem. Soc.
1965
,
87
, 734.
(17) Conversion rates are lower in mixed organic/aqueous solvents, in part
because bicarbonate solubility decreases and less catalyst can be used; however,
bicarbonate salts with alkylated ammonium cations can be used to increase
catalyst solubility (Yao, H.; Richardson, D. E., work in progress).
-
21. (b) Jones, D. P.; Griffith,
W. P.
J. Chem. Soc., Dalton Trans.
1980
, 2526
-
2532. (c) Adam, A.; Mehta,
M.
Angew. Chem., Int. Ed.
1998
,
37
, 1387
-
1388.
10.1021/ja993935s CCC: $19.00 © 2000 American Chemical Society
Published on Web 03/16/2000
 Communications to the Editor
J. Am. Chem. Soc., Vol. 122, No. 13, 2000
3221
Table 2.
Epoxidation
a
of Alkenes by Hydrogen Peroxide with
Ammonium Bicarbonate in CD
3
CN/D
2
O (3:2, v:v)
b
allylic
alcohols
is
that
the
major
products
are
usually
the
rearranged epoxides, i.e., terminal epoxides.
It is necessary to distinguish the mechanism of alkene oxida-
tions with the BAP system in CH
3
CN/H
2
O from that of Payne’s
procedure
8
in alcoholic solvent. Payne oxidations employ a slight
excess of stoichiometric acetonitrile in alkaline hydrogen peroxide
solution to produce a peroxycarboximidic acid, which oxidizes
alkenes. The byproduct acetamide is obtained stoichiometrically
from the reaction of peroxycarboximidic acid with alkene or
hydrogen peroxide. In our study, oxidation of 4-vinylbenzene-
sulfonate with the BAP system in the presence of a stoichiometric
amount of acetonitrile in D
2
O was investigated by using
1
H NMR.
Over 90% of the alkene was converted to its epoxide product in
24 h, but no acetamide was detected in the
1
H NMR spectrum.
In contrast, replacement of NaHCO
3
(pH. 8.4) or NH
4
HCO
3
(pH.
8.0) by Na
2
CO
3
(pH. 10.5) gave no oxidation products of the
alkene after 24 h, but acetamide was formed. We conclude that
the role of acetonitrile in the BAP system is to provide for
substrate solubility and maintain high solvent polarity, favoring
epoxidation by HCO
4
-
.
20
The mechanism for HCO
4
-
epoxidation may be closely related
to that for typical peracids, i.e., the generally accepted butterfly
transition state,
21
except that the proton transfer is to a carbonate-
leaving group (
A
) rather than to a carboxylates. Since the BAP
reactions here are in aqueous or mixed aqueous solution, the
intramolecular proton transfer that reduces charge separation in
the transition state could also occur by solvent participation (e.g.,
B
). Further studies on the detailed mechanism are in progress.
a
Stoichiometry: alkene
0.05 M, hydrogen peroxide
0.3 M and
ammonium
C.
b
All reactions without
bicarbonate gave negligible epoxide products after 24 h, except for
3-methyl-2-buten-1-ol (10% conversion to epoxide in 24 h). Dibasic
ammonium phosphate was employed in controls to maintain similar
ionic strength and pH of reaction media.
c
All allylic epoxides rear-
ranged to form terminal epoxides as the major product.
d
The epoxide
was not stable; decomposition products not identified.
bicarbonate
0.2
M;
25
°
e
Mixture of
statistically distributed epoxide products.
alkenes, internal alkenes, and allylic alcohols) if a mixed solvent
system is used. By using acetonitrile/water (3:2 v:v), epoxidations
of hydrophobic alkenes were accomplished with H
2
O
2
and NH
4
-
HCO
3
(
0.2 M) at room temperature (Table 2).
Oxidation of styrene was followed in CD
3
CN/D
2
O (3:2, v:v)
by using NMR. Addition of styrene (0.05 M) to a solution of
H
2
O
2
(0.3 M) and NH
4
HCO
3
(0.2 M) yielded styrene oxide (40%)
as the only product after 24 h. Because of peroxide dispropor-
tionation, excess hydrogen peroxide is needed to give a high yield
of epoxide, and the epoxidation reaction was attempted prepara-
tively in CH
3
CN/H
2
O (3:2, v:v). With 0.19 M NH
4
HCO
3
, 10 equiv
of 30% aqueous H
2
O
2
gave styrene oxide in 75% distilled yield.
18
Other unfunctionalized alkenes in Table 2 (R-methylstyrene and
norbornene) form epoxide as the major product. The rate of alkene
oxidation decreases significantly by replacement of acetonitrile
with alcohol, e.g., ethanol or
tert
-butyl alcohol. For example, only
trace oxidation products were detected for styrene after heating
to 45
Our
13
C NMR studies on H
13
CO
4
-
formation from H
13
CO
3
-
with2MH
2
O
2
in CH
3
CN/H
2
O (3:2, v:v) indicate
K
eq
(eq 1)
[HCO
4
-
][H
2
O]/[HCO
3
-
][H
2
O
2
]
35 (25 °C) with a
t
1/2
<5 min
(pH
50% of H
2
O
2
is consumed by
decomposition based on the integration ratio of H
13
CO
3
-
and
H
13
CO
4
-
in the spectrum. Therefore, decomposition of hydrogen
peroxide in acetonitrile is relatively slow compared to the
formation of HCO
4
-
. Oxidation reactions of alkenes with moder-
ate reactivity can be achieved by forming HCO
4
-
with a small
excess of H
2
O
2
despite the accompanying decomposition of H
2
O
2
in the presence of CH
3
CN as a cosolvent.
22
Catalyst lifetime is
not a major concern given the low cost and high stability of
bicarbonate ion.
We believe BAP oxidations can be useful when a mild, low
environmental impact oxidation method is desirable.
23,24
Some
limits to the utility of the method remain to be overcome (e.g.,
low conversions for less nucleophilic substrates, hydrolysis of
sensitive epoxides). Kinetic studies and development of optimal
catalysts and synthetic methods for alkenes and other substrates
are in progress.
JA993935S
)
7.4).
After
20
h,
C for 2 days in
d
6
-EtOH/D
2
O (3:2, v:v) with H
2
O
2
(0.3
M) and NH
4
HCO
3
(0.2 M).
19
BAP oxidations of various allylic alcohols were also investi-
gated. Allyl alcohol (0.1 M) and 2-cyclohexen-1-ol (0.1 M) have
the least reactive double bonds, and only trace oxidation products
are observed for dilute H
2
O
2
(0.3 M) with NH
4
HCO
3
(0.2 M) in
CD
3
CN/D
2
O after 24 h. Allylic alcohols with more substituted
double bonds are epoxidized by the BAP system under similar
conditions (Table 2). For all of the allylic alcohols epoxidation
is strongly preferred over alcohol oxidation. In the case of
geraniol, both allylic and remote alkene are oxidized with
comparable rates. A striking feature in the BAP oxidation of these
°
(20) In addition, the same reaction was carried out in mixed CD
3
CN/D
2
O
(1:7, v:v) solvent that was buffered with (NH
4
)
2
HPO
4
to maintain similar pH
and ionic strength compared to a bicarbonate solution, and only 5% of alkene
conversion was observed after 24 h. In contrast to the simplicity of the
homogeneous BAP procedure, the Payne procedure requires stirring and
continuous addition of peroxide and base,
(21) See Bach, R. D.; Glukhovtsev, M. N.; Gonzalez, C.
J. Am. Chem.
Soc.
1998
,
120
, 9902
(18) Procedure: 6.30 g of NH
4
HCO
3
(79 mmol) and 38 mL of H
2
O
2
(30%,
360 mmol) were dissolved in 130 mL water, mixed with 240 mL of
acetonitrile, and 4 mL of styrene (35 mmol) was added. The rt reaction was
allowed to proceed in the dark without stirring for 24 h. The reaction mixture
was diluted with 200 mL of water and extracted with chloroform (5
200
mL). The filtrate was washed with water (2
40 mL), dried, and concentrated
by removal of solvent. Fractional distillation of the crude product gave 3.1 g
of styrene oxide (75%).
(19) The observations of solvent dependence in the BAP epoxidations
contrast with those for the H
2
O
2
/dicyclohexylcarbodiimide (DCC) system
reported by by Majetich and co-workers.
9
The best solvents for the DCC-
activated epoxidation are hydroxylic ones such as methanol, ethanol or
2-propanol (except pure water).
9910 and references therein.
(22) As was found in Payne’s study, decomposition of H
2
O
2
is significantly
accelerated in the higher pH media of CH
3
CN/H
2
O with added Na
2
CO
3
, and
acetamide byproduct is observed.
(23) Bolm, C.; Beckman, O.; Dabard, O. A. G.
Angew. Chem., Int. Ed.
1999
,
38
, 907.
(24) Dartt, C. B.; Davis, M. E.
Ind. Eng. Chem. Res.
1994
,
33
, 2887.
-
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