The Epoxidation of Carbonyl Compounds with a Benzyne-Triggered Sulfur Ylide

Article abstract of DOI:10.1021/acs.joc.6b00760

An efficient method for the synthesis of epoxides from carbonyl compounds, sulfoxides, and benzyne is presented. The strategy involved an epoxidation by a sulfur ylide which is formed in situ from sulfoxide and benzyne through the S-O bond insertion and d

Full text of DOI:10.1021/acs.joc.6b00760

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Article
The epoxidation of carbonyl compounds with benzyne triggered sulfur ylide
Mei-Mei Lou, Han Wang, Li Song, Hong-Yi Liu, Zhong-
Qiu Li, Xiao-Shuang Guo, Fu-Geng Zhang, and Bin Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00760 • Publication Date (Web): 23 Jun 2016
Downloaded from http://pubs.acs.org on June 28, 2016
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The Journal of Organic Chemistry
The epoxidation of carbonyl compounds with benzyne triggered sulfur ylide
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MeiꢀMei Lou,† Han Wang,† Li Song,† HongꢀYi Liu,† ZhongꢀQiu Li,† XiaoꢀShuang Guo,† FuꢀGeng Zhang,*,
‡ and Bin Wang*, †
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†State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy and Tianjin Key Laboratory
of Molecular Drug Research, Nankai University, Haihe Education Park, 38 Tongyan Road, Tianjin 300353,
People’s Republic of China
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‡Tianjin Key Laboratory of Cerebral Vascular and Neurodegenerative Diseases, Tianjin Huanhu Hospital,
Tianjin 300060, People’s Republic of China
clare2006@163.com; wangbin@nankai.edu.cn
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Abstract Graphic
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ABSTRACT
An efficient method for the synthesis of epoxides from carbonyl compounds, sulfoxides and benzyne is
presented. The strategy involved an epoxidation by a sulfur ylide, which is formed in situ from sulfoxide
and benzyne through the SꢀO bond insertion and deprotonation. This oneꢀpot reaction proceeds under mild
and baseꢀfree conditions, providing a convenient way to introduce the substituted methylene groups onto
the carbonyl carbon.
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The Journal of Organic Chemistry
INTRODUCTION
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The previous methods:
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A. from thioethers
X
R2
R2
S
6
7
8
9
R3
R4
base or F
deprotonation
R3
R3
S
R1
R4
R1
C
X
path 1
path 2
alkylation
R4
R4
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M
R2
S
R3
or
R3
R4
R3
S
S
R1
C
R1
R2
R4
R2
S
R2
Br
COOH
alkylation
heat
decarboxylation
COO
S
R1
R1
CH2
path 3
path 4
R2
H
R2
C
R2
R1
C
S
R1
R3
S
R3
R3
R1
B. from sulfoxides
O
O
S
O
strong bases
deprotonation
CH3I
S
I
S
CH2
alkylation
This method:
sulfoxide and benzyne stragergy
O
S
OPh
H
O
S
R1
R1
R2
C
deprotonation
S-O bond cleavage
S-O bond insertion
S
R1
R2
R2
Scheme 1. Preparation of sulfur ylides
Since the early 1960s, sulfur ylides have emerged as reactive nucleophilic alkylidene transfer agents in
organic synthesis.1ꢀ5 This class of intermediates has been found to have wide applications in the synthesis
of epoxides,6,7 cyclopropanes,8 aziridines,9ꢀ11 terminal alkenes,12 and organoboron compounds.13, 14 The most
common method of sulfur ylide generation consists of proton abstraction from the corresponding
sulfonium salts, which are available by the direct alkylation of thioethers (Scheme 1, method A, path 1).15,
16 A less common but exceedingly useful approach for the generation of sulfur ylides involves the reaction
of a thioether with a carbene or a metal carbenoid (Scheme 1, method A, path 2).15 Forbes and coworkers
developed a new strategy for the synthesis of sulfur ylides, which is based on the alkylation of thioethers
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with 2ꢀbromoacetic acid and the decarboxylation of in situ generated sulfonium (Scheme 1, method A, path
3).17, 18 Since the early 1960s, the benzyne triggered method for the preparation of sulfur ylides has
emerged (Scheme 1, method A, path 4).19ꢀ21 The ylide was generated in situ from a thioether with benzyne,
and the trapping of ylide with Nꢀmethyl isatins gave the corresponding spiroepoxy oxindoles.22 Besides
thioethers, a practical alternative approach utilizing the sulfoxides as the starting materials for the
generation of stable ylides was chosen (Scheme 1, method B).2 However, the direct alkylation of
sulfoxides to generate the sulfoxonium salts is essentially limited to the reaction of methyl halide with
dimethyl sulfoxide (DMSO), and the subsequent deprotonation requires the use of strong bases such as
sodium hydride,2, 3, 23ꢀ26 sodium methylsulfinylmethylide27ꢀ32 and nꢀbutyllithium.33 In addition, the ylide
generated from DMSO only transfers methylene group to the electrophiles. Very recently, Xiao and our
group independently reported a SꢀO bond insertion of sulfoxides with arynes (Scheme 1).34, 35 The reaction
mechanism involves a benzannulated fourꢀmembered ring intermediate that leads to the formation of a
sulfur ylide via deprotonation and SꢀO bond cleavage. This benzyne triggered method for the production of
sulfur ylides from sulfoxides is free of bases. Moreover, the introduction of substituted methylene units
into an electrophilic carbon to prepare highly substituted epoxides is achieved in a facile manner. Herein,
we describe the epoxidation of carbonyl compounds with benzyne triggered sulfur ylide.
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The Journal of Organic Chemistry
RESULTS AND DISCUSSION
Table 1. Optimization of the reaction conditionsa
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O
O
Ph
TMS
OTf
SPh
OPh
O
[F-] ( 0.75 mmol)
solvent
+
+
+
O
S
O
Ph Bn
N
N
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1
2
3a
4a
5a
entry
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2
3
4
5
6
7
8
solvent
1,4ꢀdioxane
toluene
hexane
THF
[Fꢀ]
CsF
CsF
CsF
CsF
CsF
CsF
CsF
KF
T (°C)
25
25
25
25
25
25
50
50
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50
50
time (h)
4a yield (%)
6
6
6
6
4
0
0
0
65
93
96
98
25
41
0
DME
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
1
0.5
2.5
2.0
2.5
0.5
0.5
9
Bu4NF
NH4F
CsF
CsF
10
11
12
50b
63c
aReaction conditions: 1 (0.5 mmol), 2 (0.125 mmol), 3a (0.25 mmol) in 1 mL solvent under air; isolated full yield of two
isomers of 4a. b1: 2: 3a molar ratio = 2:1:1; c1: 2: 3a molar ratio = 3:1:2.
Kobayashi benzyne precursor 1, Nꢀmethyl isatin 2 and benzyl phenyl sulfoxide 3a were chosen as model
substrates in the optimization of reaction conditions yielding the epoxide 4a. The insertion reaction also
produced phenyl(2ꢀphenoxyphenyl) sulfane 5a, whose structure and generation mechanism were
established in our earlier work.34 An initial solvent screening with CsF as aryne initiator revealed that
1,4ꢀdioxane, toluene, and hexane failed to undergo the epoxidation within 6 h at 25 °C (Table 1, entries
1ꢀ3). Further examination indicated that the expoxidation was performed in 65% yield in THF (Table 1,
entry 4), and DME was more efficient and the reaction afforded 4a in 93% yield within 4h (Table 1, entry
5). We were delighted to discover that the reaction in acetonitrile went to completion within 1 h to give an
excellent yield of 4a (Table 1, entry 6). When the reaction temperature was increased to 50 °C, the yield of
4a was further increased to 98% within shorter reaction time (Table 1, entry 7). Screening of other fluoride
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showed that both KF and Bu4NF were less effective in the epoxidation, while NH4F was completely
ineffective under these conditions (Table 1, entries 8ꢀ10). The molar ratio of substrates of 1, 2 and 3a was
also investigated, and the results indicated that the yield of 4a was significantly decreased (from 98% to 50%
and 63%) if the molar ratio was changed from 4:1:2 to 2:1:1 or 3:1:2 (Table 1, entry 7 vs entries 11, 12).
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The Journal of Organic Chemistry
Table 2. Substrate scope of various sulfoxidesa
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aReaction conditions: 1 (1 mmol), 2 (0.25 mmol), 3a-s (0.5 mmol), CsF (1.5 mmol) in CH3CN (1 mL); isolate yield.
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The scope of the benzyneꢀtriggered epoxidation of Nꢀmethyl isatin 2 with CsF in acetonitrile was next
examined with a diverse array of sulfoxides. As summarized in Table 2, these epoxidations could be
applied to sulfoxides containing a variety of different groups, including aryl, benzyl and alkyl groups. It
should be noted that most of the epoxidations gave products as a mixture of two diastereoisomers, which
were successfully purified by column chromatography on silica gel and isolated respectively. Sulfoxide 3e,
3h, 3k, 3l,, 3o, 3q afforded the corresponding two diastereoisomers in which the major diastereoisomers
had the cis stereochemistry, while sulfoxide 3g favoured the trans product. Other sulfoxide 3a-d, 3m, 3n
led to both diastereoisomeric epoxides in roughly equal yields. The stereochemistry of these epoxides was
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readily determined from examination of the NMR (HMQC and 2D Hꢀ1H NOESY) for the corresponding
cis and trans isomers, consistent with literature examples.22, 36ꢀ38 The epoxidation of Nꢀmethyl isatin 2 with
benzyne triggered sulfur ylides proceeded efficiently in sulfoxides containing benzylic group with both
electronꢀwithdrawing (Table 2, 3bꢀg, 3i, 3j) and electronꢀdonating (Table 2, 3kꢀn) substituents. Functional
groups such as fluoro, chloro, bromo, nitro, cyano, methoxy, naphthyl group were tolerated under the
reaction conditions. Furthermore, sulfoxides with aliphatic chains (Table 2, 3p-s), including alkoxyl, ethyl,
methyl, and isopropyl substituent could also produce the corresponding epoxides in 48ꢀ92% ylide. It is
noteworthy that bromomethyl group was well tolerated in sulfoxide 3h, leading to the valuable
bromoꢀsubstituted epoxides 4ha and 4hb, which could not be prepared by the standard
alkylation/deprotonation methodology with sulfides.
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The Journal of Organic Chemistry
Table 3. Substrate scopes of various aromatic aldehydea
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6
7
O
O
S
O
1, CsF, 18-crown-6
R1
+
R1
6a-f
H
MeCN, 50 °C, 0.5 h
3a
7a-f
8
9
O
O
O
H
H
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H
H
H
O2N
O2N
O2N
6ab
NO2
7aa 23%
7ab 61%
O
NO2
O
H
6b
7b 65%
O
O
H
O
H
H
H
H
O
O
O
O
O
O
6c
7ca 19%
7cb 67%
O
O
O
O
Br
N
Br
N
H
H
H
6d
6e
7d 43%
O
H
H
I
I
7e 52%
O
NC
NC
6f
7f 59%
aReaction conditions: 1 (1 mmol), 3a (0.5 mmol), 6a-f (0.25 mmol), 18ꢀcrownꢀ6 (0.25 mmol), CsF (1.5 mmol) in CH3CN (1
mL); isolated yields. b0.25 h.
The reaction scope was subsequently explored by using benzyl phenyl sulfoxide 3a and aromatic
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aldehydes 6a-f (Table 3). Epoxidation of 4ꢀnitrobenzaldehyde 6a resulted in a good total yield of isomers
7aa and 7ab. Likewise, 2ꢀnitrobenzaldehyde 6b can easily be used in the epoxidation reaction, albeit in a
moderate yield of 65%. When the aromatic aldehyde contains other electronꢀwithdrawing groups, such as
COOMe, Br, I and CN, the epoxidation was also happened under these conditions (Table 3, 6cꢀ6f).
Unfortunately, benzaldehyde and aldehydes with electronꢀdonating groups failed to undergo the
epoxidation, most likely due to the unreactive nature of these substrates. A insertion reaction of sulfoxide
and benzyne was occurred instead, as described in our previous report.34
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CONCLUSION
In summary, we have developed a new method for the sulfur ylide generation by the insertion reaction of
benzynes with sulfoxides. In comparison to current alternative methods for epoxidation of sulfur ylides,
this system reacts under milder conditions free of bases in a oneꢀpot operation. Moreover, the substituted
methylene groups can be readily introduced onto the carbonyl carbon of Nꢀmethyl isatin and activated
aromatic aldehydes. The methodology is expected to be of high utility in the sulfur ylide chemistry.
Researchers would devise some asymmetric synthesis based on this strategy. Further studies on the
mechanistic aspects of this reaction as well as related benzyneꢀtriggered reactions are ongoing in our
laboratory.
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The Journal of Organic Chemistry
EXPERIMENTAL SECTION
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1. General remarks
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1H NMR and C NMR spectra were recorded on a 400 MHz spectrometer (400MHz for H and 100MHz
for C) using CDCl3 as a solvent. Signal positions were recorded in ppm with the abbreviations s, d, t, q,
and m denoting singlet, doublet, triplet, quartet, and multiplet respectively. All NMR chemical shifts were
referenced to residual solvent peaks or to TMS as an internal standard. NMR Spectra recorded in CDCl3
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were referenced to residual CHCl3 at 7.26 ppm for H or 77.0 ppm for C. All coupling constants J were
quoted in Hz. Data were reported as follows: chemical shift, multiplicity, coupling constant and integration.
Highꢀresolution mass spectra (HRMS) were measured using QꢀTOF LC/MS by ESIꢀFTICR technique.
Elemental analysis was carried out on a Vario EL cube analyzer. The melting point of the product was
measured with a Microscopic melting point meter. Reactions were monitored by thinꢀlayer
chromatography (TLC) on 0.25mm silica gel glass plates coated with 60 F254. Column chromatography
was performed on silica gel (200ꢀ300 mesh) using a mixture of petroleum ether (60ꢀ90°C)/ethyl acetate as
eluant. All commercially available reagents were used as received without further purification.
2. Experimental Procedures
(i) General Procedure for the Preparation of product 4.
A Schlenk tube was charged with 1ꢀmethylisatin 2 (0.25 mmol, 40.2 mg, 1 equiv.), sulfoxide 3 (0.5 mmol,
2 equiv.) and CsF (1.5 mmol, 228 mg, 6 equiv.) under air at room temperature, then 2ꢀ(trimethylsilyl)
phenyl trifluoromethanesulfonate 1 (1 mmol, 240 µL, 4 equiv.) and CH3CN (1 mL) were added. After the
mixture had been stirred at 50 °C for certain time, the residue was mixed with few silica gel and
concentrated. The resulting mixture was purified by silica gel column chromatography on silica gel with
petroleum ether/ethyl acetate (80:1) as eluent to give the desired product 4.
(ii) General Procedure for the Preparation of product 7.
A Schlenk tube was charged with benzyl phenyl sulfoxide 3a (0.5 mmol, 108 mg, 2 equiv.) and aldehyde 6
(0.25 mmol, 1 equiv.) under air at room temperature, then CsF (1.5 mmol, 228 mg, 6 equiv.), 18ꢀcrownꢀ6
(0.25 mmol, 66 mg, 1 equiv.), 2ꢀ(trimethylsilyl) phenyl trifluoromethanesulfonate 1 (1 mmol, 240 µL, 4
equiv.) and CH3CN (1 mL) were added. After the mixture had been stirred at 50 °C for certain time, the
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residue was mixed with few silica gel and concentrated. The resulting mixture was purified by silica gel
column chromatography on silica gel with petroleum ether/ethyl acetate (800:1) as eluent to give the
desired product 7. The reaction time of 6a is 0.25 h, and 6b-6f, 0.5h.
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1-methyl-3'-phenylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4aa).36, 38 Yellow solid (31.3 mg, 50%). mp:
136ꢀ137 °C. 1H NMR (400 MHz, CDCl3): δ7.60 (d, J =8.0 Hz, 2H), 7.41ꢀ7.35 (m, 4H), 7.24 (d, J = 8.0 Hz,
1H), 7.13 (m, 1H), 6.89 (d, J = 8.0 Hz, 1H), 4.67 (s, 1H), 3.15 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ169.8, 144.5, 131.6, 130.2, 128.7, 127.7, 127.4, 123.5, 122.6, 121.6, 108.6, 67.4, 61.9, 26.5; HRMS (ESI):
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+
calcd for C16H14NO2 [M+H]+: 252.1019, found 252.1021.
1-methyl-3'-phenylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4ab).36 White solid (28.2 mg, 45%). mp:
105ꢀ106 °C. 1H NMR (400 MHz, CDCl3): δ7.46ꢀ7.37 (m, 5H), 7.28 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 8.0 Hz,
13
1H), 6.77 (t, J = 8.0 Hz, 1H), 6.47 (d, J = 8.0 Hz, 1H), 4.83 (s, 1H), 3.30 (s, 3H); C NMR (100 MHz,
CDCl3): δ171.7, 145.2, 133.2, 130.1, 128.6, 128.4, 126.7, 123.6, 122.4, 120.9, 108.6, 65.0, 61.6, 26.6;
HRMS (ESI): calcd for C16H14NO2 [M+H]+: 252.1019, found 252.1022.
+
3'-(3-fluorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4ba). Yellowish solid (25.7 mg,
38%). mp: 107ꢀ108 °C. 1H NMR (400 MHz, CDCl3): δ7.43ꢀ7.34 (m, 4H), 7.23 (d, J = 8.0 Hz, 1H), 7.13 (t,
13
J = 8.0 Hz, 1H), 7.07ꢀ7.02 (m, 1H), 6.91 (d, J = 8.0 Hz, 1H), 4.65 (s, 1H), 3.17 (s, 3H); C NMR (100
1
MHz, CDCl3): δ171.3, 162.7 (d, JCꢀF = 241.5 Hz), 145.3, 135.8, 135.7, 130.4, 130.3, 130.2, 123.5, 122.6,
122.5, 122.4, 120.5, 115.8, 115.6, 113.9, 113.7, 108.7, 64.3, 64.2, 61.6, 26.7; HRMS (ESI): calcd for
+
C16H13FNO2 [M+H]+: 270.0925, found 270.0926.
3'-(3-fluorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4bb). White solid (29.5 mg,
1
44%). mp: 136ꢀ137 °C. H NMR (400 MHz, CDCl3): δ7.39ꢀ7.28 (m, 2H), 7.24ꢀ7.17 (m, 2H), 7.07 (t, J =
8.0 Hz, 1H), 6.88 (d, J = 4.0 Hz, 1H), 6.80 (t, J = 8.0 Hz, 1H), 6.49 (d, J = 8.0 Hz, 1H), 4.79 (s, 1H), 3.30
1
(s, 3H); 13C NMR (100 MHz, CDCl3): δ169.6, 162.3 (d, JCꢀF = 251.5 Hz), 144.6, 134.3, 134.2, 130.4,
129.3, 129.2, 123.1, 123.0, 122.7, 121.6, 115.8, 115.6, 114.7, 114.5, 108.7, 66.6, 66.5, 61.8, 26.5; HRMS
+
(ESI): calcd for C16H13FNO2 [M+H]+: 270.0925, found 270.0925.
3'-(3-chlorophenyl)-1-methylspiro [indoline-3,2'-oxiran]-2-one (cis-) (4ca). Yellow solid (25.6 mg,
36 %). mp: 135ꢀ136 °C. 1H NMR (400 MHz, CDCl3): δ7.58 (s, 1H), 7.51ꢀ7.50 (m, 1H), 7.41 (t, J = 8.0 Hz,
1H), 7.32 (d, J = 4.0 Hz, 2H), 7.22 (d, J = 4.0 Hz, 1H), 7.13 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H),
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13
4.63 (s, 1H), 3.16 (s, 3H); C NMR (100 MHz, CDCl3): δ169.5, 144.6, 133.8, 133.7, 130.4, 128.9, 128.9,
1
+
127.6, 125.6, 123.1, 122.7, 121.6, 108.7, 66.4, 61.8, 26.5; HRMS (ESI): calcd for C16H13ClNO2 [M+H]+:
2
3
4
5
286.0635, 287.0668, 288.0605, 289.0639, found 286.0626, 287.0654, 288.0601, 289.0633.
6
7
3'-(3-chlorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4cb). White solid (22.5 mg,
1
8
9
32%). mp: 86ꢀ87 °C. H NMR (400 MHz, CDCl3): δ7.46 (s, 1H), 7.35ꢀ7.28 (m, 4H), 6.89 (d, J = 8.0 Hz,
13
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
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27
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35
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37
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39
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41
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45
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47
48
49
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58
59
60
1H), 6.81 (t, J = 8.0 Hz, 1H), 6.47 (d, J = 8.0 Hz, 1H), 4.78 (s, 1H), 3.30 (s, 3H); C NMR (100 MHz,
CDCl3): δ171.3, 145.3, 135.3, 134.6, 130.4, 129.8, 128.9, 126.8, 124.9, 123.5, 122.6, 120.4, 108.8, 64.2,
61.6, 26.7; HRMS (ESI): calcd for C16H13ClNO2 [M+H]+: 286.0635, 287.0668, 288.0605, 289.0639,
+
found 286.0627, 287.0659, 288.0585, 289.0615.
3'-(3-bromophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4da). Yellowish solid (31.8 mg,
39 %). mp: 145ꢀ146 °C. 1H NMR (400 MHz, CDCl3): δ7.72 (s, 1H), 7.56 (d, J = 7.6 Hz, 1H), 7.47 (d, J =
8.0 Hz, 1H), 7.41 (t, J = 8.0 Hz, 1H), 7.28ꢀ7.21 (m, 2H), 7.13 (t, J = 8.0 Hz, 1H), 6.90 (d, J = 8.0 Hz, 1H),
13
4.62 (s, 1H), 3.16 (s, 3H); C NMR (100 MHz, CDCl3): δ169.5, 144.6, 134.0, 131.8, 130.4, 130.4, 129.2,
126.1, 123.1, 122.7, 121.8, 121.6, 108.7, 66.3, 61.8, 26.5; HRMS (ESI): calcd for C16H13BrNO2 [M+H] +:
+
330.0130, 331.0163, 332.0109, 333.0143, found 330.0119, 331.0153, 332.0102, 333.0136.
3'-(3-bromophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4db). Yellowish solid (29.8
mg, 36%). mp: 87ꢀ88 °C. 1H NMR (400 MHz, CDCl3): δ7.62 (s, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.38 (d, J =
8.0 Hz, 1H), 7.28 (t, J = 8.0 Hz, 2H), 6.89 (d, J = 8.0 Hz, 1H), 6,81 (t, J = 8.0 Hz, 1H), 6.47 (d, J = 8.0 Hz,
13
1H), 4.77 (s, 1H), 3.30 (s, 3H); C NMR (100 MHz, CDCl3): δ171.3, 145.3, 135.5, 131.9, 130.4, 130.1,
+
129.7, 125.3, 124.7, 123.5, 122.6, 120.4, 108.8, 64.1, 61.6, 26.7; HRMS (ESI): calcd for C16H13BrNO2
[M+H] +: 330.0130, 331.0163, 332.0109, 333.0143, found 330.0122, 331.0164, 332.0099, 333.0134.
3'-(3, 4-dichlorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4ea). White solid (28.7 mg,
40%). mp: 151ꢀ152 °C. 1H NMR (400 MHz, CDCl3): δ7.68 (s, 1H), 7.46ꢀ7.40 (m, 3H), 7.22 (d, J = 4.0 Hz,
13
1H), 7.13 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 4.60 (s, 1H), 3.17 (s, 3H); C NMR (100 MHz,
CDCl3): δ169.5, 144.6, 132.8, 132.0, 131.9, 130.5, 129.7, 129.5, 126.8, 123.4, 122.8, 121.7, 108.8, 65.9,
61.8, 26.5; HRMS (ESI) m/z calcd for C16H12Cl2NO2 [M+H]+: 320.0245, 321.0279, 322.0216, 323.0249,
+
found 320.0243, 321.0271, 322.0215, 323.0245.
3'-(3, 4-dichlorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4eb). White solid (16.8
1
mg, 21%). mp: 80ꢀ81 °C. H NMR (400 MHz, CDCl3): δ7.57 (s, 1H), 7.50 (d, J = 8.0 Hz,1H), 7.35ꢀ7.29
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(m, 2H), 6.91ꢀ6.83 (m, 2H), 6.47 (d, J = 8.0 Hz, 1H), 4.74 (s, 1H), 3.30 (s, 3H); 13C NMR (100 MHz,
1
2
3
CDCl3): δ171.0, 145.3, 133.5, 133.0, 132.9, 130.6, 130.5, 128.7, 126.0, 123.4, 122.7, 120.1, 108.9, 63.7,
+
61.7, 26.7; HRMS (ESI) m/z calcd for C16H12Cl2NO2 [M+H]+: 320.0245, 321.0279, 322.0216, 323.0249,
4
5
6
7
found 320.0240, 321.0273, 322.0212, 323.0259.
8
9
3'-(2, 5-difluorophenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (4f). White solid (43.7 mg, 61%).
mp: 119ꢀ120 °C. 1H NMR (400 MHz, CDCl3): δ7.41ꢀ7.37 (m, 1H), 7.32 (t, J= 8.0 Hz, 1H), 7.08ꢀ6.96 (m,
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11
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16
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42
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44
45
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47
48
49
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54
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59
60
13
2H), 6.90(d, J=8.0 Hz, 1H), 6.82 (t, J=8.0 Hz, 1H), 6.44 (d, J=8.0 Hz, 1H), 4.80 (s, 1H), 3.31 (s, 3H); C
1
1
NMR (100 MHz, CDCl3): δ170.9, 158.6 (d, JCꢀF = 251.5 Hz), 157.0 (d, JCꢀF = 221.3 Hz), 145.4, 130.6,
129.7, 128.5, 123.0, 122.7, 120.3, 117.1, 117.0, 116.9, 116.9, 116.8, 116.8, 116.7, 115.0, 114.8, 114.8,
108.9, 61.3, 60.5, 60.5, 26.8; HRMS (ESI): calcd for C16H12F2NO2 [M+H]+: 288.0831, found 288.0834.
+
3'-(4-chloro-2-fluorophenyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one (cis-) (4ga) Yellow solid (27.2
mg, 36%).mp: 146ꢀ147 °C.1H NMR (400 MHz, CDCl3): δ7.56 (t, J = 8.0 Hz, 1H), 7.28ꢀ7.20 (m, 2H), 7.00
(d, J = 12.0 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.76 (t, J = 8.0 Hz, 1H), 6.32 (d, J = 8.0 Hz, 1H), 4.73 (s,
13
1
1H), 3.25 (s, 3H); C NMR (100 MHz, CDCl3): δ171.0, 160.7 (d, JCꢀF = 251.5 Hz), 145.3, 135.6, 135.5,
130.5, 129.1, 129.0, 124.6, 124.6, 123.0, 122.6, 120.3, 120.0, 119.9, 116.5, 116.3, 108.9, 61.2, 60.5, 60.5,
26.7. HRMS (ESI): calcd for C16H12ClFNO2 [M+H]+: 304.0541, 305.0574, 306.0511, 307.0545, found
+
304.0536, 305.0568, 306.0509, 307.0530.
3'-(4-chloro-2-fluorophenyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one (trans-) (4gb). White solid
1
(37.1 mg, 49%).mp: 151ꢀ152 °C. H NMR (400 MHz, CDCl3): δ7.78 (t, J = 8.0 Hz, 1H), 7.42 (t, J = 8.0
Hz, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.14 (t, J = 8.0 Hz, 1H), 7.06 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 8.0 Hz,
13
1
1H), 4.76 (s, 1H), 3.18 (s, 3H); C NMR (100 MHz, CDCl3): δ169.6, 160.7 (d, JCꢀF = 241.5 Hz), 144.6,
135.4, 135.3, 130.6, 130.5, 124.0, 123.9, 122.9, 122.7, 121.9, 118.4, 118.3, 115.7, 115.5, 108.8, 61.6, 61.5,
61.4, 26.5. HRMS (ESI): calcd for C16H12ClFNO2 [M+H]+: 304.0541, 305.0574, 306.0511, 307.0545,
+
found 304.0537, 305.0559, 306.0506, 307.0535.
3'-(3-(bromomethyl)phenyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one(cis-) (4ha). White solid (26.3
1
mg, 31%).mp: 194ꢀ195°C. H NMR (400 MHz, CDCl3): δ7.64 (s, 1H), 7.55 (s, 1H), 7.41 (t, J = 8.0 Hz,
3H), 7.24 (d, J = 12.0 Hz, 1H), 7.13 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 4.0 Hz, 1H), 4.66 (s, 1H), 4.53 (s, 2H),
3.16 (s, 3H); 13C NMR (100 MHz, CDCl3): δ169.7, 144.5, 137.1, 132.4, 130.3, 129.4, 128.2, 128.1, 127.5,
+
+
123.3, 122.7, 121.6, 108.6, 67.0, 61.8, 33.3, 26.5; HRMS (ESI): calcd for C17H15BrNO2 [M+H] :
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344.0286, 345.0320, 346.0266, 347.0299, found 344.0283, 345.0308, 346.0262,347.0289.
1
2
3
4
5
6
7
3'-(3-(bromomethyl)phenyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one (trans-) (4hb). White solid
(19.3 mg, 23%).mp: 94ꢀ95 °C. 1H NMR (400 MHz, CDCl3): δ7.53 (s, 1H), 7.38 (s, 3H), 7.29 (t, J = 8.0 Hz,
1H), 6.88 (d, J = 8.0 Hz, 1H), 6.79 (t, J = 8.0 Hz, 1H), 6.51 (d, J = 8.0 Hz, 1H), 4.81 (s, 1H), 4.51 (q, J =
13
8
9
8.0 Hz, 2H), 3.30 (s, 3H); C NMR (100 MHz, CDCl3): δ171.4, 145.2, 138.1, 133.9, 130.2, 129.2, 129.0,
+
10
11
12
13
14
15
16
17
18
19
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53
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56
57
58
59
60
127.2, 126.8, 123.6, 122.5, 120.5, 108.6, 64.6, 61.6, 32.9, 26.6; HRMS (ESI): calcd for C17H15BrNO2
[M+H]+: 344.0286, 345.0320, 346.0266, 347.0299, found 344.0283, 345.0325, 346.0265, 347.0292.
1-methyl-3'-(4-nitrophenyl)spiro[indoline-3,2'-oxiran]-2-one (4i). Yellowish solid (30.6 mg, 42%). mp:
104ꢀ105 °C. 1H NMR (400 MHz, CDCl3): δ8.25 (d, J = 8.0 Hz, 2H), 7.78 (d, J = 8.0 Hz, 2H), 7.44 (t, J =
8.0 Hz, 1H), 7.25 (d, J= 8.0 Hz, 1H), 7.16 (t, J = 8.0 Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H), 4.73 (s, 1H), 3.16 (s,
13
3H); C NMR (100 MHz, CDCl3): δ169.3, 148.1, 144.7, 139.0, 130.8, 128.4, 123.0, 122.6, 121.8, 108.9,
+
65.9, 62.0, 26.6; HRMS (ESI): calcd for C16H13N2O4 [M+H]+: 297.0870, found 297.0869.
4-(1-methyl-2-oxospiro [indoline-3, 2'-oxiran]-3'-yl) benzonitrile (4j). Yellow solid (29 mg, 42%). mp:
1
151ꢀ152 °C. H NMR (400 MHz, CDCl3): δ7.70 (q, J = 8.0 Hz, 4H), 7.43 (t, J = 8.0 Hz, 1H), 7.24 (d,
J=8.0 Hz, 1H), 7.15 (t, J = 8.0 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 4.68 (s, 1H), 3.16 (s, 3H); 13C NMR (100
MHz, CDCl3): δ169.3, 144.6, 137.0, 131.4, 130.6, 128.1, 122.9, 121.7, 118.6, 112.3, 108.8, 66.0, 61.9,
+
26.5; HRMS (ESI): calcd for C17H13N2O2 [M+H]+: 277.0972, found 277.0976.
3'-(3-methoxyphenyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one (cis-) (4ka). White solid (41.5mg,
59%). mp: 97ꢀ98 °C. 1H NMR (400 MHz, CDCl3): δ7.40 (t, J = 8.0 Hz, 1H), 7.30 (d, J=8.0 Hz, 1H), 7.21
13
(s, 2H), 7.13 (t, J = 8.0 Hz, 2H), 6.90 (d, J = 4.0 Hz, 2H), 4.64 (s, 1 H), 3.84 (s, 3H); 3.16 (s, 3H); C
NMR (100 MHz, CDCl3): δ169.7, 159.0, 144.5, 133.2, 130.1, 128.7, 123.5, 122.5, 121.5, 119.7, 114.8,
112.5, 108.5, 67.4, 61.9, 55.2, 26.4; HRMS (ESI): calcd for C17H16NO3 [M+H]+: 282.1125, found
+
282.1126.
3'-(3-methoxyphenyl)-1-methylspiro[indoline-3, 2'-oxiran]-2-one (trans-) (4kb). Yellow oily liquid
(22.8 mg, 33%). 1H NMR (400 MHz, CDCl3): δ7.31 (t, J = 8.0 Hz, 2H), 7.01 (d, J = 12.0 Hz, 2H), 6.88 (t,
J = 8.0 Hz, 2H), 6.79 (t, J = 8.0 Hz, 1H), 6.55 (d, J = 8.0 Hz, 1H), 4.80 (s, 1 H), 3.81 (s, 3H), 3.30 (s, 3H);
13C NMR (100 MHz, CDCl3): δ171.7, 159.7, 145.2, 134.7, 130.2, 129.7, 123.7, 122.6, 120.9, 119.0, 114.5,
112.0, 108.7, 65.0, 61.6, 55.4, 26.7; HRMS (ESI): calcd for C17H16NO3 [M+H]+: 282.1125, found
+
282.1128.
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1-methyl-3'-(4-(trifluoromethoxy)phenyl)spiro[indoline-3,2'-oxiran]-2-one(cis-) (4la). Yellow solid
1
1
2
3
(34.2 mg, 41%). mp: 112ꢀ113 °C. H NMR (400 MHz, CDCl3): δ7.65 (d, J = 8.0 Hz, 2H), 7.42 (t, J = 8.0
4
5
Hz, 1H), 7.24 (d, J = 8.0 Hz, 3H), 7.14 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 4.65 (s, 1H), 3.17 (s,
13
6
3H); C NMR (100 MHz, CDCl3): δ169.7, 149.3, 144.5, 132.9, 130.4, 129.0, 123.1, 122.7, 121.6, 120.0,
7
+
108.7, 66.6, 61.9, 26.5; HRMS (ESI): calcd for C17H13F3NO3 [M+H]+: 336.0842, found 336.0840.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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59
60
1-methyl-3'-(4-(trifluoromethoxy)phenyl)spiro[indoline-3,2'-oxiran]-2-one (trans-) (4lb). White solid
1
(22.6 mg, 27%). mp: 148ꢀ149 °C. H NMR (400 MHz, CDCl3): δ7.50 (d, J = 8.0 Hz, 2H), 7.31 (t, J =8.0
Hz, 3H), 6.89 (d, J = 8.0 Hz, 1H), 6.80 (t, J = 8.0 Hz, 1H), 6.42 (d, J = 8.0 Hz, 1H), 4.81 (s, 1H), 3.31 (s,
13
3H); C NMR (100 MHz, CDCl3): δ171.3, 149.3, 145.3, 131.9, 130.4, 128.3, 123.4, 122.5, 120.9, 120.5,
+
108.8, 64.2, 61.6, 26.7; HRMS (ESI): calcd for C17H13F3NO3 [M+H]+: 336.0842, found 336.0845.
3'-(4-(tert-butyl) phenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4ma). Yellowish solid
1
(26.9 mg, 35%). mp: 106ꢀ107 °C. H NMR (400 MHz, CDCl3): δ7.55 (d, J = 8.0 Hz, 2H), 7.43ꢀ7.37 (m,
3H), 7.24 (t, J = 4.0 Hz, 1H), 7.12 (t, J = 8.0 Hz, 1H), 6.89 (d, J = 8.0 Hz, 1H), 4.63 (s, 1H), 3.16 (s, 3H);
1.32 (s, 9H); 13C NMR (100 MHz, CDCl3): δ170.0, 151.6, 144.5, 130.1, 128.7, 127.3, 124.7,123.7, 122.6,
121.5, 108.5, 67.7, 62.1, 34.7, 31.3, 26.5; HRMS (ESI): calcd for C20H22NO2 [M+H]+: 308.1645, found
+
308.1647.
3'-(4-(tert-butyl) phenyl)-1-methylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4mb). Yellowish solid
1
(25 mg, 33%). mp: 75ꢀ76 °C. H NMR (400 MHz, CDCl3): δ7.44ꢀ7.37 (m, 4H), 7.29 (d, J = 8.0 Hz, 1H),
6.87 (d, J = 8.0 Hz, 1H), 6.79 (t, J = 8.0 Hz, 1H), 6.54 (d, J =8.0 Hz, 1H), 4.80 (s, 1H), 3.30 (s, 3H); 1.33
(s, 9 H), 13C NMR (100 MHz, CDCl3): δ171.8, 151.8, 145.2, 130.1, 130.0, 126.4, 125.3, 123.7, 122.4,
121.1, 108.5, 65.2, 61.7, 34.7, 31.3, 26.6; HRMS (ESI): calcd for C20H22NO2 [M+H]+: 308.1645, found
+
308.1650.
1-methyl-3'-(p-tolyl)spiro[indoline-3, 2'-oxiran]-2-one (cis-) (4na). White solid (22.9 mg, 35%). mp:
125ꢀ126 °C. 1H NMR (400 MHz, CDCl3): δ7.50 (d, J = 8.0 Hz, 2H), 7.40 (t, J = 8.0 Hz, 1H), 7.24ꢀ7.11 (m,
4H), 6.90 (d, J = 4.0 Hz, 1H), 4.65 (s, 1H), 3.16 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ170.0, 144.5, 138.6, 130.1, 128.7, 128.4, 127.3, 123.7, 122.6, 121.5, 108.5, 67.6, 61.9, 26.5, 21.4; HRMS
+
(ESI): calcd for C17H16NO2 [M+H]+: 266.1176, found 266.1181.
1-methyl-3'-(p-tolyl)spiro[indoline-3, 2'-oxiran]-2-one (trans-) (4nb). Yellow solid (20.8 mg, 32%).mp:
94ꢀ95 °C. 1H NMR (400 MHz, CDCl3): δ7.34 (d, J = 4.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 1H), 7.21 (d, J = 4.0
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Hz, 2H), 6.87 (d, J = 8.0 Hz, 1H), 6.79 (t, J = 8.0 Hz, 1H), 6.52 (d, J = 8.0 Hz, 1H), 4.79 (s, 1H), 3.30 (s,
1
13
2
3
3H), 2.38 (s, 3H); C NMR (100 MHz, CDCl3): δ171.8, 145.2, 138.5, 130.1, 130.0, 129.1, 126.6, 123.7,
+
122.4, 121.2, 108.5, 65.1, 61.6, 26.6, 21.3; HRMS (ESI): calcd for C17H16NO2 [M+H]+: 266.1176, found
4
5
6
7
266.1179.
8
9
1-methyl-3'-(naphthalen-2-yl)spiro[indoline-3, 2'-oxiran]-2-one（cis-）(4oa). Yellowish solid (44.7 mg,
60 %).mp: 95ꢀ96 °C. 1H NMR (400 MHz, CDCl3): δ7.84 (t, J = 8.0 Hz, 3H), 7.49ꢀ7.42 (m, 4H), 7.35 (t, J
= 8.0 Hz, 1H), 7.20ꢀ7.13 (m, 3H), 4.80 (s, 1H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): δ169.6, 144.8,
135.0, 133.6, 132.0, 130.5, 129.6, 129.4, 128.6, 128.5, 126.5, 125.8, 125.0, 124.6, 123.6, 121.8, 108.7,
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65.5, 59.8, 21.5; HRMS (ESI): calcd for C20H16NO2 [M+H]+: 302.1176, found 302.1178.
1-methyl-3'-(naphthalen-2-yl)spiro[indoline-3, 2'-oxiran]-2-one (trans-) (4ob). White solid (20.1 mg, 27%).mp:
86ꢀ87 °C. 1H NMR (400 MHz, CDCl3): δ7.90ꢀ7.83 (m, 3H), 7.73 (d, J = 8.0 Hz, 1H), 7.58 (t, J = 8.0 Hz, 1H), 7.47ꢀ7.38
(m, 2H), 7.18 (t, J = 8.0 Hz, 1H), 6.82 (d, J = 8.0 Hz, 1H), 6.61 (t, J = 8.0 Hz, 1H), 6.32 (t, J = 8.0 Hz, 1H), 5.26 (s, 1H),
3.34 (s, 3H); 13C NMR (100 MHz, CDCl3): δ171.7, 145.0, 133.1, 130.8, 130.1, 129.3, 129.1, 128.6, 126.6, 126.1, 125.0,
+
124.5, 123.2, 122.7, 122.4, 120.8, 108.5, 64.0, 61.6, 26.7; HRMS (ESI): calcd for C20H16NO2 [M+H]+: 302.1176, found
302.1175.
3'-(methoxymethyl)-1-methylspiro[indoline-3,2'-oxiran]-2-one (4p). White solid (29.4 mg, 54%). mp:
83ꢀ84 °C. 1H NMR (400 MHz, CDCl3): δ7.39ꢀ7.35 (m, 1H), 7.08 (t, J = 4.0 Hz, 2H), 6.89 (d, J = 8.0 Hz,
1H), 4.09 (dd, J = 12.0 Hz, 8.0 Hz, 1H), 4.01ꢀ3.98 (m, 1H), 3.84ꢀ3.82 (m, 1H), 3.45 (s, 3H), 3.25 (s, 3H);
13C NMR (100 MHz, CDCl3): δ170.9, 144.5, 130.3, 123.1, 122.9, 121.8, 108.7, 68.5, 64.3, 59.2, 58.9, 26.6;
HRMS (ESI): calcd for C12H14NO3 [M+H]+: 220.0968, found 220.0969.
+
1,3'-dimethylspiro [indoline-3, 2'-oxiran]-2-one (cis-) (4qa).34, 39 White solid (22.2 mg, 47%). mp:
104ꢀ105 °C. 1H NMR (400 MHz, CDCl3): δ7.38ꢀ7.34 (m, 1H), 7.07 (t, J = 4.0 Hz, 2H), 6.90 (d, J = 8.0 Hz,
1H), 3.76ꢀ3.72 (m, 1H), 3.26 (s, 3H), 1.73 (d, J =8.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ171.6, 144.4,
+
129.9, 124.1, 122.6, 121.5, 108.5, 63.1, 59.6, 26.6, 12.2; HRMS (ESI): calcd for C11H12NO2 [M+H]+:
190.0863, found 190.0864.
1
1, 3'-dimethylspiro [indoline-3, 2'-oxiran]-2-one (trans-) (4qb). Yellow oil (14.8 mg, 32%). H NMR
(400 MHz, CDCl3): δ7.41ꢀ7.38 (m, 1H), 7.19 (d, J =8.0 Hz, 1H), 7.09 (t, J=8.0 Hz, 1H), 6.93 (d, J = 8.0
13
Hz, 1H), 3.76 (dd, J = 12 Hz, 8 Hz, 1H), 3.26 (s, 3H), 1.59 (d, J = 8.0 Hz, 3H); C NMR (100 MHz,
CDCl3): δ172.6, 145.3, 130.0, 124.7, 124.0, 122.5, 108.8, 61.3, 60.5, 26.6, 13.6; HRMS (ESI): calcd for
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C11H12NO2 [M+H]+: 190.0863, found 190.0866.
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1-methylspiro [indoline-3, 2'-oxiran]-2-one (4r).34, 36 Yellow solid (40.01 mg, 92%). mp: 84ꢀ86°C. H
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3
4
5
NMR (400 MHz, CDCl3): δ7.37 (t, J= 8.0 Hz, 1H), 7.10ꢀ7.05 (m, 2H), 6.91 (d, J = 8.0 Hz, 1H), 3.57 (d, J
13
6
7
= 4.0 Hz, 1H), 3.42 (d, J = 8.0 Hz, 1H), 3.26 (s, 3H); C NMR (100 MHz, CDCl3): δ171.7, 145.0, 130.3,
122.8, 122.6, 122.0, 108.8, 56.3, 54.0, 26.6; HRMS (ESI): calcd for C10H9NO2Na+ [M+Na]+, 198.0525,
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found 198.0525.
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1, 3', 3'-trimethylspiro[indoline-3,2'-oxiran]-2-one (4s). White solid (12.2 mg, 48 %). mp: 85ꢀ86 °C. H
NMR (400 MHz, CDCl3): δ 7.37 (t, J = 8.0 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 7.08ꢀ7.05 (m, 1H), 6.90 (d, J
= 8.0 Hz, 1H), 3.25 (s, 3H), 1.77 (s, 3H), 1.62 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 172.9, 145.0, 129.6,
124.5, 123.4, 122.1, 108.4, 66.7, 64.8, 26.6, 21.1, 18.6. HRMS (ESI): calcd for C12H14NO2 [M+H]+:
+
204.1019, found 204.1017.
2-(4-nitrophenyl)-3-phenyl-oxirane（cis-）(7aa). White solid (13.6 mg, 23%). mp: 123ꢀ125 °C. 1H NMR
(400 MHz, CDCl3): δ 8.03 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.18 (t, J = 4.0 Hz, 5H), 4.46 (d, J
= 4.0 Hz, 1H), 4.41 (d, J = 4.0 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 147.3, 142.0, 133.2, 128.0, 128.0,
127.6, 126.6, 123.0, 60.0, 58.8. MS, m/z: 241.0. Anal. Calcd for C14H11NO3: C, 69.70; H, 4.60; N, 5.81;
O, 19.90. Found C, 69.72; H, 4.61; N, 5.82; O, 19.92.
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2-(4-nitro-phenyl)-3-phenyl-oxirane (trans-) (7ab). Colorless oil (36.7 mg, 61%). H NMR (400 MHz,
CDCl3): δ 8.24 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.41ꢀ7.35 (m, 5H), 3.99 (s, 1H), 3.87 (s, 1H).
13C NMR (100 MHz, CDCl3): δ 147.8, 144.4, 136.0, 128.8, 128.7, 126.2, 125.5, 123.8, 63.3, 61.6. MS, m/z:
241.1.
2-(2-nitrophenyl)-3-phenyloxirane (7b).40 Yellow solid (38.8 mg, 65%). mp: 95ꢀ96 °C. H NMR (400
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MHz, CDCl3): δ 8.17 (d, J = 8.0 Hz, 1H), 7.72(d, J=8.0 Hz, 2H), 7.51 (t, J = 8.0 Hz, 1H), 7.39 (d, J=8.0
Hz, 5H), 4.51 (s, 1H), 3.80 (s, 1H). 13C NMR (100 MHz, CDCl3): δ 136.1, 134.3, 133.9, 130.3, 128.6,
+
+
128.6, 127.0, 125.8, 124.7, 120.4, 62.2, 59.9. HRMS (ESI): calcd for C14H12NO3 [M+H] : 242.0812,
found 242.0806.
Methyl 4-(3-phenyloxiran-2-yl)benzoate (cis-) (7ca).37 White solid (12 mg, 19%). mp: 85ꢀ86 °C. H
1
NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.0 Hz, 2H), 7.24 (s, 2H), 7.15 (s, 5H), 4.40 (d, J = 4.0 Hz, 1H),
13
4.37 (d, J = 4.0 Hz, 1H), 3.83 (s, 3H). C NMR (100 MHz, CDCl3) δ 166.7, 139.6, 133.7, 129.3, 129.0,
127.8, 127.7, 126.7, 126.7, 59.8, 59.3, 52.0. HRMS (ESI): calcd for C16H15O3 [M+H]+: 255.1016, found
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Methyl 4-(3-phenyloxiran-2-yl)benzoate (trans-) (7cb). White solid (42.6 mg, 67%). mp: 87ꢀ88 °C. H
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4
5
NMR (400 MHz, CDCl3): δ 8.06 (d, J = 8.0 Hz, 2H), 7.43ꢀ7.34 (m, 7H), 3.93 (s, 4H), 3.87 (s, 1H). C
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8
9
NMR (100 MHz, CDCl3): δ 166.7, 142.2, 136.6, 130.0, 129.8, 128.6, 128.5, 125.5, 125.4, 63.0, 62.2, 52.1.
MS, m/z: 254.1. Anal. Calcd for C16H14O3: C, 75.57; H, 5.55; O, 18.88. Found C, 75.59; H, 5.56; O, 18.92.
1-bromo-6-(3-phenyloxiran-2-yl) pyridine (7d). White oil (29.6 mg, 43%). 1H NMR (400 MHz, CDCl3):
δ 7.58 (t, J = 8.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.39ꢀ7.29 (m, 6H), 4.05 (s, 1H), 3.98 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 158.2, 141.8, 139.2, 136.0, 128.6, 128.5, 127.6, 125.7, 118.3, 62.2, 62.1. HRMS
(ESI): calcd for C13H11BrNO+[M+H]+: 276.0024, 277.0058, 278.0004, 279.0037, found 276.0021,
277.0051, 278.0003, 279.0031.
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2-(4-iodophenyl)-3-phenyloxirane (cis-) (7e). White oil (41.7 mg, 52%). H NMR (400 MHz, CDCl3): δ
7.50 (d, J = 8.0 Hz, 2H), 7.21ꢀ7.15 (m, 5H), 6.91 (d, J = 8.0 Hz, 2H), 4.36 (d, J = 4.0 Hz, 1H), 4.28 (d, J =
13
4.0 Hz, 1H). C NMR (100 MHz, CDCl3): δ 136.8, 134.1, 133.9, 128.7, 127.9, 127.7, 126.7, 93.2, 59.7,
59.2. MS, m/z: 322.1. Anal. Calcd for C14H11IO: C, 52.20; H, 3.44; O, 4.97. Found C, 52.21; H, 3.40; O,
4.96.
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3-(3-phenyloxiran-2-yl) benzonitrile (7f). Yellow solid (32.2 mg, 59 %). mp: 88ꢀ89 °C. H NMR (400
MHz, CDCl3): δ 7.64ꢀ7.58 (m, 3H), 7.50 (t, J = 8.0 Hz, 1H), 7.40–7.33 (m, 5H), 3.91 (s, 1H), 3.83 (s, 1H).
13C NMR (100 MHz, CDCl3): δ 138.8, 136.1, 131.8, 129.8, 129.4, 129.0, 128.7, 128.7, 125.5, 118.5, 112.9,
63.1, 61.5. MS, m/z: 221.1. Calcd for C15H11NO: C, 81.43; H, 5.01; N, 6.33; O, 7.23. Found C, 81.46; H,
5.03; N, 6.34; O, 7.26.
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ASSOCIATED CONTENT
Supporting Information
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The Supporting Information is available free of charge on the ACS Publications website at DOI: XXXX
1H, 13C NMR and MS spectra for products 4 and 7.
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HMQC and 2D 1Hꢀ1H NOESY spectra for products 4aa, 4ab, 4ca, 4cb, 7aa, 7ab, 7ca and 7cb.
AUTHOR INFORMATION
Corresponding Authors
*Eꢀmail: clare2006@163.com.
*Eꢀmail: wangbin@nankai.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We gratefully acknowledge the Natural Science Foundation of China (NSFC) (Grant Nos. 21172120 and
21472093), Tianjin Municipal Science and Technology Commission (No. 14JCYBJC20600) and National
University Student Innovation Program (No. 201510055118) for the funding support.
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