Efficient synthetic method for the preparation of allyl- and propargyl-epoxides by allylation and propargylation of α-haloketones with organozinc reagents

Article abstract of DOI:10.1039/c1ob06071f

A simple, efficient, and non-metal catalyzed synthetic method for the preparation of substituted allyl- and propargyl-epoxides by allylation and propargylation of α-halo ketones with organozinc reagents in mild conditions is reported in this paper. The present method complements the existing synthetic methods due to some advantageous properties of the organozinc reagents such as availability, selectivity, operational simplicity and low toxicity.

Full text of DOI:10.1039/c1ob06071f

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PAPER
Efficient synthetic method for the preparation of allyl- and propargyl-epoxides
by allylation and propargylation of a-haloketones with organozinc reagents†
Jie Pan, Min Zhang and Songlin Zhang*
Received 3rd July 2011, Accepted 2nd November 2011
DOI: 10.1039/c1ob06071f
A simple, efficient, and non-metal catalyzed synthetic method for the preparation of substituted allyl-
and propargyl-epoxides by allylation and propargylation of a-halo ketones with organozinc reagents in
mild conditions is reported in this paper. The present method complements the existing synthetic
methods due to some advantageous properties of the organozinc reagents such as availability,
selectivity, operational simplicity and low toxicity.
known for more than 150 years,12 the applications of organozinc
Introduction
reagents in organic synthesis were limited to very rare reactions
Epoxides, with their reactive oxirane groups, are versatile organic
due to their moderate reactivity. The reagents were replaced by
tools as both building blocks and synthetic intermediates in
the more reactive organomagnesium and organolithium reagents
various organic syntheses.1 These epoxides are widely used as
which were found to have broad applications in organic synthesis.
epoxy resins, paints, and surfactants in various organic chemistry
However, it became apparent that this high reactivity has also
applications. Most epoxides are frequently used as electrophiles
some drawbacks, such as low chemoselectivity and excessively
in ring-opening nucleophilic addition reactions,2 especially, one of
high reactivity for some functional groups. It was noticed that
the useful reactions is the Meinwald rearrangement from epoxides
organozinc reagents could be easily prepared and could have
to afford carbonyl compounds with a number of reagents including
a variety of Lewis acids.3
Epoxides are prepared in a number of ways: epoxidation of
higher functional group compatibility in comparison with organo-
lithium and Grignard reagents. Furthermore, the low reactivity
of organozinc reagents could be increased by adding transition
olefins,4 Darzens reaction,5 catalytic reactions of a-halo ketones
with organometallic reagents,6 and so on.7 Most epoxides are
prepared by epoxidation of olefins, especially asymmetric epox-
idation, which is the focus of methodological developments.8
This method has two types: a convenient type is the oxidation
of olefins with hydrogen peroxide or alkyl peroxides in the
presence of transition metal complexes.9 However, in general,
the activity of the catalyst is limited and the metal catalyst, as
well as modifying ligands, has to be separated after the reaction.
Another type is the oxidation of olefins with hydrogen peroxide
in the presence of acetic or formic acid.10 A drawback of this
method is the potential side reactions of the acid. Epoxidation
of alkenes using peroxyacids is also one of the most fundamental
reactions in organic chemistry.11 However, these methods for the
epoxidation of olefins cannot be used to selectively synthesize
epoxides which contain other functional groups. For these reasons,
the development of an effective preparation procedure for epoxides
would be significant.
metal catalyst.13 Nowadays, organozinc reagents have been widely
used in organic synthesis,14 and are important reagents in organic
chemistry.15
Research work on organozinc halides has been performed in
our laboratory over the past few years. We have reported a
novel environmentally benign reaction of allylzinc bromide with
a-haloketones leading to three different products depending on
the different reaction conditions.16 Allylic epoxides were obtained
without any additives (Scheme 1). Based on these initial results we
proceeded to examine the scope of this reaction. We report herein
a full account of our research that has efficiently prepared a series
of epoxides by various organozinc halides with a-haloketones.
Results and discussion
In our initial study, a-bromoacetophenone (1a) was chosen as a
model substrate to react with organozinc bromides (2) in THF
at room temperature (Scheme 2), and then different epoxides (3)
were obtained. As shown in Table 1, this reaction procedure is
applicable to several highly reactive substituted allylzinc reagents
and one propargylzinc reagent.
Treatment of 1a with allylzinc reagents (2a, 2c and 2d) at
room temperature for 2 h gave the corresponding epoxides (3a,
3c and 3d) in moderate to good yields (Table 1, entries 1, 3 and
4). Cinnamylzinc bromide (2b) was also used in this reaction,
Zinc is a relatively non-toxic metal and it is an essential element
for humans and all forms of plant and animal life. Although
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chem-
istry. Chemical Engineering and Materials Science of Soochow University,
Suzhou, 215123, People’s Republic of China. E-mail: zhangsl@suda.edu.cn
† Electronic supplementary information (ESI) available: 1H and 13C NMR
spectra. See DOI: 10.1039/c1ob06071f
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Table 1 Comparison of different organozinc bromides react with a-
bromoacetophenonea
Entry Organozinc bromide Time (h) Product
Yield (%)b
90
1
2
2
2
53 dr = 58 : 42c
92 dr > 20 : 1c
3
2
4
5
2
3
82 dr > 20 : 1c
75
Scheme 1 Products obtained by the allylation of a-haloketones with
allylzinc bromide.
6
7
24
24
—
—
none
none
Scheme
bromides.
2 Reactions of a-bromoacetophenone with organozinc
8
24
—
none
which displayed no marked stereoselectivity (Table 1, entry 2).
The reaction of 1a took place in the case of propargylzinc bromide
(2e) to give 3e in 75% yield (Table 1, entry 5). However, alkylzinc
bromides (2f and 2g) and phenylzinc iodide (2h) in this reaction
did not give the corresponding epoxides (Table 1, entries 6–8).
To research our methodology synthetically, we investigated
the generality of this method. A number of a-halo ketones
were further subjected to reaction with several highly reactive
substituted acyclic allylzinc reagents, cyclic allylzinc reagents and
propargylzinc reagent.
First of all, the results of a-bromoketones with acyclic allylic
organozinc bromides are summarized in Table 2. We investigated
the factors electronic effect and steric hindrance at the phenyl-
and halo-substituted compounds. The results clearly show that
electronic features have a very great impact on the processes.
Electron-deficient groups at the para position of the phenyl ring
were well tolerated and we obtained the product in good yields
(Table 2, entries 1–3). However, an electron-rich group at the para
position resulted in relatively diminished efficiency (Table 2, entry
4). Examination of the result of the investigation reveals that high
reactivity was observed for 2-bromoacetylnaphthalene (Table 2,
entry 5). Substrates bearing big sterically hindered groups could
not yield the corresponding epoxide, but allyl-ketone (4f) can be
obtained in 76% yield (Table 2, entry 6). The reactions of a-
bromoketones with cinnamylzinc bromide reveal that an electron-
deficient group at the para position of the phenyl ring was little
better than an electron-rich group (Table 2, entries 7–8). And the
diastereo-selectivity was also poor (57 : 43, 60 : 40).
a Reaction conditions: a-bromoacetophenone (0.5 mmol), organozinc
bromide (1.0 mmol) and THF (6 mL) at room temperature under
nitrogen. b Isolated yield based on 1a after silica gel chromatography.
c Diastereomeric ratio (dr) determined by 1H NMR analysis, relative
stereochemistry not determined.
From the results of cyclohexenylzinc bromide and cy-
clooctenylzinc bromide with a-haloketones (Table 3), we can
see that cyclohexenylzinc bromide could yield more epoxides
compared with cyclooctenylzinc bromide. For the two cyclic
allylic organozinc bromides, electron-deficient groups at the para
position of the phenyl ring were well tolerated in good yields
(Table 3, entries 1–3). However, an electron-rich group at the para
position resulted in a slightly lower yield (Table 3, entry 4). We also
found that sterically hindered epoxides can be obtained in good
yield (Table 3, entry 5). Furthermore, epoxide (5cf) also can be
obtained in 89% yield (Table 3, entry 6). For the aliphatic ketones,
when X = Cl, the reaction showed a lower product yield (61%) than
X = Br of 78%. The reason, probably, is that the leaving ability of
the Br atom is higher than Cl (Table 3, entries 7–8).
At last, we performed the reaction of propargylzinc bromide
with other a-bromoketones. Some experimental results are sum-
marised in Table 4. It was clear that bromoketones bearing
electron-deficient groups at the para position of the phenyl ring
underwent reaction smoothly to afford the desired products with
moderate yields (Table 4, entries 1–3). Substrates bearing more
sterically hindered groups still yielded the corresponding product
(6d) in good yield; the diastereomeric ratio was up to 93 : 7
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Table 2 Products obtained by the allylation of a-bromoketones with
Table 3 Products obtained by the allylation of a-haloketones with cyclic
acyclic allylic organozinc bromidesa,b
allylic organozinc bromidesa
Entry
1
a-Haloketones
Product
Yield (%)c
89
Entry R1
R2
X
R3–ZnBr Product
Yield (%)b,c
A
90 dr > 20 : 1
2
90
1
p-ClC6H4
H
Br
3
4
91
63
B
81 dr > 20 : 1
A
B
92 dr > 20 : 1
80 dr > 20 : 1
5
6
89
76
2
p-BrC6H4
H
Br
3
4
p-FC6H4
H
H
Br
Br
A
A
A
88 dr > 20 : 1
65 dr > 20 : 1
80
7d
8e
72
56 dr = 57 : 43f
p-CH3C6H4
9e
44 dr = 60 : 40f
5
C6H5
CH3 Br
a Reaction conditions: a-bromoketone (0.5 mmol), acyclic allylic organo-
zinc bromide (1.0 mmol) and THF (6 mL) at room temperature under
nitrogen. b R1 = R2 = CH3. c Isolated yield based on 1 after silica gel
chromatography. d R1 = H, R2 = H. e R1 = H, R2 = Ph. f Diastereomeric
B
75
1
ratio (dr) determined by H NMR analysis, relative stereochemistry not
determined.
6
7
2-Naphthyl
t-Butyl
H
H
Br
Cl
A
89 dr > 20 : 1
(Table 4, entry 4). And 2-bromoacetylnaphthalene also afforded
the corresponding epoxide in good yield (Table 4, entry 5).
Conclusions
B
61 dr > 20 : 1
In summary, we have successfully developed a cost effective,
environmentally benign, highly efficient, non-metal catalyzed and
simple manner for the synthesis of a series of epoxides by
allylation and propargylation of a-haloketones with organozinc
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Table 3 (Contd.)
conditions using organozinc reagents, which are the most common
commercially available organometallic reagents.
Experimental section
General
Tetrahydrofuran was distilled from sodium and benzophenone
immediately prior to use. All reactions were conducted under a
nitrogen atmosphere. Metallic zinc and all other solvents were
purchased from a commercial source, without further purification
before use. The flash column chromatography was carried out on
Merck silica gel (300–400 mesh). The IR spectra was measured
on a Varian 1000 FT-IR spectrometer as KBr disks (4000–400
Entry R1
R2
H
X
R3–ZnBr Product
Yield (%)b,c
8
t-Butyl
Br
B
78 dr > 20 : 1
1
cm-1). H and 13C NMR spectra were recorded in CDCl3 on a
Varian Mercury 300 or 400 MHz spectrometer. Chemical shifts
1
in H NMR spectra are reported in parts per million (ppm, d)
a Reaction conditions: a-haloketone (0.5 mmol), cyclic allylic organozinc
bromide (1.0 mmol) and THF (6 mL) at room temperature under nitrogen.
b Isolated yield based on 1 after silica gel chromatography. c Diastereomeric
downfield from the internal standard Me4Si (TMS). Chemical
shifts in 13C NMR spectra are reported relative to the central
line of the chloroform signal (d = 77.50 ppm). High-resolution
mass spectra were obtained with a GCT-TOF instrument.
1
ratio (dr) determined by H NMR analysis, relative stereochemistry not
determined.
General procedure for the synthesis of epoxides
Table 4 Products obtained by the propargylation of a-bromoketones
with propargylzinc bromidea
The solution of substrate (a-haloketones, 0.5 mmol, in 3 mL THF)
was added to the mixture of organozinc bromide (1 mmol) in
dry THF (3 mL). The reaction mixture was stirred for 2 h (the
reaction was monitored by TLC) and then was quenched with
water. The resulting mixture was extracted with diethyl ether (3 ¥
10 mL), and the organic layer was dried over anhydrous Na2SO4.
The solvent was removed by evaporation under reduced pressure.
Purification by column chromatography on silica gel afforded
epoxides (petroleum ether and ethyl acetate as eluent).
Entry
1
Ar
R
Product
Yield (%)b
69
p-FC6H4
H
Preparation of organozinc bromides (2a–2e)16
Bromide 2a (1 mmol) and zinc powder (1.25 mmol, 0.080 g) were
added to dry THF (3 mL) under a nitrogen atmosphere at room
temperature. The mixture was stirred for about 15–30 min, and
the zinc powder disappeared. Stirring was continued for one hour
to complete the synthesis of the organozinc reagent.
2
3
p-ClC6H4
p-BrC6H4
H
H
70
72
Preparation of organozinc bromides (2f–2h)17
Anhydrous LiCl (1 mmol) was placed in an N2-flushed flask and
dried for 20 min at 150–170 ◦C under high vacuum (1 mbar). Zinc
powder (1.4 mmol, 1.4 equiv.) was added under N2 and the reaction
flask was evacuated and refilled with nitrogen three times. THF (1
mL) was added and the Zn was activated with BrCH2CH2Br (5
mol%) and Me3SiCl (1 mol%). 2f (1 mmol) was then added neat
at room temperature. The insertion reaction was complete after
24 h.
4
5
C6H5
CH3
H
68 dr = 93 : 7c
2-Naphthyl
67
General procedure for the prepare of acyclic and cyclic allylic
bromide cinnamyl bromide18
a Reaction conditions: a-bromoketone (0.5 mmol), propargylzinc bromide
(1.0 mmol) and THF (6 mL) at room temperature under nitrogen. b Isolated
yield based on 1 after silica gel chromatography. c Diastereomeric ratio (dr)
determined by 1H NMR analysis, relative stereochemistry not determined.
Triphenylphosphine (5.32 g, 20.4 mmol) was dissolved in 20 mL of
dry acetonitrile, and then Br2 (3.2 g, 20 mmol) was added dropwise
over a 15 min period with cooling to maintain the solution at T =
0–10 ◦C. The solution was allowed to warm to room temperature,
and cinnamyl alcohol (2.7 g, 20 mmol) was added in acetonitrile
reagents. This high yielding procedure is very attractive for large-
scale preparations since it is performed under mild reaction
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(5 mL) whereupon an exotherm occurred (T = 32 ◦C). After being
stirred at this temperature for 1 h, the mixture was poured into
500 mL of ether. Triphenylphosphine oxide precipitated from this
solution upon standing overnight. The solution was filtered, and
the solvent was removed by evaporation under reduced pressure.
Purification by column chromatography on silica gel afforded the
product. 1H NMR (400 MHz, CDCl3): d (ppm) 7.41–7.24 (m, 5H),
6.70–6.62 (m, 1H), 6.46–6.37 (m, 1H), 4.17 (d, J = 8.0 Hz, 2H).
23.36; HRMS (EI+) calcd for C13H1535ClO (M+): 222.0811; found:
222.0806.
2-(4-Bromophenyl)-2-(2-methylbut-3-en-2-yl)oxirane (4c)
Colourless oil. Isolated yield 91%. Compound purity: 100%
(confirmed by HPLC). IR (KBr): 3053, 2971, 2932, 2874, 1637,
1592, 1489, 1448, 1415, 1393, 1169, 1070, 1010, 919, 823, 776,
701, 564, 536 cm-1; 1H NMR (400 MHz, CDCl3): d (ppm) 7.45–
7.40 (s, 2H), 7.23–7.21 (m, 2H), 5.94–5.87 (m, 1H), 5.06–4.96 (m,
2H), 3.06 (s, 1H), 2.59 (s, 1H), 1.05–1.02 (d, 6H); 13C NMR (100
MHz, CDCl3): d (ppm) 143.81, 138.26, 130.70, 130.63, 121.64,
113.58, 65.64, 50.96, 39.91, 23.90, 23.14; HRMS (EI+) calcd for
C13H1579BrO (M+): 266.0306; found: 266.0310; C13H1581BrO (M+):
268.0286; found: 268.0260.
3-Bromocyclohexene19
To a suspension of AIBN and N-bromosuccinimide (NBS, 23.1 g,
0.13 mol) in tetrachloromethane (75 mL), cyclohexene (20 mL, 0.2
mol), was added under argon. The mixture was refluxed until the
disappearance of NBS. The mixture was then filtered, concentrated
◦
and distilled under vacuum (63–64 C, 15 mbar). The colourless
1
liquid was stored in the absence of light (12.8 g, 61% yield). H
2-(2-Methylbut-3-en-2-yl)-2-p-tolyloxirane (4d)
NMR (400 MHz, CDCl3): d (ppm) 5.94–5.90 (m, 1H), 5.85–5.80
(m, 1H), 4.86–4.84 (m, 1H), 2.30–1.64 (m, 6H).
Colourless oil. Isolated yield 63%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.24–7.22 (m, 2H), 7.09–7.07 (m, 2H), 5.97–5.90 (m, 1H),
5.03–4.95 (m, 2H), 3.03 (d, J = 5.2 Hz, 1H), 2.60 (d, J = 5.2 Hz,
1H), 2.32 (s, 3H), 1.06 (s, 3H), 1.03 (s, 3H); 13C NMR (100 MHz,
CDCl3): d (ppm) 144.29, 137.21, 136.30, 129.00, 128.18, 113.12,
66.01, 51.06, 40.08, 24.10, 23.31, 21.43; HRMS (EI+) calcd for
C14H18O (M+): 202.1358; found: 202.1356.
(Z)-3-Bromocyclooct-1-ene20
A mixture of the cyclooctene (20 mL, 154 mmol), NBS (27.4 g,
154 mmol), and benzoyl peroxide (70%, 100 mg, 0.29 mmol) in
CCl4 (100 mL) was heated at reflux for 1 h. The reaction mixture
was cooled to 0 ◦C then filtered. The filtrate was washed with 5%
aq. NaHCO3 then dried and concentrated in vacuo. Purification
via fractional distillation at reduced pres◦sure gave the product as
a colourless oil (17.8 g, 61%); bp: 68–70 C (3 mmHg). 1H NMR
(400 MHz, CDCl3): d (ppm) 5.82–5.74 (m, 1H), 5.65–5.57 (m,
1H), 5.00–4.90 (m, 1H), 2.30–1.24 (m, 10H).
2-(2-Methylbut-3-en-2-yl)-2-(naphthalen-3-yl)oxirane (4e)
Colourless oil. Isolated yield 89%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.80–7.72 (m, 4H), 7.49–7.43 (m, 3H), 6.02–5.95 (m, 1H),
5.06–4.97 (m, 2H), 3.10 (d, J = 5.1 Hz, 1H), 2.69 (d, J = 5.1 Hz,
1H), 1.11 (s, 3H), 1.08 (s, 3H); 13C NMR (100 MHz, CDCl3):
d (ppm) 138.58, 131.25, 127.29, 127.11, 122.65, 122.41, 122.26,
121.58, 121.36, 120.71, 120.65, 107.82, 60.74, 45.63, 34.67, 18.59,
17.80; HRMS (EI+) calcd for C17H18O (M+): 238.1358; found:
238.1361.
2-(2-Methylbut-3-en-2-yl)-2-phenyloxirane (3a)
Colourless oil. Isolated yield 90%. Compound purity: 100%
(confirmed by HPLC). IR (KBr): 3058, 2972, 2932, 2874, 1637,
1603, 1495, 1469, 1446, 1414, 1342, 1178, 1053, 1023, 918, 837,
753, 702, 564 cm-1; 1H NMR (400 MHz, CDCl3): d (ppm) 7.40–
7.20 (m, 5H), 5.97–5.90 (m, 1H), 5.04–4.96 (m, 2H), 3.05 (d, J =
4.7 Hz, 1H), 2.63 (d, J = 4.7 Hz, 1H), 1.07 (s, 3H), 1.04 (s, 3H);
13C NMR (100 MHz, CDCl3): d (ppm) 144.16, 139.22, 129.08,
127.59, 127.48, 113.22, 66.13, 50.96, 40.02, 24.06, 23.29; HRMS
(EI+) calcd for C13H16O (M+): 188.1201; found: 188.1201.
1-(2-Methylbut-3-en-2-yl)-1H-inden-2(3H)-one (4f)
Colourless oil. Isolated yield 76%. IR (KBr): 3081, 2964, 2930,
2871, 1707, 1608, 1597, 1464, 1364, 1275, 1205, 1096, 1001, 916,
1
749, 685 cm-1; H NMR (300 MHz, CDCl3): d (ppm) 7.71–7.52
(m, 2H), 7.43–7.24 (m, 2H), 5.84 (dd, J = 10.8 Hz, J = 17.4 Hz,
1H), 5.02–4.93 (m, 2H), 3.14 (dd, J = 8.0 Hz, J = 17.5 Hz, 1H),
2.91 (dd, J = 3.8 Hz, J = 17.5 Hz, 1H), 2.58 (dd, J = 4.0 Hz,
J = 7.9 Hz, 1H), 1.24 (s, 3H), 1.14 (s, 3H); 13C NMR (75 MHz,
CDCl3): d (ppm) 207.53, 153.62, 145.81, 138.12, 134.72, 127.41,
126.43, 123.76, 112.09, 55.61, 40.23, 30.52, 26.15, 23.63; HRMS
(EI+) calcd for C14H16O (M+): 200.1201; found: 200.1203.
2-(4-Fluorophenyl)-2-(2-methylbut-3-en-2-yl)oxirane (4a)
1
Colourless oil. Isolated yield 89%. H NMR (400 MHz,CDCl3):
d (ppm) 7.33–7.30 (m, 2H), 6.99–6.94 (t, 2H), 5.95–5.87 (m, 1H),
5.05–4.95 (m, 2H), 3.06 (d, J = 5.0 Hz, 1H), 2.60 (d, J = 5.0 Hz,
1H), 1.06 (s, 3H), 1.03 (s, 3H); 13C NMR (100 MHz, CDCl3):
d (ppm) 144.15, 130.91, 130.83, 114.69, 114.48, 113.64, 65.80,
51.24, 40.22, 24.14, 23.36; HRMS (EI+) calcd for C13H15OF(M+):
206.1107; found: 206.1106.
2-Allyl-2-(pyren-6-yl)oxirane (4g)
Colourless oil. Isolated yield 72%. 1H NMR (300 MHz, CDCl3):
d (ppm) 8.33–8.30 (m, 1H), 8.14–7.91 (m, 8H), 5.85–5.71 (m, 1H),
5.07–5.00 (m, 2H), 3.28 (d, J = 5.2 Hz, 1H), 3.02 (d, J = 5.2 Hz,
1H), 3.00–2.91 (m, 1H), 2.87–2.79 (m, 1H); 13C NMR (75 MHz,
CDCl3): d (ppm) 134.16, 132.93, 131.63, 131.30, 131.05, 128.47,
128.31, 127.86, 127.76, 126.43, 126.00, 125.81, 125.69, 125.12,
124.97, 124.90, 123.86, 119.13, 61.17, 53.44, 42.46; HRMS (EI+)
calcd for C21H16O (M+): 284.1201; found: 284.1200.
2-(4-Chlorophenyl)-2-(2-methylbut-3-en-2-yl)oxirane (4b)
Colourless oil. Isolated yield 90%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.30–7.24 (m, 4H), 5.94–5.89 (m, 1H), 5.05–4.95 (m,
2H), 3.06 (d, J = 5.0 Hz, 1H), 2.60 (d, J = 5.0 Hz, 1H), 1.05 (s,
3H), 1.02 (s, 3H); 13C NMR (100 MHz, CDCl3): d (ppm) 144.07,
137.98, 133.67, 130.59, 127.91, 113.77, 65.82, 51.21, 40.17, 24.13,
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2-Phenyl-2-(1-phenylallyl)oxirane (3b)
563 cm-1; 1H NMR (400 MHz, CDCl3): d (ppm) 7.44 (d, J = 7.9
Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 5.81 (d, J = 9.5 Hz, 1H), 5.67
(d, J = 10.0 Hz, 1H), 3.03 (d, J = 4.6 Hz, 1H), 2.68 (d, J = 4.4
Hz, 1H), 2.60 (s, 1H), 1.93 (s, 2H), 1.74–1.71 (m, 2H), 1.50–1.38
(m, 2H); 13C NMR (75 MHz, CDCl3): d (ppm) 138.82, 131.34,
130.65, 129.19, 125.84, 121.70, 63.05, 52.86, 40.44, 25.65, 25.18,
21.40; HRMS (EI+) calcd for C14H1579BrO (M+): 278.0306; found:
278.0305; C14H1581BrO (M+): 280.0286; found: 280.0303.
Colourless oil. Isolated yield 53%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.26–7.10 (m, 10H), 6.18–5.96 (m, 1H), 5.25–5.01 (m,
2H), 4.02–3.99 (m, 1H), 3.15–2.65 (m, 2H); 13C NMR (75 MHz,
CDCl3): d (ppm) 140.70, 139.72, 139.67, 139.46, 137.31, 136.76,
129.41, 128.94, 128.60, 128.23, 128.15, 127.76, 127.50, 127.31,
126.91, 118.42, 118.00, 62.90, 62.76, 54.36, 54.17, 53.39, 53.12;
HRMS (EI+) calcd for C17H16O (M+): 236.1201; found: 236.1199.
2-(Cyclohex-2-enyl)-2-(4-fluorophenyl)oxirane (5cc)
2-(4-Bromophenyl)-2-(1-phenylallyl)oxirane (4h)
Colourless oil. Isolated yield 88%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.36–7.32 (m, 2H), 7.02–6.98 (m, 2H), 5.81 (d, J = 8.5
Hz, 1H), 5.70 (d, J = 10.1 Hz, 1H), 3.03 (d, J = 5.0 Hz, 1H), 2.71
(d, J = 5.0 Hz, 1H), 2.59 (s, 1H), 1.94 (s, 2H), 1.77–1.70 (m, 2H),
1.51–1.38 (m, 2H); 13C NMR (100 MHz, CDCl3): d (ppm) 130.64,
129.44, 129.36, 126.27, 115.37, 115.16, 63.27, 53.12, 41.03, 25.83,
25.37, 21.60; HRMS (EI+) calcd for C14H15FO (M+): 218.1107;
found: 218.1134.
Colourless oil. Isolated yield 56%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.37–7.06 (m, 9H), 6.13–5.92 (m, 1H), 5.25–5.01 (m,
2H), 3.98–3.92 (m, 1H), 3.15–2.60 (m, 2H); 13C NMR (75
MHz, CDCl3): d (ppm) 140.39, 139.08, 138.82, 136.94, 136.39,
131.77, 131.70, 131.35, 131.30, 129.33, 129.09, 128.84, 128.74,
128.66, 128.62, 127.41, 127.06, 121.79, 121.50, 118.72, 118.26,
62.50, 62.35, 54.03, 54.00, 53.36, 53.09; HRMS (EI+) calcd for
C17H1579BrO (M+): 314.0306; found: 314.0310.
2-(Cyclohex-2-enyl)-2-p-tolyloxirane (5cd)
2-(1-Phenylallyl)-2-p-tolyloxirane (4i)
Colourless oil. Isolated yield 65%. 1H NMR (400 MHz, CDCl3).
d (ppm) 7.26 (d, J = 7.4 Hz, 2 H), 7.12 (d, J = 7.5 Hz, 2H), 5.79
(d, J = 7.5 Hz, 1H), 5.71 (d, J = 10.2 Hz, 1H), 3.01 (d, J = 4.9 Hz,
1H), 2.70 (d, J = 4.9 Hz, 1H), 2.61 (s, 1H), 2.33 (s, 3H), 1.93 (s,
2H), 1.76–1.71 (m, 2H), 1.48–1.42 (m, 2H); 13C NMR (100 MHz,
CDCl3): d (ppm) 137.53, 136.99, 130.36, 129.09, 127.58, 126.64,
63.58, 53.11, 40.94, 25.88, 25.44, 21.73, 21.62; HRMS (EI+) calcd
for C15H18O (M+): 214.1358; found: 214.1361.
Colourless oil. Isolated yield 44%. 1H NMR (400 MHz, CDCl3):
d (ppm) 6.97–7.28 (m, 9H), 5.95–6.14 (m, 1H), 5.01–5.24 (m,
2H), 3.97–3.99 (d, 1H), 2.64–3.14 (m, 2H), 2.23–2.29 (d, 3H); 13
C
NMR (100 MHz, CDCl3): d (ppm) 141.01, 139.81, 137.63, 137.57,
137.27, 137.09, 136.92, 136.84, 129.59, 129.15, 129.12, 129.04,
128.77, 128.73, 127.41, 127.02, 118.53, 118.07, 62.92, 62.82, 54.60,
54.35, 53.68, 53.38, 21.63, 21.57; HRMS (EI+) calcd for C18H18O
(M+): 250.1358; found: 250.1360.
2-(Cyclohex-2-enyl)-3-methyl-2-phenyloxirane (5ce)
2-(Cyclohex-2-enyl)-2-phenyloxirane (3c)
Colourless oil. Isolated yield 80%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.33–7.26 (m, 5H), 5.78–5.71 (t, 2H), 3.28–3.24 (m, 1H),
2.50 (s, 1H), 1.91 (s, 2H), 1.73–1.68 (m, 2H), 1.48–1.46 (m, 2H),
1.13 (d, J = 5.3 Hz; trans, 3H), 0.98 (d, J = 5.3 Hz; cis, 3H);
13C NMR (75 MHz, CDCl3): d (ppm) 137.85, 130.06, 128.13,
127.92, 127.35, 126.31, 68.36, 57.80, 42.21, 25.81, 25.22, 21.55,
15.47; HRMS (EI+) calcd for C15H18O (M+): 214.1358; found:
214.1358.
Colourless oil. Isolated yield 92%. Compound purity: 99.50%
(confirmed by HPLC). IR (KBr): 3026, 2933, 2861, 2835, 1651,
1603, 1495, 1447, 1377, 1252, 1138, 1026, 937, 910, 829, 761, 700,
1
653 cm-1; H NMR (400 MHz, CDCl3): d (ppm) 7.38–7.24 (m,
5H), 5.80 (d, J = 9.8 Hz, 1H), 5.71 (d, J = 10.1 Hz, 1H), 3.04 (d,
J = 5.0 Hz, 1H), 2.72 (d, J = 5.0 Hz, 1H), 2.65 (s, 1H), 1.93 (s,
2H), 1.76–1.71 (m, 2H), 1.51–1.41 (m, 2H); 13C NMR (75 MHz,
CDCl3): d (ppm) 139.81, 130.32, 128.21, 127.70, 127.43, 126.25,
63.51, 52.84, 40.57, 25.65, 25.24, 21.50; HRMS (EI+) calcd for
C14H16O (M+): 200.1201; found: 200.1199.
2-(Cyclohex-2-enyl)-2-(naphthalen-3-yl)oxirane (5cf)
Colourless oil. Isolated yield 89%. Compound purity: 99.12%
(confirmed by HPLC). IR (KBr): 3054, 3022, 2930, 2860, 1633,
1601, 1506, 1448, 1352, 1140, 950, 896, 858, 815, 748, 702, 478
2-(4-Chlorophenyl)-2-(cyclohex-2-enyl)oxirane (5ca)
Colourless oil. Isolated yield 90%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.31 (s, 4H), 5.81 (d, J = 9.8 Hz, 1H), 5.68 (d, J = 10.0
Hz, 1H), 3.04 (d, J = 5.1 Hz, 1H), 2.70 (d, J = 5.1 Hz, 1H), 2.60 (s,
1H), 1.94 (s, 2H), 1.76–1.71 (m, 2H), 1.53–1.38 (m, 2H); 13C NMR
(75 MHz, CDCl3): d (ppm) 138.34, 133.53, 130.60, 128.86, 128.40,
125.91, 62.99, 52.89, 40.51, 25.66, 25.20, 21.42; HRMS (EI+) calcd
for C14H1535ClO (M+): 234.0811; found: 234.0810. C14H1537ClO
(M+): 236.0782; found: 236.0813.
1
cm-1; H NMR (400 MHz, CDCl3): d (ppm) 7.84–7.77 (m, 4H),
7.51–7.44 (m, 3H), 5.80–5.74 (m, 2H), 3.10 (d, J = 5.0 Hz, 1H),
2.78 (d, J = 5.0 Hz, 2H), 1.92 (s, 2H), 1.77–1.72 (m, 2H), 1.52–1.45
(m, 2H); 13C NMR (75 MHz, CDCl3): d (ppm) 137.40, 133.17,
132.96, 130.69, 130.49, 128.23, 127.89, 126.40, 126.32, 126.22,
126.18, 125.39, 63.69, 52.99, 40.51, 25.74, 25.24, 21.51; HRMS
(EI+) calcd for C18H18O (M+): 250.1358; found: 250.1357.
2-(Cyclooct-2-enyl)-2-phenyloxirane (3d)
2-(4-Bromophenyl)-2-(cyclohex-2-enyl)oxirane (5cb)
Colourless oil. Isolated yield 82%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.42–7.26 (m, 5H), 5.80–5.73 (m, 1H), 5.32 (t, J = 9.6 Hz,
1H), 3.30–3.24 (m, 1H), 3.01 (d, J = 4.9 Hz, 1H), 2.62 (d, J = 4.9 Hz,
1H), 2.25–2.05 (m, 2H), 1.69–1.23 (m, 8H); 13C NMR (75 MHz,
Colourless oil. Isolated yield 92%. Compound purity: 100%
(confirmed by HPLC). IR (KBr): 3024, 2932, 2860, 2835, 1651,
1593, 1488, 1448, 1394, 1253, 1140, 1071, 1010, 912, 824, 749, 725,
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CDCl3): d (ppm) 140.77, 131.27, 128.95, 128.42, 127.49, 126.53,
62.43, 53.93, 39.00, 31.49, 29.84, 27.32, 27.26, 25.57; HRMS (EI+)
calcd for C16H20O (M+): 228.1514; found: 228.1513.
1H), 2.90 (s, 2H), 2.80 (d, J = 5.0 Hz, 1H), 2.08 (s, 1H); 13C NMR
(100 MHz, CDCl3): d (ppm) 128.19, 128.11, 115.85, 115.63, 79.14,
71.86, 57.99, 56.05, 26.70; HRMS (EI+) calcd for C11H9O F(M+):
176.0637; found: 176.0635.
2-(4-Chlorophenyl)-2-(cyclooct-2-enyl)oxirane (5da)
2-(4-Chlorophenyl)-2-(prop-2-ynyl)oxirane (6b)
Colourless oil. Isolated yield 81%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.36–7.29 (m, 4H), 5.81–5.74 (m, 1H), 5.29 (t, J = 9.6 Hz,
1H), 3.26–3.21 (m, 1H), 3.01 (d, J = 4.9 Hz, 1H), 2.59 (d, J = 4.8 Hz,
1H), 2.22–2.10 (m, 2H), 1.67–1.20 (m, 8H); 13C NMR (75 MHz,
CDCl3): d (ppm) 139.38, 133.28, 131.53, 128.61, 127.93, 127.24,
62.01, 53.86, 38.87, 31.39, 29.77, 27.30, 27.22, 25.50; HRMS (EI+)
calcd for C16H1935ClO (M+): 262.1124; found: 262.1122.
Colourless oil. Isolated yield 70%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.39–7.25 (m, 4H), 3.22 (d, J = 5.0 Hz, 1H), 2.91 (s, 2H),
2.80 (d, J = 5.0 Hz, 1H), 2.08 (s, 1H); 13C NMR (100 MHz, CDCl3):
d (ppm) 137.61, 134.12, 128.81, 127.56, 78.81, 71.73, 57.73, 54.93,
26.27; HRMS (EI+) calcd for C11H935ClO (M+): 192.0342; found:
192.0340. C14H1537ClO (M+): 194.0312; found: 194.0340.
2-(4-Bromophenyl)-2-(prop-2-ynyl)oxirane (6c)
2-(4-Bromophenyl)-2-(cyclooct-2-enyl)oxirane (5db)
Colourless oil. Isolated yield 72%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.48 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.3 Hz, 2H), 3.21 (d,
J = 5.2 Hz, 1H), 2.90 (s, 2H), 2.79 (d, J = 5.1 Hz, 1H), 2.08 (s, 1H);
13C NMR (100 MHz, CDCl3): d (ppm) 138.34, 131.97, 128.09,
122.48, 79.00, 72.00, 57.99, 55.13, 26.40; HRMS (EI+) calcd for
C11H979BrO (M+): 235.9837; found: 235.9835; C11H981BrO (M+):
237.9816; found: 237.9811.
Colourless oil. Isolated yield 80%. 1H NMR (400 MHz,CDCl3): d
(ppm) 7.46 (d, J = 8.2 Hz, 1H), 7.29 (d, J = 8.2 Hz, 1H), 5.80–5.74
(m, 1H), 5.28 (t, J = 9.8 Hz, 1H), 3.26–3.20 (m, 1H), 3.01 (d, J = 5.1
Hz, 1H), 2.58 (d, J = 5.1 Hz, 1H), 2.22–2.08 (m, 2H), 1.70–1.20 (m,
8H); 13C NMR (75 MHz, CDCl3): d (ppm) 139.92, 131.54, 128.91,
128.58, 128.27, 121.43, 62.02, 53.81, 38.79, 31.39, 29.77, 27.31,
27.23, 25.50; HRMS (EI+) calcd for C16H1979BrO (M+): 306.0619;
found: 306.0603; C14H1581BrO (M+): 308.0599; found: 308.0577.
3-Methyl-2-phenyl-2-(prop-2-ynyl)oxirane (6d)
2-(Cyclooct-2-enyl)-3-methyl-2-phenyloxirane (5dc)
Colourless oil. Isolated yield 68%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.49–7.26 (m, 5H), 3.48–3.44 (m, 1H), 2.85 (s, 1H), 2.04
(s, 1H), 1.51 (d, J = 5.4 Hz; trans, 3H), 1.01 (d, J = 5.3 Hz; cis,
3H); 13C NMR (75 MHz, CDCl3): d (ppm) 137.86, 128.39, 127.96,
127.20, 79.33, 71.33, 63.26, 59.30, 28.37, 14.66; HRMS (EI+) calcd
for C12H12O (M+): 172.0888; found: 172.0888.
Colourless oil. Isolated yield 75%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.33 (s, 5H), 5.79–5.72 (m, 1H), 5.33 (t, J = 9.9 Hz, 1H),
3.23–3.20 (m, 1H), 3.11 (t, J = 9.3 Hz, 1H), 2.24–2.08 (m, 2H),
1.70–1.22 (m, 8H), 1.08 (d, J = 5.3 Hz; trans, 1H), 0.93 (d, J = 5.2
Hz; cis, 1H); 13C NMR (75 MHz, CDCl3): d (ppm) 138.72, 131.12,
128.92, 128.13, 127.63, 127.26, 67.68, 58.37, 40.77, 31.73, 29.86,
27.37, 27.27, 25.52, 14.83; HRMS (EI+) calcd for C17H22O (M+):
242.1671; found: 242.1667.
2-(Naphthalen-6-yl)-2-(prop-2-ynyl)oxirane (6e)
Colourless oil. Isolated yield 67%. 1H NMR (400 MHz, CDCl3):
d (ppm) 7.91–7.81 (m, 4H), 7.51–7.46 (m, 3H), 3.29 (d, J = 5.2 Hz,
1H), 3.04 (s, 2H), 2.90 (d, J = 5.1 Hz, 1H), 2.08 (s, 1H); 13C NMR
(75 MHz, CDCl3): d (ppm) 136.51, 133.23, 133.14, 128.45, 128.27,
128.86, 126.59, 126.48, 125.36, 123.69, 79.10, 71.57, 58.30, 54.95,
26.35; HRMS (EI+) calcd for C15H12O (M+): 208.0888; found:
208.0887.
2-tert-Butyl-2-(cyclooct-2-enyl)oxirane (5dd)
Colourless oil. Isolated yield 78%. 1H NMR (400 MHz, CDCl3):
d (ppm) 5.66–5.59 (m, 1H), 5.39 (t, J = 9.8 Hz, 1H), 3.15–3.09 (m,
1H), 2.76 (d, J = 4.1 Hz, 1H), 2.67 (d, J = 4.0 Hz, 1H), 2.23–2.07
(m, 2H), 1.75–1.08 (m, 8H), 0.96 (s, 9H); 13C NMR (75 MHz,
CDCl3): d (ppm) 131.24, 128.45, 66.38, 48.31, 35.38, 34.59, 34.16,
29.83, 27.17, 27.03, 26.57, 25.55; HRMS (EI+) calcd for C14H24O
(M+): 208.1827; found: 208.1802.
Acknowledgements
We gratefully acknowledge a project funded by the Priority
Academic Program Development of Jiangsu Higher Education
Institutions and the National Natural Science Foundation of
China (No. 21072143) for financial support.
2-Phenyl-2-(prop-2-ynyl)oxirane (3e)
Colourless oil. Isolated yield 75%. Compound purity: 99.99%
(confirmed by HPLC). IR (KBr): 3302, 3077, 2923, 2854, 1638,
1604, 1554, 1422, 1383, 1261, 1128, 1017, 899, 804, 746, 636 cm-1;
1H NMR (400 MHz, CDCl3): d (ppm) 7.44–7.29 (m, 5H), 3.23 (d,
J = 4.8 Hz, 1H), 2.90 (s, 2H), 2.82 (d, J = 4.7 Hz, 1H), 2.06 (s,
1H); 13C NMR (75 MHz, CDCl3): d (ppm) 139.43, 128.95, 128.54,
126.40, 79.44, 71.80, 58.40, 55.09, 26.60; HRMS (EI+) calcd for
C11H10O (M+): 158.0732; found: 158.0735.
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