Asymmetric epoxidation of olefins with hydrogen peroxide by an in situ-formed manganese complex

Article abstract of DOI:10.1021/jo501178k

Asymmetric epoxidation of a variety of cis, trans, terminal, and trisubstituted olefins in excellent yields (up to 94%) and enantioselectivities (>99% ee) by an in situ-formed manganese complex using H₂O ₂ has been developed. A relationship between the hydrophobicity of the catalyst imposed by ligand and the catalytic activity has been observed. The influence of the amount and identity of the acid additive was examined, and improved enantioselectivities were achieved through the use of a catalytic amount of a carboxylic acid additive.

Full text of DOI:10.1021/jo501178k

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Article
Asymmetric epoxidation of olefins with hydrogen
peroxide by an in situ formed manganese complex
Wen Dai, Sensen Shang, Bo Chen, Guosong Li, Lianyue Wang, Lanhui Ren, and Shuang Gao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo501178k • Publication Date (Web): 27 Jun 2014
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Asymmetric epoxidation of olefins with hydrogen peroxide by an
in situ formed manganese complex
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Wen Dai,†,‡,§ Sensen Shang,†,‡,§ Bo Chen,†,‡,§ Guosong Li,†,‡,§ Lianyue Wang,†,‡
Lanhui Ren†,‡,§ and Shuang Gao*,†,‡
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†Dalian Institute of Chemical Physics, the Chinese Academy of Sciences, Dalian,
116023, People’s Republic of China
‡Dalian National Laboratory for Clean Energy, People’s Republic of China
§University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of
China
*E-mail: sgao@dicp.ac.cn
ABSTRACT
Asymmetric epoxidation of a variety of cis-, trans-, terminal and trisubstituted
olefins in excellent yields (up to 94%) and enantioselectivities (>99% ee) by an in situ
formed manganese complex using H2O2 has been developed. A relationship between
the hydrophobicity of catalyst imposed by ligand and the catalytic activity has been
observed. The influence of the amount and identity of acid additives is examined, and
the improved enantioselectivities are achieved through the use of the catalytic amount
of carboxylic acid additives.
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INTRODUCTION
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Optical pure epoxides play a significant role in organic chemistry.1 In addition, they
have also been extensively applied in constituting pharmacophores in drug molecules,
including several marketed pharmaceuticals such as L-carnitine, Timolol and
Propranolol.2 Asymmetric epoxidation (AE) provides a powerful synthetic method
towards optical pure epoxides.3 In line with toughening environmental concerns,
current challenges for asymmetric epoxidation lay in exploring more sustainable and
efficient catalyst system. To address these questions, extensive research focused on
studies towards development of biomimetic methods by mimicking the reactivity of
natural metalloenzymes owing to metalloenzyme-catalyzed reactions often exhibiting
exquisite substrate specificity and operating under green processes.4 Cytochromes
P450 as a superfamily of heme enzymes can catalyze oxygenation reaction of a
variety of substrates.5 Inspired by the cytochrome P450 enzyme, substantial efforts
have been focused on the development of biomimetic metalloporphyrins catalysts
capable to catalyze AE of olefins. Notably, as early as 1983, Groves and Meyers
reported an iron-porphyrin-catalyzed AE of styrenes.6 Since then, the Fe, Ru and Mn
complexes bearing chiral porphyrin ligands that can catalyze AE of olefins have been
identified.7 Despite these advances, however, metalloporphyrin-type catalysts for AE
of olefins have not been sufficiently refined to find application in preparation of
natural products and pharmaceuticals. First, the synthesis of the chiral porphyrin
ligands containing a variety of functional groups is a formidable challenge, rendering
the optimization and screening of a desired catalyst notoriously difficult. In addition,
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the substrate scope is limited. Consequently, the development of catalytic systems
with high conversion and selectivity that utilize a readily available, cheap and
non-toxic catalyst and environmentally benign oxidants is strongly desired.
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Scheme 1. Strategy for the development of asymmetric epoxidation method.
Inspired by the metalloporphyrins, we previously developed a new class of
manganese complexes featuring chiral oxazoline moieties and proved they were
efficient catalysts for asymmetric epoxidation of olefins with H2O2 in the presence of
acetic acid (Scheme 1).4s In 2012, Lyakin et al. first disclosed that different carboxylic
acid (CA) additives in organometallic catalyst had a significant influence on the
enantioselectivity of AE of olefins. In this case, the best enantioselectivities up to 93%
ee were obtained in the presence of 2-ethylhexanoic acid.8 Very recently, Miquel
Costas et al demonstrated that the ligands could synergistically cooperate with the CA
in promoting efficient O-O cleavage effect in the epoxidation of olefins with
hydrogen peroxide and excellent yields and enantioselectivities were achieved for
epoxidation of various olefins (up to 99% ee and 99% yield).4i With this background
in mind, extensive ligands and CA additives were screened in attempt to further
optimize our catalyst system. Herein, we report a rapid, efficient and highly
enantioselective epoxidation method with H2O2 by an in situ formed manganese
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complex, providing a broad range of epoxides in high yields. The improved
enantioselectivities are attained through the use of the catalytic amount of carboxylic
acid additives.
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RESULTS AND DISCUSSION
Firstly, the effect of CA additives was investigated in an attempt to optimize the
catalyst system and, in particular, to improve the epoxidation stereoselectivity. The
o
epoxidation of indene (1a) was initially performed in acetonitrile at -10 C with the
manganese complexes generated in situ from 1 mol% Mn(OTf)2 and 1 mol% L9 in
the presence of H2O2/HCOOH. Only the low conversion was observed (Table 1, entry
1). Then reaction was carried out by replacing the HCOOH with acetic acid. The
corresponding epoxide 2a was obtained in 76% yield and 63% ee (Table 1, entry 2).
Poor activity was observed when the acetic acid was replaced by the strong acid
CF3SO3H or p-Toluenesulfonic acid, inorganic acid H3PO4 or sodium acetate (Table 1,
entries 3-5 and 18). The results indicated that both the proton and carboxylic group
were needed to accelerate and favor the O-O cleavage in the epoxidation process.
Replacing the acetic acid with a wide variety of aliphatic acids led a notable
improvement in terms of reactivity and enantioselectivity (Table 1, entries 6-15).
Among these aliphatic acids, the adamantane carboxylic acid (aca) provided the best
result (90% yield, 76% ee; Table 1, entry 11). Perhaps the sterically hindered
adamantane carboxylic acid which could impart highly rigid environment around the
metal center resulted in significantly increased enantioselectivity. Interestingly, the
heterocyclic aromatic carboxylic acid such as nicotinic acid was also compatible with
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our catalyst system with high yield and modest enantioselectivity (Table 1, entry 17).
In addition to the racemic CA additives, the chiral carboxylic acid was also tested.
Unfortunately, only the low yield was obtained (Table 1, entry 16). After testing CA
loading, the amount of CA was successfully lowered to 50 mol% with no decrease of
yield and enantioselectivity (Table 1, entries 19-20). Further lowering the acid loading
to 30 mol% showed a decrease in yield, albeit with an almost identical
enantioselectivity (Table 1, entry 21).
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Table 1. Catalytic activity with regard to amount and identity of the additives.
entry
additive
HCO2H
CH3CO2H
AcONa
yield(%)
< 5
76
ee(%)a
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7
-
63
-
< 5
< 5
<5
CF3CO2H
H3PO4
-
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67
O
90
OH
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aca
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-
< 5
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20c
21d
aca
aca
aca
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92
86
72
75
76
a
b
c
Determined by chiral HPLC analysis. aca (1.0 equiv). aca
(0.5 equiv). d aca (0.3 equiv).
An extensive ligand study was then performed to find the optimum ligand for our
catalyst system. Replacing of ligand L9 containing bis-substituted oxazolines with
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ligands containing mono-substituted oxazolines resulted in a significant increase in
enantioselectivity (Table 2, entries 1-7). However, the ligand L8 bearing
methyl-substituted oxazolines performed poorly in terms of both yield and
enantioselectivity (Table 2, entry 8). The results implied that ligands with large
hydrophobic groups had an obvious advantage over ligand L8 with small hydrophobic
groups. Presumably, this unfortunate situation was largely attributed to the
hydrophobic structure of ligands making the substrate approach the active center of
catalysts more easily. In addition, the decomposition of hydrogen peroxide could be
greatly reduced. Following a broad screening of ligands, we identified L2 as the
ligand producing the best yield and enantioselectivity (Table 2, entry 2). It is
noteworthy that the catalyst loading was successfully lowered to 0.5 mol% with no
decrease of yield and enantioselectivity (Table 2, entry 9). Remarkably, further
lowering the catalyst loading to 0.25 mol % showed a slight decrease in yield and
enantioselectivity (Table 2, entry 10). Then the loading of H2O2 was also investigated.
We found that 4 equiv of H2O2 were necessary in order to obtain a good yield (Table
2, entries 2 and 11). Finally, the influence of temperature was examined. The
enantioselectivity had a slight decrease when the temperature was increased to 0 oC
(Table 2, entry 12). The enantioselectivity almost remained the same by further
lowering the temperature to -30 oC (Table 2, entry 13).
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Table 2. Investigation of effect of ligand structure.
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entry
ligand
% yield
% eea
1
2
L1
L2
L3
L4
L5
L6
L7
L8
L2
L2
L2
L2
L2
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< 5
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a
b
Determined by chiral HPLC analysis.
Mn(OTf)2 (0.5
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c
mol%), L2 (0.5 mol%). Mn(OTf)2 (0.25 mol%), L2 (0.25
9
d
mol%). Mn(OTf)2 (0.5 mol%), L2 (0.5 mol%), H2O2 (3.5
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e
o
f
equiv).
Mn(OTf)2 (0.5 mol%), L2 (0.5 mol%), 0 C.
Mn(OTf )2 (0.5 mol%), L2 (0.5 mol%), -30 oC.
After the optimized conditions were identified, the scope of the asymmetric
epoxidation was investigated. As expected, a series of cyclic cis-olefins including
chromene derivatives, indene and 1,2-dihydronaphthalene could be efficiently
epoxidized within short times, providing the corresponding chromene derivatives
(Table 3, entries 2-9), indene (Table 3, entry 1), and 1,2-dihydronaphthalene (Table 3,
entry 10) epoxides in high yields and excellent enantioselectivities. The substrates
could bear a wide range of groups, such as nitrile, ester, acetyl amino and phenyl. It is
noteworthy that good yield and high enantioselectivity were also obtained for the
reaction of acyclic cis-olefin cis-β-methylstyrene (Table 3, entries 11-12). Encouraged
by these results, we turned our attention to the challenging terminal olefins. Initial
epoxidation of styrene using adamantane carboxylic acid provided moderate yield and
low enantioselectivity (Table 3, entry 13). The enantioselectivity and yield could be
improved when employing 3 equiv cyclohexanecarboxylic acid (Table 3, entries
14-15). After replacing ligand L2 with L6, the reaction of styrene proceeded with a
better enantioselectivity, albeit with a decreased yield (Table 3, entry 16). The yield
could be significantly promoted when the catalyst loading was increased to 2.0 mol%
(Table 3, entries 17-18). The reaction of 4-methylphenylene gave the epoxide with
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good yield and remarkable enantioselectivity (Table 3, entry 19). To further explore
the generality of the current catalyst system, we investigated the epoxidation for
trans-olefins. The reaction of trans-stilbene gave the epoxide with excellent
enantioselectivity and low yield (Table 3, entry 20). Meanwhile, the epoxidation of
trans-β-methyl styrene gave moderate yield and enantioselectivity (Table 3, entry 21).
Finally, good yield and moderate enantioselectivity were also obtained for the
reaction of trisubstituted olefin 1-phenylcyclohexene when the reaction was carried
out under 1 mol% Mn(OTf)2 and ligand L2 in the presence of 3 equiv acetic acid
(Table 3, entries 22- 23).
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Table 3. Substrate scope of epoxidation.
entry
1
alkene
product
% yield
92
% eea
93
(1a)
2a
2b
3b
R = CN (1b)
R = COOMe
(1c)
2b
2c
90
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98
>99
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5b
R = Ph (1d)
R = NHAc (1e)
2d
2e
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6b
7b
R = CN (1f)
2f
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>99
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R = COOMe
(1g)
2g
8b
9b
R = Ph (1h)
R = NHAc (1i)
2h
2i
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>99
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10b
(1j)
2j
11
67
90
83
84
(1k)
(1k)
2k
2k
12c
13
14d
15e
R = H (1l)
R = H (1l)
R = H (1l)
2l
2l
2l
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70
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16f
R = H (1l)
2l
2l
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17g
R = H (1l)
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18h
19h
R = H (1l)
2l
74
88
69
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R = Me (1m)
2m
20
21
22
R = ph (1n)
R = Me (1o)
2n
2o
17
32
42
97
67
51
(1p)
(1p)
2p
2p
23i
85
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a Determined by chiral HPLC analysis. b Mn(OTf)2 (0.25 mol%),
c
d
L2 (0.25 mol%). Mn(OTf)2 (1.0 mol%), L2 (1.0 mol%).
e
cyclohexanecarboxylic acid (0.5 equiv). cyclohexanecarboxylic
f
acid (3.0 equiv).
Mn(OTf)2 (0.5 mol%), L6 (0.5 mol%),
g
cyclohexanecarboxylic acid (3.0 equiv). Mn(OTf)2 (1.0 mol%),
h
L6 (1.0 mol%), cyclohexanecarboxylic acid (3.0 equiv).
Mn(OTf)2 (2.0 mol%), L6 (2.0 mol%), cyclohexanecarboxylic
i
acid (3.0 equiv). Mn(OTf)2 (1.0 mol%), L2 (1.0 mol%), 50%
H2O2 (4.0 equiv), acetic acid (3.0 equiv).
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Based on our previous study and the pertinent literature, we proposed a possible
catalytic cycle (Scheme 2).4i,4j,4s,8-9 The (L)Mn(II) is initially converted to the
intermediate 3. Then the active species Mn(V)-oxo complex 4 is formed via
carboxylic acid assisted heterolysis cleavage of the O−O bond in the intermediate 3.
The active species 4 epoxidizes the olefins to the corresponding products along with
the formation of intermediate 3.
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Scheme 2. A proposed catalytic cycle.
To investigate the tolerance to water of our catalyst system, the experiment was
performed at 1% H2O2, affording the desired product 2a in 90% yield and 92% ee.
The result indicated that the reaction could proceed at a low concentration of H2O2
which made the procedure safe (Scheme 3).
Scheme 3. Water-tolerance of the reaction.
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To further evaluate the practical utility of the catalyst system, the AE of 1a was
enlarged to a gram scale under the optimized conditions, and the desired product was
furnished with 93% yield and 92% ee (Scheme 4).
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Scheme 4. The gram-scale synthesis of epoxide 2a.
CONCLUSION
In summary, the catalytic AE of a variety of olefins based on an inexpensive and
readily available in situ formed manganese complex with H2O2 has been developed.
The optically active epoxides with excellent enantioselectivities (>99% ee) are
obtained in synthetically valuable yields (up to 94%). Improvement of
enantioselectivity is attained by the use of catalytic amount of carboxylic acid
additives. Furthermore, suitable hydrophobicity of catalyst imposed by ligand is
essential to the catalytic activity, providing a useful guiding principle for future
rational design of a catalyst. Extension of the strategy to other reactions is in progress.
EXPERIMENTAL SECTION
General Information. Unless otherwise stated, all reactions and manipulations
were carried out under argon atmosphere using standard Schlenk techniques or in an
argon-filled glove-box. All chemicals were obtained from commercial sources and
were used without further purification. Solvents were treated prior to use according to
the standard methods. Column chromatography was carried out on silica gel (300–400
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mesh) using a forced flow of eluent at 0.3–0.5 bar pressure. NMR Spectra were
recorded at room temperature in CDCl3 on 400 MHz spectrometers. The chemical
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shifts for H NMR were recorded in ppm downfield from tetramethylsilane (TMS)
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with CDCl3 (7.26 ppm) as the internal standard. The chemical shifts for 13C NMR
were recorded in ppm downfield using the central peak of CDCl3 (77.16 ppm) as the
internal standard. 13C NMR was broad-band decoupled from hydrogen nuclei.
Coupling constants (J) are reported in Hertz and refer to apparent peak
multiplications.
Characterization of Starting Materials
The ligands L6-L9 were prepared following the procedure described in the
reported literature.4s,10 L1-L5 known compounds.4s
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L6. Yellow solid, 2.14 g, 42% yield; H NMR (400 MHz, CDCl3) δ 10.38 (2H, s),
7.71 (2H, d, J = 7.8 Hz), 7.46 (2H, m), 7.17 (4H, d, J = 3.5 Hz), 7.10 – 6.98 (2H, m),
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6.68 (2H, m), 4.17 (2H, m), 3.87 – 4.0 (4H, m), 0.66 (18H, s); C {1H} NMR (100
MHz, CDCl3) δ 163.9, 146.6, 135.9, 132.2, 130.2, 124.1, 123.8, 117.2, 113.7, 111.3,
67.5, 56.3, 33.9, 26.3; HRMS (ESI-TOF) m/z calcd for C32H39N4O2 [M+H]+ 511.3073,
found 511.3073.
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L7. Yellow solid, 2.08 g, 46% yield; H NMR (400 MHz, CDCl3) δ 10.34 (2H, s),
7.72 (2H, dd, J = 8.0, 1.2 Hz), 7.47 (2H, m), 7.23 – 7.11 (4H, m), 7.09 – 7.03 (2H, m),
6.73 – 6.61 (2H, m), 4.29 (2H, m), 4.12 – 3.94 (2H, m), 3.82 (2H, t, J = 7.9 Hz), 1.39
(4H, m), 0.74 (6H, t, J = 7.4 Hz); 13C {1H} NMR (100 MHz, CDCl3) δ 163.8, 146.6,
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135.6, 132.3, 130.2, 124.2, 124.0, 117.1, 113.7, 111.2, 71.1, 68.7, 29.4, 10.6; HRMS
(ESI-TOF) m/z calcd for C28H31N4O2 [M+H]+ 455.2447, found 455.2473.
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L8. Yellow solid, 1.66 g, 39% yield; H NMR (400 MHz, CDCl3) δ 10.29 (2H, s),
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7.72 (2H, dd, J = 7.6, 1.6 Hz), 7.48 (2H, m), 7.22 – 7.15 (2H, t, J =7.6), 7.09 (4H, m),
6.69 (2H, t, J = 7.6), 4.39 – 4.27 (2H, m), 4.25 – 4.10 (2H, m), 3.74 (2H, t, J = 7.8 Hz),
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1.08 (6H, d, J = 6.6 Hz); C {1H} NMR (100 MHz, CDCl3) δ 163.7, 146.8, 135.7,
132.3, 130.2, 124.5, 117.1, 113.6, 111.1, 72.8, 62.6, 21.9; HRMS (ESI-TOF) m/z
calcd for C26H27N4O2 [M+H]+ 427.2134, found 427.2157.
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L9. Yellow solid, 3.65 g, 52% yield; H NMR (400 MHz, CDCl3) δ 10.36 (2H, s),
7.79 (2H, dd, J = 7.9, 1.3 Hz), 7.54 – 7.43 (2H, m), 7.40 – 7.30 (6H, m), 7.29 – 7.25
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(4H, m), 7.18 – 7.02 (16H, m), 6.69 – 6.63 (2H, m), 5.03 (4H, m); C {1H} NMR
(100 MHz, CDCl3) δ 164.6, 147.0, 140.8, 132.7, 130.6, 129.4, 129.0, 127.9, 126.9,
126.6, 124.6, 124.4, 117.3, 114.0, 87.6, 79.0; HRMS (ESI-TOF) m/z calcd for
C48H39N4O2 [M+H]+ 703.3073, found 703.3077.
Representative Procedures for the Asymmetric Epoxidation of Olefins.
A solution of Mn(OTf)2 (0.0084 M solution in CH3CN, 0.25 mL, 0.0021 mmol)
was added to L2 (0.0084 M solution in CH3CN, 0.25 mL, 0.0021 mmol) at room
temperature. The reaction mixture was stirred at room temperature for 4 h. To the
solution of manganese complex was directly added substrate (0.42 mmol), CA (0.21
mmol, diluted with 0.5 mL CH3CN) and CH3CN (1 mL). Then decrease the
temperature to -10 °C, 50 % H2O2 (1.68 mmol, diluted with 0.5 mL CH3CN) was
rapidly added and the mixture was stirred at -10 °C for 2.0 h. At this point, a saturated
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aqueous solution of NaHCO3 (8 mL) was added and the resulting mixture was
extracted with EtOAc (10 mL x 3). Then, the organic layer was combined and washed
with brine, dried over MgSO4 and concentrated at reduced pressure. The residue was
purified by silica gel column chromatography to afford the corresponding epoxide.
(1aS,6aR)-6,6a-dihydro-1aH-indeno[1,2-b]oxirene (2a).11 Colorless oil, purified
by column chromatography on silica gel (5% EtOAc in petroleum ether) (51.0 mg, 92%
yield, 93% ee). 1H NMR (400 MHz, CDCl3) δ 7.51 (1H, m), 7.27 – 6.67 (3H, m), 4.28
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(1H, s), 4.14 (1H, s), 3.22 (1H, d, J = 18.0 Hz), 2.98 (1H, d, J = 18.1 Hz); C {1H}
NMR (101 MHz, CDCl3) δ 144.1, 141.4, 129.1, 126.8, 126.7, 125.8, 59.71, 58.3, 35.2;
MS (EI) m/z 132 (M+); HPLC (DAICEL OJ-H, hexane/isopropanol 80:20, flow rate:
0.5 mL/min, 220 nm): tr (minor) = 16.6 min, tr (major) = 18.9 min.
(1aS,7bS)-2,2-dimethyl-2,7b-dihydro-1aH-oxireno[2,3-c]chromene-6-carbonitril
e (2b).1c White solid, purified by column chromatography on silica gel (20% EtOAc
in petroleum ether) (76.1 mg, 90% yield, 98% ee). 1H NMR (400 MHz, CDCl3) δ 7.65
(1H, d, J = 2.0 Hz), 7.52 (1 H, dd, J = 8.5 Hz, 2.1 Hz), 6.86 (1H, d, J = 8.5 Hz), 3.91
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(1H, d, J = 4.4 Hz), 3.54 (1H, d, J = 4.4 Hz), 1.60 (3H, s), 1.30 (3H, s); C {1H}
NMR (100 MHz, CDCl3) δ 156.5, 134.4, 133.8, 121.1, 119.0, 118.7, 104.4, 74.7, 62.3,
49.9, 25.5, 23.0; MS (EI) m/z 201 (M+); HPLC (DAICEL OJ-H, hexane/isopropanol
50:50, flow rate: 0.5 mL/min, 254 nm): tr (minor) = 17.2 min, tr (major) = 28.0 min.
(1aS,7bS)-methyl2,2-dimethyl-2,7b-dihydro-1aH-oxireno[2,3-c]chromene-6-carb
oxylate (2c).1c White solid, purified by column chromatography on silica gel (10%
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EtOAc in petroleum ether) (89.5 mg, 91% yield, >99% ee). H NMR (400 MHz,
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CDCl3) δ 8.07 (1H, d, J = 2.2 Hz), 7.93 (1H, dd, J = 8.1, 2.2 Hz), 6.83 (1H, d, J = 8.5
Hz), 3.95 (1H, d, J = 4.4 Hz), 3.89 (3H, s), 3.52 (1H, d, J = 4.4 Hz), 1.60 (3H, s), 1.28
(3H, s); 13C {1H} NMR (100 MHz, CDCl3) δ 166.4, 156.8, 132.1, 131.6, 123.0, 119.7,
118.0, 74.2, 62.4, 52.0, 51.6, 25.6, 23.0; MS (EI) m/z 234 (M+); HPLC (DAICEL
OJ-H, hexane/isopropanol 90:10, flow rate: 0.5 mL/min, 254 nm): tr = 37.3 min.
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(1aS,
7bS)-2,2-dimethyl-6-phenyl-2,7b-dihydro-1aH-oxireno[2,3-c]chromene
(2d).1c White solid, purified by column chromatography on silica gel (10% EtOAc in
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petroleum ether) (97.4 mg, 92% yield, 97% ee). H NMR (400 MHz, CDCl3) δ 7.55
(3H, m), 7.47 (1H, dd, J = 8.4, 2.3 Hz), 7.42 (3H, m), 7.31 (1H, m), 6.88 (1H, d, J =
8.4 Hz), 3.96 (1H, d, J = 4.4 Hz), 3.52 (1H, d, J = 4.4 Hz), 1.60 (3H, s), 1.30 (3H, s);
13C NMR {1H} (100 MHz, CDCl3) δ 152.1, 140.5, 134.3, 129.0, 128.8, 128.3, 126.9,
126.7, 118.4, 73.3, 62.8, 51.1, 25.7, 22.7; MS (EI) m/z 252 (M+); HPLC (DAICEL
OD-H, hexane/isopropanol 95:5, flow rate: 0.5 mL/min,220 nm): tr (minor) = 14.3
min, tr (major) =17.7 min.
N-((1aS,7bS)-2,2-dimethyl-2,7b-dihydro-1aH-oxireno[2,3-c]chromen-6-yl)aceta
mide (2e ).1c Yellow solid, purified by column chromatography on silica gel (50%
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EtOAc in petroleum ether) (92.0 mg, 94% yield, >99% ee). H NMR (400 MHz,
CDCl3) δ 7.65 (1H, d, J = 2.2 Hz), 7.34 (1H, s), 7.15 (1H, dd, J = 8.6, 2.3 Hz), 6.73
(1H, d, J = 8.6 Hz), 3.86 (1H, d, J = 4.3 Hz), 3.47 (1H, d, J = 4.4 Hz), 2.14 (3H, s),
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1.56 (3H, s), 1.23 (3H, s); C {1H} NMR (100 MHz, CDCl3) δ 168.3, 149.3, 131.3,
122.4, 122.0, 120.3, 118.3, 77.3, 77.0, 76.7, 73.1, 62.8, 51.0, 25.6, 24.3, 22.5; MS (EI)
m/z 233 (M+); HPLC (DAICEL OJ-H, hexane/isopropanol 50:50, flow rate: 0.5
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mL/min, 254 nm): tr = 10.1 min.
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(1a'S,7b'S)-1a',7b'-dihydrospiro[cyclohexane-1,2'-oxireno[2,3-c]chromene]-6'-c
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arbonitrile (2f).1c White solid, purified by column chromatography on silica gel (20%
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EtOAc in petroleum ether) (91.1 mg, 90% yield, >99% ee). H NMR (400 MHz,
CDCl3) δ 8.35 – 7.37 (1H, m), 7.46 (1H, d, J = 8.5 Hz), 6.85 (1H, d, J = 8.5 Hz), 3.82
(1H, d, J = 4.3 Hz), 3.48 (1H, d, J = 4.3 Hz), 2.03–1.30 (10H, m); C {1H} NMR
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(100 MHz, CDCl3) δ 156.8, 134.9, 134.3, 122.6, 119.7, 119.4, 104.7, 75.9, 62.5, 50.0,
34.4, 31.3, 25.7, 21.7, 21.3; MS (EI) m/z 241 (M+); HPLC (DAICEL OJ-H,
hexane/isopropanol 50:50, flow rate: 0.5 mL/min, 254 nm): tr =23.3 min.
(1a'S, 7b'S)-methyl 1a', 7b'- dihydrospiro[cyclohexane-1,2'-oxireno [2,3-c]
chromene]-6'-carboxylate (2g).1c White solid, purified by column chromatography on
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silica gel (10% EtOAc in petroleum ether) (102.4 mg, 89% yield, 98% ee). H NMR
(400 MHz, CDCl3) δ 8.05 (1H, d, J = 1.7 Hz), 7.93 (1H, dd, J = 8.5, 1.8 Hz), 6.88 (1H,
d, J = 8.5 Hz), 3.91 (1H, d, J = 4.4 Hz), 3.89 (3H, s), 3.51 (1H,d, J = 4.4 Hz), 2.10
(1H, m), 1.85 (1H, m), 1.76 – 1.33 (10H, m); C {1H} NMR (100 MHz, CDCl3) δ
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166.5, 156.6, 132.1, 131.6, 123.0, 120.5, 118.0, 74.8, 62.0, 51.9, 50.1, 34.0, 30.7, 25.3,
21.2, 20.8; MS (EI) m/z 274 (M+); HPLC (DAICEL OJ-H, hexane/isopropanol 50:50,
flow rate: 0.5 mL/min, 254 nm): tr (minor) = 15.4 min, tr (major) =16.7 min.
(1a'S,7b'S)-6'-phenyl-1a',7b'-dihydrospiro[cyclohexane-1,2'-oxireno[2,3-c]chrom
ene] (2h).1c White solid, purified by column chromatography on silica gel (10%
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EtOAc in petroleum ether) (115.3 mg, 94% yield, 95% ee). H NMR (400 MHz,
CDCl3) δ 7.54 (3H, d, J = 7.7 Hz), 7.46 (1H, d, J = 8.3 Hz), 7.41 (2H, m), 7.30 (1H,
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m), 6.92 (1H, d, J = 8.4 Hz), 3.92 (1H, d, J = 4.3 Hz), 3.51 (1H, d, J = 4.3 Hz), 1.97
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(2H, m), 1.68 (5H, m), 1.54 – 1.34 (3H, m); C {1H} NMR (100 MHz, CDCl3) δ
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152.4, 141.1, 134.8, 129.5, 129.3, 128.8, 127.4, 127.3, 121.7, 119.0, 74.4, 63.0, 51.2,
34.7, 30.9, 26.0, 21.8, 21.5; MS (EI) m/z 292 (M+); HPLC (DAICEL OD-H,
hexane/isopropanol 90:10, flow rate: 0.5 mL/min, 254 nm): tr (minor) = 11.9 min, tr
(major) =15.9 min.
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N-((1a'S,7b'S)-1a',7b'-dihydrospiro[cyclohexane-1,2'-oxireno[2,3-c]chromen]-6'-
yl)acetamide (2i).1c Yellow solid, purified by column chromatography on silica gel
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(50% EtOAc in petroleum ether) (107.8 mg, 93% yield, >99 % ee). H NMR (400
MHz, CDCl3) δ 7.62 (d, J = 2.6 Hz, 1H), 7.26 (s, 1H), 7.17 (1H, dd, J = 8.6, 2.6 Hz),
6.79 (1H, d, J = 8.6 Hz), 3.83 (1H, d, J = 4.4 Hz), 3.46 (1H, d, J = 4.4 Hz), 2.14 (3H,
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s), 1.92 – 1.78 (1H, m), 1.72 – 1.48 (7H, m), 1.41 – 1.30 (2H, m); C {1H} NMR
(100 MHz, CDCl3) δ 168.2, 149.0, 131.2, 122.3, 122.0, 121.2, 118.4, 73.7, 62.4, 50.5,
34.1, 30.1, 25.4, 24.3, 21.1, 20.9; MS (EI) m/z 273 (M+); HPLC (DAICEL OJ-H,
hexane/isopropanol 50:50, flow rate: 0.5 mL/min, 254 nm): tr = 22.9 min.
(1aR,7bS)-1a,2,3,7b-tetrahydronaphtho[1,2-b]oxirene (2j).11 Colorless oil,
purified by column chromatography on silica gel (5% EtOAc in petroleum ether)
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(57.0 mg, 92% yield, 95% ee). H NMR (400 MHz, CDCl3) δ 7.39 (1H, d, J = 7.3
Hz,), 7.28 – 7.18 (2H, m), 7.08 (1H, d, J = 7.3 Hz), 3.84 (1H, d, J = 4.2 Hz), 3.73 (,
1H, d, J = 4.2 Hz), 2.89 – 2.71 (m, 1H), 2.54 (1H, m), 2.41 (1H, m), 1.76 (1H, m); 13C
{1H} NMR (100 MHz, CDCl3) δ 137.3, 130.1, 129.0, 129.0, 55.7, 53.3, 25.0, 22.4;
MS (EI) m/z 146 (M+); HPLC (DAICEL OB-H, hexane/isopropanol 99:1, flow rate:
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0.5 mL/min,220 nm): tr (major) = 22.6 min, tr (minor) = 29.2 min.
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Cis-2-methyl-3-phenyloxirane(2k).4i,12 Colorless oil, purified by column
chromatography on silica gel (1% EtOAc in petroleum ether) (51.0 mg, 90% yield, 84%
ee). 1H NMR (400 MHz, CDCl3) δ 7.36 – 7.26 (5H, m), 4.06 (1H, d, J = 4.2 Hz), 3.34
(1H, m), 1.09 (3H, d, J = 5.4 Hz); 13C NMR {1H} (101 MHz, CDCl3) δ 135.50, 128.0,
127.5, 126.6, 57.6, 55.2, 12.5; HPLC (DAICEL OD-H, hexane/isopropanol 99:1, flow
rate: 0.5 mL/min, 220 nm), tr (major) = 10.1 min, tr (minor) =13.0 min.
2-phenyloxirane(2l).4s Colorless oil, purified by column chromatography on silica
gel (5% EtOAc in petroleum ether) (37.3 mg, 74% yield, 69% ee). HPLC (DAICEL
OD-H, hexane/isopropanol 99:1, flow rate: 0.5 mL/min, 220 nm): tr (major) = 11.2
min, tr (minor) =14.1 min.
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2-(p-tolyl)oxirane (2m).4s Colorless oil, purified by column chromatography on
silica gel (5% EtOAc in petroleum ether) (49.5 mg, 88% yield, 68% ee). HPLC
(DAICEL OD-H, hexane/isopropanol 99:1, flow rate: 0.5 mL/min, 220 nm): tr (major)
= 11.5 min, tr (minor) =12.7 min.
(2S,3S)-2,3-diphenyloxirane(2n).4s White solid, purified by column
chromatography on silica gel (1% EtOAc in petroleum ether) (14.0 mg, 17% yield, 97%
1
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ee). H NMR (400 MHz, CDCl3) δ 7.36 (10H, s), 3.87 (2H, s); C NMR {1H} (101
MHz, CDCl3) δ 137.7, 129.2, 128.9, 126.1, 63.4; MS (EI) m/z 196 (M+); HPLC
(DAICEL OD-H, hexane/isopropanol 99:1, flow rate: 0.5 mL/min, 220 nm): tr (major)
= 16.7 min, tr (minor) =20.7 min.
Trans-2-methyl-3-phenyloxirane(2o).4i,12 Colorless oil, purified by column
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chromatography on silica gel (1% EtOAc in petroleum ether) (18.0 mg, 32% yield, 67%
ee). 1H NMR (400 MHz, CDCl3) δ 7.36 – 7.24 (5H, m), 3.57 (1H, d, J = 2.1 Hz), 3.03
(1H, dq, J = 5.1, 2.1 Hz), 1.45 (3H, d, J = 5.1 Hz); 13C {1H} NMR (101 MHz, CDCl3)
δ 137.8, 128.4, 128.0, 125.6 , 59.5, 59.0, 17.9; HPLC (DAICEL OD-H,
hexane/isopropanol 99:1, flow rate: 0.5 mL/min, 220 nm): tr (minor) = 12.0 min, tr
(major) =12.4 min.
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1-phenyl-7-oxabicyclo[4.1.0]heptane(2p).12 Colorless oil, purified by column
chromatography on silica gel (1% EtOAc in petroleum ether) (62.2 mg, 85% yield, 59%
ee).1H NMR (400 MHz, CDCl3) δ 7.42 – 7.29 (4H, m), 7.28 – 7.21 (1H, m), 3.07 (1H,
d, J = 3.1 Hz), 2.33 – 2.22 (1H, m), 2.12 (1H, m), 2.03 – 1.95 (2H, m), 1.66 – 1.46
(3H, m), 1.36 – 1.26 (1H, m); 13C {1H} NMR (101 MHz, CDCl3) δ 142.6, 128.3,
127.2, 125.3, 61.9, 60.2, 28.9, 24.7, 20.1, 19.8; HPLC (DAICEL OD-H,
hexane/isopropanol 99:1, flow rate: 0.5 mL/min, 220 nm): tr (major) = 11.1 min, tr
(minor) =12.7 min.
Experimental Procedure for the Gram Scale Synthesis of 2a.
A mixture of Mn(OTf)2 (0.018 g, 0.05 mmol) and L2 (0.024 g, 0.05 mmol) in
CH3CN (10 mL) was stirred at room temperature for 8 h. To the solution of
manganese complex was added indene (1.16 g, 10 mmol) and adamantane carboxylic
acid (0.90 g, 5.0 mmol). Then decrease the temperature to -10 °C, 50 % H2O2 (2.72 g,
40 mmol, diluted with 2.5 mL CH3CN) was added dropwise to the stirring reaction
over 2 min and the mixture was stirred at -10 °C for 2 h, the reaction was quenched by
adding the sat. aq. NaHCO3 (15 mL), and extracted with EtOAc (15 mL x 4). The
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organic layer was separated and washed with brine, dried over MgSO4 and
concentrated at reduced pressure. The residue was purified by silica gel column
chromatography to afford the 2a (1.21 g, 92% yield, 93% ee).
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ACKNOWLEDGMENTS
This work was gratefully financially supported by the National Basic Research
Program of China (2009CB623505).
Supporting information
1H and 13C NMR spectra are available for compounds L6-L9, 2a-2k and 2n-2p.
HPLC data are available for epoxides 2a-2p. This material is available free of charge
via the internet at http://pubs.acs.org.
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