SO2F2-Mediated Epoxidation of Olefins with Hydrogen Peroxide

Article abstract of DOI:10.1021/acs.joc.9b01784

An inexpensive, mild, and highly efficient epoxidation protocol has been developed involving bubbling SO₂F₂ gas into a solution of olefin, 30% aqueous hydrogen peroxide, and 4 N aqueous potassium carbonate in 1,4-dioxane at room temperature for 1 h with the formation of the corresponding epoxides in good to excellent yields. The novel SO₂F₂/H₂O₂/K₂CO₃ epoxidizing system is suitable to a variety of olefinic substrates including electron-rich and electron-deficient ones.

Full text of DOI:10.1021/acs.joc.9b01784

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Article
SO2F2-Mediated Epoxidation of Olefins with Hydrogen Peroxide
Chengmei Ai, Fuyuan Zhu, Yanmei Wang, Zhaohua Yan, and Sen Lin
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01784 • Publication Date (Web): 22 Aug 2019
Downloaded from pubs.acs.org on August 23, 2019
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The Journal of Organic Chemistry
SO2F2-Mediated Epoxidation of Olefins with Hydrogen Peroxide
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Chengmei Ai, Fuyuan Zhu, Yanmei Wang, Zhaohua Yan,* Sen Lin*
College of Chemistry, Nanchang University, Nanchang 330031, PR China
Supporting Information
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ABSTRACT: An inexpensive, mild, and highly efficient epoxidation protocol has been developed involving bubbling SO2F2 gas
into a solution of olefin, 30% aqueous hydrogen peroxide and 4 N aqueous potassium carbonate in 1,4-dioxane at room temperature
for 1 h with the formation of the corresponding epoxides in good to excellent yields. The novel SO2F2/H2O2/K2CO3 epoxidizing
system is suitable to a variety of olefinic substrates including electron-rich and electron-deficient ones.
nitriles, heterocycles, ethenesulfonyl fluorides, diarylmethanes,
INTRODUCTION
arylcarboxylic acids, alkynes, nitriles and amides11. Over the past
decade, we have been devoted to the study on the application of
poly(per)fluorosulfonyl fluoride (RfSO2F, for example n-
C4F9SO2F) in organic synthesis12. In 2004, we reported an
efficient epoxidizing system of RfSO2F/H2O2/NaOH. Inspired by
Epoxides are versatile intermediates for the synthesis of a large
number of valuable compounds and pharmaceuticals. The
epoxidation of olefins is the most convenient method for the
synthesis of epoxides1. Peracids and dioxiranes (for example 3-
chloroperbenzoic acid and dimethyl dioxirane) are the most
classic oxidants for this transformation2. Organo sulfonic peracid,
as a new family of highly active oxidant species, was gradually
recognized and investigated by chemists until recent decades3.
Organo sulfonic peracids cannot be isolated because of their
instability but they displayed some unique oxidizing properties4.
In 1983, Oae5 first reported the reaction of sulfonyl chlorides with
KO2 under argon atmosphere via a radical process leading to the
formation of sulfonic peracid anions [Scheme 1. (a)]. Later,
Schulz6 disclosed in situ generation of organo sulfonic peracids
through the reaction of arylsulfonyl imidazolides with 30%
aqueous hydrogen peroxide in the presence of a base (NaOH or
K2CO3). [Scheme 1. (b)]. It is noteworthy that the treatment of
sulfonyl chlorides with H2O2 did not result in the formation of
persulfonic acids7. In 2007, Kim8 described the use of
tetrabutylammonium peroxydisulfate as a kind of oxidant in the
presence of H2O2 and NaOH [Scheme 1. (c)]. All the above in situ
generated organo sulfonic peracids or peroxysulfate salt exhibited
highly efficient epoxidizing abilities resulting in the smooth
conversion of alkenes into epoxides. However, these known
approaches for the in situ generation of sulfonic peracids still have
disadvantages of the use of harsh reaction conditions and
expensive or explosive reagents, and restricted substrate scope.
Therefore, it is still a challenging task for chemists to develop
inexpensive, mild, green and highly efficient approach for the
epoxidation of olefins. On the other hand, sulfuryl fluoride gas
(SO2F2) has been used as a fumigant for several decades, and its
application as chemical reagent in organic synthesis was revived
recently9. In 2014, Sharpless reported a new kind of click
chemistry based on sulfur (VI) fluoride exchange (SuFEx) which
offers a rapid and highly efficient access to diverse chemical
functionality10. Sulfuryl fluoride is inexpensive and stable reagent
(Currently, SO2F2 gas steel cylinder is commercially available in
China). Since 2014, besides its application in SuFEx-based click
reactions, SO2F2 has been widely used in other chemical
transformations. Recently, Qin reported the elegant application of
SO2F2 in the syntheses of a variety of compounds including aryl
our preliminary research results, we envisioned that SO2F2 will
－
similarly be able to react with HOO
anion to form an
intermediate FSO2OOH which will also serve as an efficient
epoxidizing agent. Herein, we reports a highly efficient and mild
SO2F2-mediated epoxidation of olefins with 30% H2O2 aqueous
solution at room temperature.
RESULTS AND DISCUSSION
To initiate our studies, we selected cinnamic alcohol (1a) as a
model substrate to explore the optimum reaction conditions. The
effect of base on epoxidation reaction was first investigated. A
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variety of bases were used to perform the reaction in CH3OH at
result. The further screening of solvents was subsequently
performed. The results shown in Table 1 revealed that 1,4-dioxane
was the best choice of solvent (Table 1, entries 8-12). It is of
interest to note that, when the amounts of K2CO3 and H2O2 were
reduced to 4 equivalents, it nearly has no any negative effect on
the reaction (Table 1, entry 13). Therefore, the optimum reaction
conditions are as follows: 1a (0.50 mmol), 30% aqueous H2O2
(2.0 mmol), K2CO3 (4 N) (2.0 mmol), 1,4-dioxane (2 mL),
bubbling SO2F2 gas (Caution! SO2F2 is toxic, and the reaction
should be run in a fume hood) into the solution at room
temperature for 1 h.
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room temperature. The molar ratio of 1a : base : H2O2 is 1 : 8 : 8.
When NaOH (4 N NaOH aqueous solution was used) was tested
as a base, the corresponding epoxide product 2a was obtained
only in a low yield of 18% (Table 1, entry 1). The strong
alkalinity of NaOH might cause the ring opening of epoxyl group
resulting in the low yield of 2a. Next, two weaker inorganic bases,
NaHCO3 (4 N aqueous solution) and K2CO3 (4 N aqueous
solution) were then tested. To our delight, the yields of 2a were
dramatically increased to 70% and 75% respectively (Table 1,
entries 2 and 3). The use of two organic bases, Et3N and DBU,
provided 2a in slightly lower yields of 60% and 69% (Table 1,
entries 4 and 5). In addition, use of solid K2CO3 and 1 N aqueous
K2CO3 solution instead of 4 N aqueous K2CO3 solution had
slightly reduced
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To further explore the application of the above methodology,
an array of olefins were subjected to SO2F2/H2O2/K2CO3
epoxidizing system in dioxane at room temperature. Results were
displayed in Table 2. Allylic alcohol, like cinnamyl alcohol 1a
(Table 2, entry 1), is a good substrate for this transformation.
Then a variety of monosubstituted terminal olefins (1b-1g) was
investigated, and the corresponding epoxides were smoothly
formed in 75-87% yields (Table 2, entries 2-7). The ester group of
1c was not hydrolyzed under the reaction conditions even after
stirring for 24 h. Phenyloxy, benzyloxy and phenolic hydroxy
groups are all tolerable to this system. For 1g, the formation of
aryl fluorosulfonate resulting from the reaction of phenolic
hydroxy with SO2F2 was not observed. Two separated electron-
rich double bonds in substrates 1h (racemate) and 1i (racemate)
were successfully di-epoxidized leading to the formation of
diepoxyl products in good yields (Table 2, entries 8 and 9). From
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their H and 13C NMR spectra, 2h is still a racemate and 2i is a
mixture of diastereoisomers. Styrenes with different substituents
(Cl, Br, OAc and NO2) on benzene ring offered epoxides in
moderate to good yields (Table 2, entries 10-13).
reactivity offering 2a in 65% and 70% yields, respectively (Table
1, entries 6 and 7). K2CO3 (4 N) as base thus generated the best
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For sterically hindered trans-stilbene (1n) and cis-stilbene (1o),
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the epoxidation proceeded very well with the formation of the
corresponding epoxides in excellent yields (Table 2, entries 14
and 15). At the same time, the complete retention of configuration
was observed for 2n and 2o. A tetrasubstituted sterically hindered
olefin, tetra(4-cyanophenyl)ethylene (1p), provided the epoxide in
75% yield after 3 h when 8 equiv. of H2O2 and 8 equiv. of K2CO3
were used (Table 2, entry 16). SO2F2/H2O2/K2CO3 epoxidizing
system is also amenable to the epoxidation of the challenging
electron-deficient alkenes (entry 17-19). In the case of diethyl
maleate (1t), an extremely electron-poor alkene, its epoxidation
occurred smoothly affording cis-epoxyl product in 94% yield
(Table 2, entry 20). As a comparison with results in literatures, it
was reported that when 1t was subjected to HOF and Mn(OTf)2/2-
PyCOOH system for epoxidation, 2t was obtained only with low
to moderate yields13. It should be noted that in the epoxidation of
1r, the Baeyer-Villiger14 oxidation product was not observed.
Finally, the epoxidation of two optically pure steroidal
homoallylic alcohols 1u and 1v worked quite well (Table 2,
entries 21 and 22), and the epoxides were afforded in 90% and
89% yields, respectively15. From their H-1 NMR spectra, both 2u
and 2v are all mixtures of 5,6-α-epoxide and 5,6-β-epoxide with
α : β isomer being 1.5 : 1.
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To demonstrate the potential application value of
SO2F2/H2O2/K2CO3 epoxidizing system in organic synthesis, a
gram-scale epoxidation of 1a was examined. As shown in Scheme
2, the epoxidation of 2.02 grams of 1a provided 2a in 78% yield
after 3 h at room temperature, which confirmed this method can
be used in organic synthesis and even in industrial manufacturing.
To clarify the reaction mechanism, some control experiments
are conducted (scheme 4). We selected cinnamyl alcohol (1a) as a
representative electron-rich alkene, and chalcone (1r) as a
representative electron-deficient alkene. In the absence of H2O2,
no reaction was observed for 1a and 1r, indicating that H2O2 is an
oxidant of the reaction. However, in the absence of sulfuryl
fluoride or K2CO3, H2O2 cannot epoxidize cinnamyl alcohol. It
showed that H2O2 reacts with SO2F2 in the presence of K2CO3 to
form a new oxidant species, which enables alkene to be
epoxidized. In addition, in the absence of SO2F2, chalcone can be
epoxidized by H2O2/K2CO3 in much lower yield than by
SO2F2/H2O2/K2CO3 system. This also showed that SO2F2 was
involved in the epoxidation process.
In order to explore the chemical selectivity, we subsequently
investigated the reactions of two substrates with aldehyde group
(1w) and thioether group (1x) with SO2F2/H2O2/K2CO3 system.
Results were shown in Scheme 3. The double bond in 1w can
smoothly and quickly be epoxidized to 2w in 84% yield with
aldehyde group untouched [Scheme 3, (a)]. However, in the case
of 1x, only sulfur atom was selectively oxidized to sulfone and the
double bond was kept inert [Scheme 3, (b)]. When the same
amount of cinnamyl alcohol 1a and N,N-dimethylaniline 1y was
subjected to SO2F2/H2O2/K2CO3 system, 2y was selectively
formed in 89% yield and 2a was just detected in trace amount
[Scheme 3, (b)]. The above results demonstrated that tertiary
amine and thioether can be preferentially oxidized than olefinic
double bond. Next, we used the same amount of cinnamyl alcohol
1a and methyl cinnamate 1s to study the regioselectivity [Scheme
3, (d)]. The results showed that electron-rich double bond is
preferentially epoxidized than electron-deficient one. However,
with the prolongation of reaction time, electron-deficient double
bond was also efficiently epoxidized. The result in (e) of Scheme
3 indicated that SO2F2/H2O2/K2CO3 oxidation system did not have
apparent selectivity to monosubstituted and trisubstituted double
bonds.
Based on the above control experiments and literature
descriptions4, 5a, 7, a plausible epoxidation mechanism is outlined
below. Firstly, H2O2 is deprotonated by K2CO3 to form anion
HOO－ , which may attack SO2F2 through substitution reaction to
provide fluorosulfonic peracid FSO2OOH. Then in situ generated
FSO2OOH can epoxidize alkenes like traditional peracids. It has
been reported in literatures4,5a that peroxysulfur species is not
stable and can not be detected and isolated. Similarly, due to the
instability of in situ generated FSO2OOH, this oxidant species
also was not detected nor isolated in the course of our study.
CONCLUSION
In conclusion, SO2F2-mediated epoxidation of a variety of
electron-rich and electron-deficient alkenes with H2O2/K2CO3 was
developed. The in situ generated fluorosulfonic peracid
intermediate served as an oxidizing species in the epoxidation
process. The main advantages of the epoxidation method is its
inexpensiveness, high efficiency, environmentally benigh and
mild reaction conditions. Neutral to weak alkaline reaction
medium makes the novel method specially suitable for the
epoxidation
of
acid-sensitive
alkenes.
In
addition,
SO2F2/H2O2/K2CO3 system can efficiently epoxidize extremely
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electron-poor and highly sterically hindered olefinic substrates.
Therefore, we expect it to be used as a practical alternative
epoxidation system in organic synthesis.
J = 7.3, 1.2 Hz, 1H), 6.90 – 6.85 (m, 2H), 4.64 (d, J = 1.7 Hz, 2H),
4.51 (dd, J = 12.2, 2.9 Hz, 1H), 3.98 (ddd, J = 12.3, 6.4, 1.9 Hz,
1H), 3.18 (td, J = 4.1, 2.1 Hz, 1H), 2.79 (t, J = 4.5 Hz, 1H), 2.59
(dt, J = 4.8, 2.2 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ
168.7, 157.6, 129.6, 121.8, 114.6, 65.6, 65.0, 49.0, 44.6.
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EXPERIMENTAL SECTION
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2-(oxiran-2-ylmethyl)phenol (2g):18 colorless oil; 56 mg, 75 %;
1H NMR (400 MHz, CDCl3) δ 7.16 (td, J = 7.7, 1.8 Hz, 1H), 7.09
(dd, J = 7.5, 1.7 Hz, 1H), 7.00 (s, 1H), 6.92 – 6.82 (m, 2H), 3.29
(tt, J = 6.7, 2.8 Hz, 1H), 3.19 (dd, J = 15.1, 2.7 Hz, 1H), 2.91 (t, J
= 4.2 Hz, 1H), 2.74 – 2.67 (m, 2H). 13C{1H} NMR (101 MHz,
CDCl3) δ 155.5, 131.0, 128.8, 123.2, 120.6, 117.0, 53.6, 48.1,
34.8.
General Information. Unless otherwise stated, all reagents
were obtained from commercial suppliers and used without
further purification. All reactions were performed in a double-
1
necked flask. H NMR spectra were recorded on 400 MHz and
13C NMR spectra were recorded on 101 MHz, and
tetramethylsilane as an internal standard. The chemical shifts are
referenced to signals at 7.25 and 77.0 ppm (CDCl3). Column
chromatography was carried out on silica gel with petroleum
ether/ethyl acetate as the eluent.
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2,4-Methano-2H-indeno[1,2-b:5,6-b']bisoxirene
(2h):2e
colorless solid; mp 179-181 ℃; 63 mg, 85 %; 1H NMR (400 MHz,
CDCl3) δ 3.50 (s, 1H), 3.37 (d, J = 2.5 Hz, 1H), 3.23 (d, J = 3.4
Hz, 1H), 3.19 (d, J = 3.5 Hz, 1H), 2.65 (d, J = 4.4 Hz, 1H), 2.57
(dd, J = 8.2, 4.4 Hz, 1H), 2.46 (d, J = 3.4 Hz, 2H), 1.87 (dd, J =
15.4, 8.8 Hz, 1H), 1.80 – 1.78 (m, 1H), 1.42 – 1.37 (m, 1H), 0.82
(d, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 61.7, 58.6, 48.9, 48.7,
48.3, 44.6, 39.9, 39.1, 29.6, 26.9.
General procedure for the epoxidation of alkenes. To a 50
mL double-necked flask was added 0.5 mmol alkene, 2 mL
dioxane, 30% H2O2 (0.23 mL, 2 mmol). Then K2CO3 (4 N
aqueous solution. 0.5 mL, 2 mmol) was slowly added to the
mixture. Meanwhile, SO2F2 gas was bubbling into the reaction
mixture by a balloon combined with a syringe needle. The
reaction mixture was stirred for 1 h at room temperature. The
reaction mixture was diluted with 5 mL of water, and extracted
with CH2Cl2 (3×20 mL). The combined organic layer was dried
over anhydrous Na2SO4 and concentrated under vacuum. The
crude product was further purified through flash column
chromatography using the mixture of petroleum ether and ethyl
acetate as eluent.
1,2-Epoxy-4-(2-oxiranyl)cyclohexane (2i):2c colorless oil; 50 mg,
1
81 %; H NMR (400 MHz, CDCl3) δ 3.29 – 3.00 (m, 2H), 2.84 –
2.56 (m, 2H), 2.53 – 2.37 (m, 1H), 2.22 – 1.98 (m, 2H), 1.84 (ddt,
J = 16.3, 11.5, 6.1 Hz, 1H), 1.71 – 1.63 (m, 1H), 1.56 – 1.46 (m,
1H), 1.44 – 1.21 (m, 1H), 1.19 – 1.00 (m, 1H). 13C{1H} NMR
(101 MHz, CDCl3) δ 55.9, 55.6, 55.5, 52.4, 52.4, 52.3, 52.2, 51.6,
51.5, 50.9, 50.8, 46.1, 46.0, 45.6, 45.3.
2-(4-Bromophenyl)oxirane (2j):19 colorless oil; 61 mg, 61 %; 1H
NMR (400 MHz, CDCl3) δ 7.46 (dd, J = 8.4, 2.0 Hz, 2H), 7.14 (d,
J = 7.9 Hz, 2H), 3.83 – 3.79 (m, 1H), 3.13 (dt, J = 5.5, 2.9 Hz,
1H), 2.74 (dt, J = 5.5, 2.2 Hz, 1H). 13C{1H} NMR (101 MHz,
CDCl3) δ 136.7, 131.6, 127.1, 122.0, 51.8, 51.2.
3-Phenyl-2-oxiranemethanol (2a):2c colorless oil; 64 mg, 85 %;
1H NMR (400 MHz, CDCl3) δ 7.39 – 7.19 (m, 5H), 4.04 (dd, J =
12.8, 2.5 Hz, 1H), 3.93 (d, J = 2.3 Hz, 1H), 3.79 (dd, J = 12.7, 3.9
Hz, 1H), 3.24 – 3.18 (m, 1H), 1.24 (s, 1H). 13C{1H} NMR (101
MHz, CDCl3) δ 136.6, 128.5, 128.4, 125.7, 62.5, 61.1, 55.5.
2-(4-Chlorophenyl)oxirane (2k):19 colorless oil; 49 mg, 63 %;
1H NMR (400 MHz, CDCl3) δ 7.32 – 7.27 (m, 2H), 7.21 – 7.16
(m, 2H), 3.81 (dd, J = 4.1, 2.5 Hz, 1H), 3.12 (dd, J = 5.5, 4.0 Hz,
1H), 2.73 (dd, J = 5.5, 2.6 Hz, 1H). 13C{1H} NMR (101 MHz,
CDCl3) δ 136.7, 131.6, 127.1, 122.0, 51.8, 51.2.
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2-Octyloxirane (2b):2c colorless oil; 68 mg, 87 %; H NMR (400
MHz, CDCl3) δ 2.87 (dd, J = 6.4, 3.3 Hz, 1H), 2.71 (t, J = 4.5 Hz,
1H), 2.43 (dd, J = 5.1, 2.7 Hz, 1H), 1.51 – 1.46 (m, 2H), 1.25 (d, J
= 8.9 Hz, 12H), 0.86 (d, J = 6.4 Hz, 3H).13C{1H} NMR (101 MHz,
CDCl3) δ 52.3, 47.0, 32.4, 31.8, 29.5, 29.4, 29.2, 25.9, 22.6, 14.0.
4-Methoxycarbonylstyrene oxide (2l):19 colorless oil; 58 mg,
Diethyl 2-(oxiran-2-ylmethyl)propanedioate (2c):16 colorless oil;
88 mg, 82 %; 1H NMR (400 MHz, CDCl3) δ 4.20 – 4.10 (m, 4H),
3.48 (dd, J = 8.6, 6.1 Hz, 1H), 2.96 (dp, J = 6.8, 2.2 Hz, 1H), 2.73
– 2.70 (m, 1H), 2.48 – 2.45 (m, 1H), 2.20 (ddd, J = 14.4, 8.6, 4.6
Hz, 1H), 1.99 – 1.91 (m, 1H), 1.22 (td, J = 7.1, 3.8 Hz, 6H).13C
{1H} NMR (101 MHz, CDCl3) δ 168.8, 168.8, 61.59, 61.56, 49.8,
48.9, 47.2, 31.6, 13.98, 13.95.
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65 %; H NMR (400 MHz, CDCl3) δ 7.28 – 7.24 (m, 2H), 7.06 –
7.03 (m, 2H), 3.83 (dd, J = 4.1, 2.5 Hz, 1H), 3.10 (dd, J = 5.5, 4.0
Hz, 1H), 2.74 (dd, J = 5.4, 2.6 Hz, 1H), 2.26 (d, J = 1.4 Hz, 3H).
13C{1H} NMR (101 MHz, CDCl3) δ 169.4, 169.4, 150.5, 135.2,
126.5, 121.7, 51.9, 51.2, 21.1.
2-(4-nitrophenyl)oxirane (2m):19 colorless solid; mp 80-86 ℃ ;
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66 mg, 80 %; H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 8.4 Hz,
oxiran-2-ylmethyl 3-cyclohexylpropanoate (2d): colorless oil;
2H), 7.41 (d, J = 8.3 Hz, 2H), 3.93 (t, J = 3.3 Hz, 1H), 3.19 (t, J =
4.8 Hz, 1H), 2.74 (dd, J = 5.6, 2.5 Hz, 1H).13C{1H} NMR (101
MHz, CDCl3) δ 147.7, 145.3, 126.2, 123.8, 51.7, 51.4.
1
90 mg, 85 %; H NMR (400 MHz, CDCl3) δ 4.36 (dd, J = 12.3,
3.0 Hz, 1H), 3.86 (dd, J = 12.3, 6.3 Hz, 1H), 3.16 (dq, J = 6.4, 3.1
Hz, 1H), 2.80 (t, J = 4.5 Hz, 1H), 2.60 (dd, J = 4.9, 2.6 Hz, 1H),
2.31 (t, J = 7.9 Hz, 2H), 1.68 – 1.60 (m, 5H), 1.51 – 1.46 (m, 2H),
1.21 – 1.09 (m, 4H), 0.84 (td, J = 11.7, 8.6 Hz, 2H). 13C {1H}
NMR (101 MHz, CDCl3) δ 173.8, 64.7, 49.3, 44.6, 37.1, 32.9,
32.2, 31.6, 26.5, 26.2. HRMS (ESI-TOF) m/z: [M+H]+ calcd for
C12H20O3 213.1485; Found: 213.1491.
trans-Stilbeneoxide (2n):1e colorless solid; mp 66-68 ℃; 85 mg,
1
80 %; H NMR (400 MHz, CDCl3) δ 7.38 (q, J = 6.2, 5.7 Hz,
10H), 3.89 (s, 2H). 13C{1H} NMR (101 MHz, CDCl3) δ 137.1,
128.6, 128.3, 125.5, 62.9.
cis-Stilbeneoxide (2o):1e colorless solid; mp 66-69 ℃ ; 88 mg,
1
2-[(Phenylmethoxy)methyl]oxirane (2e):17 colorless oil; 67 mg,
82 %; 1H NMR (400 MHz, CDCl3) δ 7.38 – 7.24 (m, 5H), 4.58 (q,
J = 11.9 Hz, 2H), 3.76 (dd, J = 11.5, 3.0 Hz, 1H), 3.43 (dd, J =
11.4, 5.9 Hz, 1H), 3.18 (dq, J = 6.4, 3.0 Hz, 1H), 2.79 (t, J = 4.6
Hz, 1H), 2.61 (dd, J = 5.1, 2.7 Hz, 1H). 13C{1H} NMR (101 MHz,
CDCl3) δ 137.8, 128.4, 127.7, 73.3, 70.8, 50.9, 44.3.
80 %; H NMR (400 MHz, CDCl3) δ 7.26 – 7.13 (m, 10H), 4.39
(s, 2H). 13C{1H} NMR (101 MHz, CDCl3) δ 134.4, 127.8, 127.5,
59.8.
2,2,3,3-tetraphenyloxirane (2p): colorless solid; mp 402-404 ℃;
75 %, 159 mg; 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.1 Hz,
8H), 7.30 (d, J = 8.2 Hz, 8H). 13C{1H} NMR (101 MHz, CDCl3) δ
140.7, 132.2, 128.5, 117.8, 112.6, 73.2. HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C30H16N4O 449.1397; Found: 449.1375.
phenoxyacetyl-2,3-epoxipropyl ester (2f):24 colorless oil; 86 mg,
85 %; 1H NMR (400 MHz, CDCl3) δ 7.30 – 7.23 (m, 2H), 6.97 (tt,
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rac-2-Oxiraneacetic Acid Phenylmethyl Ester (2q):20 colorless
oil; 82 mg, 92 %; H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 4.0
Supporting Information
1
1
2
3
4
5
6
7
8
Hz, 5H), 5.24 – 5.15 (m, 2H), 3.45 (dd, J = 4.2, 2.4 Hz, 1H),
2.97 – 2.89 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3) δ 169.1,
135.0, 128.6, 128.6, 128.4, 67.2, 47.3, 46.3.
The Supporting Information is available free of charge on the
ACS Publications website at DOI:
1H NMR and 13C NMR spectra for all the products.
Phenyl(3-phenyl-2-oxiranyl)methanone (2r):8 colorless solid;
1
mp 86-88℃; 71 %, 90 mg; H NMR (400 MHz, CDCl3) δ 8.01 –
AUTHOR INFORMATION
7.97 (m, 2H), 7.63 – 7.57 (m, 1H), 7.47 (t, J = 7.8 Hz, 2H), 7.37
(tq, J = 6.6, 3.6, 3.0 Hz, 5H), 4.29 (d, J = 1.9 Hz, 1H), 4.06 (d, J =
1.9 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 193.1, 135.5,
135.5, 134.0, 129.0, 128.9, 128.8, 128.3, 125.8, 61.0, 59.4.
Corresponding authors: Zhaohua Yan (Prof. and PhD), email
yanzh@ncu.edu.cn; Sen Lin (Prof. and PhD), Email senlin@
ncu.edu.cn.
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1-Phenyl-2-methoxycarbonyloxirane (2s):1e colorless oil; 82 mg,
1
92 %; H NMR (400 MHz, CDCl3) δ 7.33 (dd, J = 5.3, 2.0 Hz,
ACKNOWLEDGMENTS
3H), 7.29 – 7.24 (m, 2H), 4.08 (d, J = 1.8 Hz, 1H), 3.81 – 3.78 (m,
3H), 3.50 (d, J = 1.9 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ
168.6, 134.9, 129.0, 128.6, 125.8, 57.9, 56.6, 52.5.
We are grateful for the financial support from the National
Natural Science Foundation of China (21362022).
Diethyl 2,3-oxiranedicarboxylate (2t):13c colorless oil; 93 mg,
1
94 %; H NMR (400 MHz, CDCl3) δ 4.14 (ddq, J = 7.2, 5.4, 3.0
REFERENCE
Hz, 4H), 3.60 (q, J = 3.0 Hz, 2H), 1.18 (tdd, J = 6.9, 4.2, 2.5 Hz,
6H). 13C{1H} NMR (101 MHz, CDCl3) δ 165.6, 61.8, 52.4, 13.9.
(1) For a review, see: (a) wong, O. A.; Shi, Y. Organocatalytic
Oxidation. Asymmetric Epoxidation of Olefins Catalyzed by
Chiral Ketones and Iminium Salts. Chem. Rev. 2008, 108, 3958-
3987. (b) Xia, Q.; Ge, Q.; Ye, C. P.; Liu, Z. M.; Su, K. X.
Advances in Homogeneous and Heterogeneous Catalytic
Asymmetric Epoxidation. Chem. Rev. 2005, 105, 1603-1662. For
books see: (c) Yudin, A. K. Aziridine and Epoxides in Organic
Synthesis; Yudin, A. K. Ed; Wiley-VCH: Weinheim, 2006. (d)
Centi, G.; Perathoner, S.; Abate, S. In Modern Heterogeneous
Oxidation Catalyst: Design, Reaction and Characterization;
Mizuno, N., Wiley-VCH: Weinheim, 2009. (e) Igarashi, Y.;
Betsuyaku, T. Kitamura, M.; Hirata, K.; Hioki, K.; Kunishima, M.
An Isolable and Bench-Stable Epoxidizing Reagent Based on
Triazine: Triazox. Org. Lett. 2018, 20, 2015-2019.
3-hydroxy-9a,11b-dimethyltetradecahydrocyclopenta[1,2]
phenanthro[8a,9-b]oxiren-9(2H)-one (2u):21 colorless solid; mp
172-174 ℃; 89 %, 179 mg; mixture of diastereomers (α:β=60:40);
1H NMR (400 MHz, CDCl3) δ 3.79 (m, J = 10.9, 0.6H), δ 3.6 (m,
J = 4.7, 0.4H), 3.04 (d, 0.4H), 2.87 (d, 0.6H). 13C{1H} NMR (101
MHz, CDCl3) δ 220.9, 220.69, 220.66, 69.0, 68.2, 65.8, 63.3, 63.1,
58.7, 51.8, 51.4, 51.1, 47.6, 47.4, 42.8, 42.0, 39.6, 37.2, 35.7, 35.6,
35.0, 35.0, 32.4, 31.4, 31.4, 31.0, 30.9, 30.8, 29.4, 29.4, 27.6, 21.7,
21.6, 21.2, 19.9, 17.0, 15.9, 13.5, 13.4.
9a,11b-dimethyl-9-(6-methylheptan-2-yl)
hexadecahydrocyclopenta[1,2]phenanthro[8a,9-b]oxiren-3-ol
(2v):2c colorless solid; mp 142-144 ℃; 91 %, 90 mg; mixture of
1
diastereomers (α:β=60:40); H NMR (400 MHz, CDCl3) δ 3.86
(2) (a) Katsuki, T.; Sharpless, K. B. The First Practical Method
for Asymmetric Epoxidation. J. Am. Chem. Soc. 1980, 102,
5974−5976. (b) Mello, R.; Fiorentino, M.; Sciacovelli, O.; Curci,
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(Trifluoromethyl) Dioxirane. J. Org. Chem. 1988, 53, 3890-3891.
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An Organocatalyst for an Environmentally Friendly Epoxidation
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Curci, R.; Edwards, J. O. Dioxiranes: a New Class of Powerful
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from Tris (cetylpyridinium) 12-Molybdophosphate and Hydrogen
Peroxide. J. Org. Chem. 1987, 52, 1868-1870.
(m, J = 10.5, 0.6H), 3.66 (m, J = 5.3, 0.6H), 2.87 (d, J = 4.3 Hz,
0.4H). 2.87 (d, J = 4.3 Hz, 0.6H). 13C{1H} NMR (101 MHz,
CDCl3) δ 69.3, 68.6, 65.7, 63.7, 62.9, 59.3, 56.8, 56.2, 56.2, 55.8,
51.3, 42.5, 42.3, 42.3, 42.2, 39.8, 39.8, 39.5, 39.4, 37.2, 36.1, 35.7,
34.8, 32.6, 32.4, 31.0, 31.0, 29.9, 29.7, 28.8, 28.1, 28.04, 27.96,
24.2, 24.0, 23.8, 23.8, 22.8, 22.5, 22.0, 20.6, 18.6, 17.0, 15.9, 11.8,
11.7.
5-(3,3-dimethyloxiran-2-yl)-3-methylpentanal (2w):22 colorless
oil; 71.4 mg, 84 %; 1H NMR (400 MHz, CDCl3) δ 9.71 (d, J = 2.3
Hz, 1H), 2.67 – 2.63 (m, 1H), 2.41 – 2.34 (m, 1H), 2.22 (dddd, J
= 16.2, 8.0, 3.8, 2.4 Hz, 1H), 2.07 (p, J = 6.7 Hz, 1H), 1.49 (ddd, J
= 11.0, 7.1, 2.8 Hz, 2H), 1.45 – 1.35 (m, 2H), 1.25 (s, 3H), 1.21 (d,
J = 1.5 Hz, 3H), 0.93 (d, J = 6.7 Hz, 3H). 13C{1H} NMR (101
MHz,CDCl3) δ 202.6, 202.5, 64.2, 64.2, 58.3, 58.2, 50.9, 50.8,
33.5, 27.8, 26.3, 26.3, 24.8, 19.8, 19.7, 18.7, 18.6.
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pent-4-en-1-ylsulfonyl)benzene (2x):23 colorless oil; 97 mg,
1
87 %; H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 7.9 Hz, 2H),
7.31 (d, J = 7.9 Hz, 2H), 5.62 (ddt, J = 13.3, 9.8, 6.7 Hz, 1H),
4.98 – 4.91 (m, 2H), 3.05 – 2.99 (m, 2H), 2.40 (s, 3H), 2.07 (q, J
= 7.1 Hz, 2H), 1.79 – 1.71 (m, 2H). 13C{1H} NMR (101 MHz,
CDCl3) δ 144.6, 136.3, 136.1, 129.9, 128.0, 116.4, 55.5, 32.0,
21.8, 21.6.
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1
61 mg, 89 %; H NMR (400 MHz, CDCl3) δ 7.62 (td, J = 7.8, 2.2
Hz, 2H), 7.10 – 6.96 (m, 3H), 3.21 (dd, J = 8.0, 2.3 Hz, 6H).
13C{1H} NMR (101 MHz, CDCl3) δ 153.9, 128.8, 128.5, 119.6,
62.8.
ASSOCIATED CONTENT
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