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Development of a Ruthenium-Catalyzed Asymmetric Epoxidation Procedure with Hydrogen Peroxide as the Oxidant.

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Angewandte
Chemie
Homogeneous Catalysis
Development of a Ruthenium-Catalyzed
Asymmetric Epoxidation Procedure with
Hydrogen Peroxide as the Oxidant**
Man Kin Tse, Christian Dbler, Santosh Bhor,
Markus Klawonn, Wolfgang Mgerlein, Herbert Hugl,
and Matthias Beller*
The need of environmentally benign and clean oxidation
reactions remains an important goal of chemical research.
Although oxidation reactions constitute core technologies for
converting bulk chemicals into useful higher-value products,[1]
they are among the more problematic processes with regard
to general usage. Even today most of the known textbook
oxidation methods[2] lead to a significant amount of waste and
therefore should be avoided. Criteria for state-of-the-art
oxidation technologies should include high atom economy
and selectivity, broad substrate scope, usage of environmentally benign oxidation reagents, and sufficient catalyst
stability and productivity. By comparing different oxidation
methods, it is apparent that the oxidant used in the respective
transformation defines the quality and applicability of the
method. Clearly, molecular oxygen is the most ideal oxidant
for a number of oxidation reactions.[3] However, mostly only
one oxygen atom of an oxygen molecule is used productively
for oxidation (50 % atom efficiency),[4, 5] thus at least stoichiometric amounts of unwanted by-products are generated
during the reactions. One of the few examples in which both
oxygen atoms are used efficiently is the aerobic dihydroxylation of olefins, which we developed some time ago.[6, 7] Apart
from molecular oxygen, hydrogen peroxide is an environmentally benign oxidant, which theoretically generates only
water as a by-product.[8] Also it is advantageous compared to
other oxidants because of the availability and low price
(< 0.6 E kg 1 of 100 % H2O2).[9] Owing to its characteristic
physical properties H2O2 is particularly useful for liquid-phase
oxidations for the synthesis of fine chemicals, pharmaceuticals, agrochemicals, and electronic materials. Hence, the
discovery of new catalysts using H2O2 is an important goal in
oxidation chemistry.[10, 11]
[*] Dr. M. K. Tse, Dr. C. Dbler, Dipl.-Chem. S. Bhor,
Dipl.-Chem. M. Klawonn, Prof. Dr. M. Beller
Leibniz-Institut f'r Organische Katalyse (IfOK)
Universit-t Rostock e.V.
Buchbinderstrasse 5–6, 18055 Rostock (Germany)
Fax: (+ 49) 381-466-9324
E-mail: matthias.beller@ifok.uni-rostock.de
Dr. W. M-gerlein, Dr. H. Hugl
Bayer AG
51368 Leverkusen (Germany)
[**] This work has been financed by the State of Mecklenburg-Western
Pommerania, the Bundesministerium f'r Bildung und Forschung
(BMBF), and the Deutsche Forschungs. M.K.T. thanks the Alexander
von Humboldt Stiftung for granting him an AvH-fellowship.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2004, 43, 5255 –5260
For the enantioselective epoxidations of olefins to date
transition-metal complexes based on titanium (Sharpless
epoxidation)[12] and manganese (Jacobsen–Katsuki epoxidation)[13] have been the most successful catalysts. In addition,
significant progress using organic catalysts based on chiral
ketones (ketone catalysts from Shi, Yang, and co-workers)[14, 15] was reported recently. However, in spite of extensive
research efforts, the development of a general and catalytic
asymmetric-epoxidation method using H2O2 has not been
achieved.[16] Herein we report the development of a new
catalytic asymmetric-oxidation method that uses H2O2 in the
presence of ruthenium complexes, allows for general epoxidation of olefins in high yield with ee values up to 84 %, and is
simple to employ. In addition a novel class of chiral tridentate
ligands (pyboxazines) is presented.
We looked for ruthenium complexes[17] with a combination of two meridional ligands which should provide the
ability to tune both the activity and the asymmetric induction
of the catalyst separately. Therefore, we chose the ruthenium
(R2pybox)(pyridinedicarboxylate) complex 1 (pybox = 2,6-di4,5-dihydro-1,3-oxazol-2-yl pyridine) which has been
reported by Nishiyama et al. to catalyze the epoxidation of
trans-stilbene in the presence of PhI(OAc)2 as the stoichiometric oxidant.[18] Although transition-metal complexes rapidly decompose H2O2,[19] we thought after initial tests with
RuCl3/2,6-pyridinedicarboxylic acid[20] that it should be possible to tune complex 1 to a more general asymmetric
epoxidation catalyst with H2O2 (Scheme 1).
Scheme 1. Strategy of catalyst design.
Clearly, the enantioselective induction could be controlled
by the readily accessible pybox or new pyboxazine type
ligands (pyboxazine = 2,2’-pyridine-2,6-diyl bis(5,6-dihydro4H-1,3-oxazine)), which can be synthesized from commercially available a- or b-amino acids.[21] Changing the donating
atoms (S, C, N, or O) in the pyridinedicarboxylate ligand
should influence the reactivity and the selectivity of the
catalyst.
The epoxidation of styrene using hydrogen peroxide is
amongst the more challenging asymmetric epoxidation reactions both with regard to chemo- and enantioselectivity. We
used our recently developed in situ catalyst system[17d,e] and
investigated the influence of different ligands and reaction
conditions (Table 1).
DOI: 10.1002/anie.200460528
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5255
Communications
Table 1: Effects of ligands on ruthenium catalyzed asymmetric epoxidation of styrene.[a]
known complexes, [Ru{(S,S)-Ph2pybox}(pydic)] (1 a) and [Ru{(S,S)-iPr2pybox}(pydic)]
(1 e) new complexes, [Ru{H2-(S,S)-Ph2pybox}(pydic)] (1 b), [Ru{(S,S)-indanol2pybox}(pydic)] (1 c), and [Ru{(R,R)-Ph2(S,S)-Ph
(1 d),
which
2
[b]
[b]
[c]
[d]
2pybox}(pydic)]
Entry
L
t [h]
Conv. [%]
Yield [%]
Selec. [%]
ee [%]
derived from known pybox ligands, were
1
–
–
12
20
0
0
also synthesized.[21]
All the [Ru(pybox)(pydic)] complexes
2
12
80
49
61
24[e]
catalyzed the epoxidation of styrene with
30 % H2O2 in good yield (Table 2, entries 1–
3[f ]
12
> 99
70
70
31[e]
5). All reactions were run with 5 mol % of
Ru catalyst. However, a similar level of
4
12
20
8
40
n.d.[g]
efficiency is reached with 0.5 mol % of
catalyst (Table 3, entry 12). Moreover, the
5
12
20
10
50
n.d.[g]
catalytic system had a 67 % efficiency with
respect to H2O2 (Table 3, entry 13). Sub6
12
40
22
55
9[e]
stituents on the 4-position of the 4,5-dihydrooxazol ring positively influence the
[e]
7
–
12
31
14
45
13
enantioselectivity of the reaction more
8[h]
12
22
6
27
–
than those on the 5-position since the 4position is closer to the metal center
[a] Reaction conditions: In a 25-mL Schlenk tube, [{Ru(p-cymene)Cl2}2] (0.0125 mmol) and L1
(Table 2, entries 1 and 2). Moreover, a
(0.025 mmol) were stirred at room temperature in 2-methylbutan-2-ol (2 mL) under Ar for 10 min. A
flexible aryl ring in the substituent seems
solution of L2 (0.025 mmol) and Et3N (1.2 equiv per acid group) in 2-methylbutan-2-ol (2 mL) was added
to be essential (Table 2, entries 1 and 3) for
by cannular. The whole reaction mixture was heated at 65 8C for 1 h. After cooling to room temperature,
high enantioselectivity. The presence of the
the catalyst solution was diluted with 2-methylbutan-2-ol (5 mL), followed by the addition of styrene
comparatively sterically bulky iso-propyl
(0.5 mmol) and dodecane (GC internal standard, 100 mL). To this reaction mixture, a solution of 30 %
group gave a system that was not as reactive
H2O2 (170 mL, 1.5 mmol) in 2-methylbutan-2-ol (830 mL) was added over 12 h by a syringe pump.
[b] Determined by comparing with authentic sample on GC-FID. [c] Chemoselectivity for epoxide
and showed lower enantioselectivity
formation. [d] Determined by HPLC. [e] (R)-(+)-styrene oxide was the major enantiomer. [f ] The defined
(Table 2, entries 1 and 5). The epoxidation
complex 1 a was used. [g] Not determined. [h] Performed without L1.
of 1-methylcyclohexene in the standard
conditions with 5 mol % 1 a led to 100 %
conversion with 86 % yield, however, with
less than 5 % ee. This result suggests that a p–p interaction
The reactions were run at room temperature in the
between the ligand and the substrate may be present.[22]
presence of 2.5 mol % of [{Ru(p-cymene)Cl2}2] and 5 mol %
of each ligand. In general all experiments were performed
For the first time we employed pyboxazine ligands, which
with three equivalents of H2O2 (30 % in water), which was
are structurally related to pybox, and can be synthesized
easily from b-amino acid derivatives. The b-amino acid was
slowly dosed into the reaction mixture over 12 h. With
reduced by LiAlH4 directly or its methyl ester was reduced by
[{Ru(p-cymene)Cl2}2] alone (Table 1, entry 1), no epoxide was
detected, only unspecific decomposition of H2O2 and styrene.
NaBH4 in the presence of acid to the corresponding b-amino
To our delight, a combination of (S,S)-Ph2-pybox and H2pydic
alcohol.[21b] Cyclization of the b-amino alcohol with dimethyl
(pydic = pyridine dicarboxylate) led to a remarkable increase
pyridine-2,6-dicarboximidate in anhydrous CH2Cl2 gave the
in activity and chemoselectivity (61 %) with a moderate
pyboxazine ligand, which can be used directly for complex
enantioselectivity (Table 1, entry 2). Using the pre-made
formation.[21c,e] The metal complex, [Ru(S,S)-Ph2pyboxacomplex 1 a gave better yield (70 %) as well as a higher
zine)(pydic)] (2 a), was obtained accordingly. Enlargement
enantioselectivity (31 % ee) presumably owing to the higher
of the five-membered ring to a six-membered ring resulted in
concentration of the well-defined catalyst (Table 1, entry 3).
a system that increased the ee value to 48 % (Table 2, entry 6).
Modification of the pydic ligand resulted in a significant loss
These results show some important factors which can
of reactivity (Table 1, entries 2–6). In the presence of only one
rationalize the development of a new H2O2 catalyst: 1) the
of the ligands (pybox or pydic) only a small amount of
combination of pybox and pydic ligands at a ruthenium center
epoxide is formed (Table 1, entries 7 and 8). This result
provides the reactivity and enantioselectivity, 2) an aryl group
suggests that the combination of these meridional ligands,
on the 4-position of the dihydrooxazole ring results in good
pybox and pydic, plays a crucial role in the reactivity and
ee values with aromatic olefins, 3) a sterically bulky aryl
enantioselectivity and offers the opportunity to epoxidize
substituent may further improve the enantioselective inducolefins with 30 % H2O2.
tion, 4) the newly developed six-membered “pyboxazine” is
better than the five-membered “pybox” with respect to
Different ruthenium complexes were tested in the epoxenantioselectivity. Following these principles, we designed
idation of styrene (Table 2). All ruthenium catalysts were
and synthesized [Ru{(R,R)-1-naphthyl2pyboxazine}(pydic)]
directly prepared from the corresponding pybox ligand,
Na2pydic, and [{Ru(p-cymene)Cl2}2].[18] Apart from the
(2 b) and [Ru{(R,R)-2-naphthyl2pyboxazine}(pydic)] (2 c;
5256
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5255 –5260
Angewandte
Chemie
Table 2: [Ru(pybox))(pydic)]-
and
[Ru(pyboxazine)(pydic)]-catalyzed
epoxidation
of
styrene.[a]
t [h]
Conv. [%][b]
Yield [%][b]
Selec. [%][c]
ee [%][d]
1
12
> 99
70
70
31[e]
2
12
100
66
66
3[f ]
3
20
91
59
65
18[e]
4
12
100
78
78
18[f ]
5
20
72
45
63
19[e]
6
12
81
56
69
48[e]
7
12
100
65
65
38[e]
8
12
82
59
72
48[e]
Entry
Catalyst
[a] In a 25-mL Schlenk tube, the catalyst (0.025 mmol) was stirred at room temperature in 2methylbutan-2-ol (9 mL) for 10 min. Styrene (0.5 mmol) and dodecane (GC internal standard, 100 mL)
were added. To this reaction mixture, a solution of 30 % H2O2 (170 mL, 1.5 mmol) in 2-methylbutan-2-ol
(830 mL) was added over 12 h by a syringe pump. [b] Determined by comparing with authentic samples
on GC-FID. [c] Chemoselectivity for epoxide formation. [d] Determined by HPLC. [e] (R)-(+)-styrene
oxide was the major enantiomer. [f ] (S)-( )-styrene oxide was the major enantiomer.
Angew. Chem. Int. Ed. 2004, 43, 5255 –5260
www.angewandte.org
Table 2, entries 7 and 8). In the
epoxidization, 2 b give a lower
enantioselectivity while 2 c gave
the same ee value as 2 a under
non-optimized conditions. However, after optimization 2 c was
the best catalyst.
Different aromatic olefins were
oxidized in the presence of catalyst
2 c in good to excellent yield with
good ee values under mild conditions (Table 3). With styrene, in the
presence of acetic acid (HOAc) as
cocatalyst (20 mol %), it was found
that the yield increased to 85 %
and the ee value increased to 59 %
with 2 c as the catalyst (Table 3,
entries 1 and 2). To our knowledge,
this is the highest ee value for
asymmetric epoxidation of styrene
using H2O2 as the oxidant. Mechanistic studies indicated that HOAc
accelerates the reaction, possibly
by stabilizing the active intermediates against self-degradation. The
water content increases with the
addition of H2O2 as the oxidant,
this means that the faster the
reaction is, the higher the enantioselectivity. We have also demonstrated that over-dosage of H2O in
the epoxidation of trans-stilbene
catalyzed by 1 a using PhI(OAc)2 as
the oxidant decreased the ee value.[17d] So this additive effect is
most prominent with less reactive
substrates and is diminished when
electron-rich olefins are employed.
The highest ee value (84 %) was
obtained with 2-methyl-1-phenyl1-propene at 0 8C with 20 mol %
HOAc and 1.5 equivalents of 50 %
H2O2 (Table 3, entry 16). To date
the new catalytic system has been
applied successfully to mono-, di-,
and trisubstituted olefins (Table 3).
The best results are obtained with
trans disubstituted olefins and trisubstituted olefins. Hence, the new
procedure complements the known
manganese-catalyzed asymmetric
epoxidations. Apart from differently substituted aromatic olefins,
allylic acetates and even allylic
chloride could be epoxidized in
high yield (Table 3, entries 15 and
16).
Preliminary mechanistic studies of the active species indicate
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5257
Communications
Table 3: Asymmetric epoxidation catalyzed by 2 c.[a]
Entry
R1
1
2
3
4
5
6
7
8
9
10
11[h]
12[i]
13
14
15
16
17
18
Substrate
R2
Ph
Ph
p-Cl-C6H4
p-F-C6H4
p-CF3-C6H4
p-CH3-C6H4
o-CH3-C6H4
o-Cl-C6H4
Ph
Ph
Ph
Ph
p-CH3O-C6H4
Ph
Ph
Ph
Ph
Ph
t [h]
Conv. [%][b]
Yield [%][b]
Selec. [%]
ee [%][c]
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
26
12
12
82
100
100
100
65
100
100
86
100
100
93
100
100
100
100
94
84
79
59
85
76
82
57
80
> 99
78
100
95
90
67[j]
> 99
> 99
93
91
83
68
72
85
76
82
88
80
> 99
91
100
95
97
67
> 99
> 99
93
97
99
86
48[d]
59[d],[e]
54[e]
60[e]
55[e]
58[e]
64[e]
58[e]
54[f ]
72[d],[g]
70[d],[g]
74[d],[g]
53
79
80
84[e][k]
48[e]
28[e]
R3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Ph
H
CH3
H
CH3
H
CH3
H
CH3
H
1,1-cyclohexyl
CH3
CH3
CH3
CH3
CH2OAc
H
CH2Cl
H
the so-called pyboxazines. It is expected
that these ligands will complement nicely
the catalytic behavior of the well-known
pybox derivatives.[23] The use of two different ligands significantly simplifies structural
variations on the catalyst thus allowing easy
tuning of the catalytic properties. This
situation is an important advantage compared to most catalysts and ligands used in
asymmetric oxidation catalysis. Full experimental detail can be found in the Supporting Information.
Received: April 30, 2004
.
Keywords: asymmetric catalysis ·
epoxidations · homogeneous catalysis ·
ruthenium
[1] K. Weissermel, H.-J. Arpe, Industrial
Organic Chemistry, 4th ed., Wiley-VCH,
Weinheim, 2003.
[a] In a 25-mL Schlenk tube, the catalyst (0.025 mmol) was stirred at room temperature in 2[2] For example, epoxides can be produced by
methylbutan-2-ol (9 mL) for 10 min. Olefin (0.5 mmol) and dodecane (GC internal standard, 100 mL)
cyclization of halohydrins or 1,2-glycols,
were added. To this reaction mixture, a solution of 30 % H2O2 (170 mL, 1.5 mmol) in 2-methylbutan-2-ol
epoxidation of olefins by peracids, reaction
(830 mL) was added over 12 h by a syringe pump. [b] Determined by comparing with authentic samples
of carbonyl compounds with gem-dihalides
on GC-FID. [c] Determined by HPLC, absolute configurations were not determined unless mentioned.
and Li or nBuLi, condensation between
[d] (R)-(+)-styrene oxide was the major enantiomer. [e] 20 mol % of HOAc was added. [f] (S,S)-( )aldehydes
and
a-halo
esters,
-ketones, or -amides, addition of sulfur
stilbene oxide was the major enantiomer. [g] (R,R)-(+)-1-Phenyl-1-propene oxide was the major
enantiomer. [h] In a 25-mL Schlenk tube, 2 a (0.0025 mmol) was stirred at room temperature in 2ylides or diazomethane to aldehydes or
ketones, and bimolecular reduction of aldemethylbutan-2-ol (9 mL) for 10 min. trans-1-Phenyl-1-propene (0.5 mmol), HOAc (5.7 mL, 0.10 mmol)
and dodecane (GC internal standard, 100 mL) were added. Cooled to 0 8C, a solution of 50 % H2O2
hydes or ketones. See: J. March, Advanced
(102 mL, 1.5 mmol) in 2-methylbutan-2-ol (898 mL) was added over 12 h by a syringe pump. [i] In a 25-mL
Organic Chemistry, 3rd ed., Wiley, New
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Schlenk tube, 2 a (0.025 mmol) was stirred at room temperature in 2-methylbutan-2-ol (9 mL) for
10 min. trans-1-Phenyl-1-propene (0.6 mmol), HOAc (5.7 mL, 0.10 mmol), and dodecane (GC internal
[3] R. A. Sheldon, J. K. Kochi, Metal-Catalyzed
Oxidations of Organic Compounds, Acastandard, 100 mL) were added. To this reaction mixture, a solution of 50 % H2O2 (34 mL, 0.5 mmol) in 2demic Press, New York, 1981.
methylbutan-2-ol (966 mL) was added 12 h by a syringe pump. [j] Yield based on H2O2. [k] 0 8C, a solution
of 50 % H2O2 (51 mL, 0.75 mmol) in 2-methylbutan-2-ol (949 mL) was added by syringe pump.
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P. R. Giles, M. Tsukazaki, S. M. Brown, C. J.
Urch, Science 1996, 274, 2044 – 2046; b) G.-J.
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Cavazzini, S. Quici, P. Knochel, Tetrahedron Lett. 2000, 41,
tBuOOH, and H2O2, UV/Vis spectroscopy showed that the
4343 – 4346; d) Y. Ishii, S. Sakaguchi, T. Iwahama, Adv. Synth.
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Catal. 2001, 343, 393 – 427; e) Y. Nishiyama, Y. Nakagawa, N.
spectrometry of the reaction mixture showed molecular ion
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Nakagawa, N. Mizuno, Stud. Surf. Sci. Catal. 2003, 145, 255 – 258;
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[6] a) C. DNbler, G. Mehltretter, M. Beller, Angew. Chem. 1999, 111,
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5258
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Angew. Chem. Int. Ed. 2004, 43, 5255 –5260
Angewandte
Chemie
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