One-pot synthesis of cyclopropane derivatives with a cis : Trans stereoselectivity by Wittig olefination-sulfur ylide cyclopropanation sequence

Article abstract of DOI:10.3184/174751913X13692098347208

Cyclopropane derivatives were synthesised in one pot from aromatic aldehydes, phenacyltriphenylphosphonium bromide, and S-phenacylthiolanium bromide by a Wittig olefination-sulfur ylide cyclopropanation sequence. When Cs2CO3 was used as the base and CH3CN/water (8:2, v/v) as the solvent, the major product was the cis-1,2-dibenzoyl cyclopropane. In contrast, when using DBU as the base and MeOH as the solvent, the major product was transdibenzoyl cyclopropane. In some cases, the major isomer was obtained in high purity and good yield by simple filtration.

Full text of DOI:10.3184/174751913X13692098347208

380 RESEARCH PAPER
JUNE, 380–384
JOURNAL OF CHEMICAL RESEARCH 2013
One-pot synthesis of cyclopropane derivatives with a cis:trans stereo-
selectivity by Wittig olefination-sulfur ylide cyclopropanation sequence
Wenhua Huang* and Lai-Ling Wang
Department of Chemistry, Tianjin University, Tianjin 300072, P. R. China
Cyclopropane derivatives were synthesised in one pot from aromatic aldehydes, phenacyltriphenylphosphonium
bromide, and S-phenacylthiolanium bromide by a Wittig olefination-sulfur ylide cyclopropanation sequence. When
Cs2CO3 was used as the base and CH3CN/water (8:2, v/v) as the solvent, the major product was the cis-1,2-dibenzoyl
cyclopropane. In contrast, when using DBU as the base and MeOH as the solvent, the major product was trans-
dibenzoyl cyclopropane. In some cases, the major isomer was obtained in high purity and good yield by simple
filtration.
Keywords: Wittig olefination, cyclopropanation, sulfur ylide, phosphorus ylide, stereoselectivity, cyclopropanation, cyclopropane
Cyclopropanes are not only found in a wide range of naturally
occurring compounds1 but have also been used as versatile
synthetic intermediates in organic chemistry.2 Three major
methods have been developed for the synthesis of cyclopro-
panes: (1) Simmons–Smith cyclopropanation, (2) transition
metal-catalysed decomposition of diazoalkanes, and (3)
Michael-initiated ring closure.3,4 As an example of the third
method, the reaction of a sulfur ylid with an α,β-unsaturated
carbonyl compound to afford a cyclopropane, i.e., sulfur ylide
cyclopropanation, has recently attracted interest.4–13 The α,β-
unsaturated carbonyl component is readily prepared via the
reaction of a stabilised phosphorus ylide with an aldehyde or a
ketone, i.e., Wittig olefination.14 A one-pot synthesis, in which
two or more reactions are combined into a single pot without
isolation of intermediatesis often considered for economic
reasons.15 Therefore, we examined the possibility that a
Wittig olefination and sulfur ylide cyclopropanation might be
combined into one pot. In fact, Taylor and co-workers have
reported16,17 a combination of oxidation, Wittig olefination,
and sulfur ylide cyclopropanation to synthesise functionalised
cyclopropanes starting from α-hydroxyketones. However, this
three-reaction sequence is restricted to α-hydroxyketones, or
highly activated α-keto aldehydes for the Wittig-sulfur ylide
cyclopropanation sequence. Applying the Wittig-sulfur ylide
cyclopropanation sequence starting from a typical aldehyde in
order to synthesise cyclopropane derivatives is still a chal-
lenge. We now report a one-pot synthesis of cyclopropane 7
starting from an aromatic aldehyde 1, phosphonium salt 2,
and sulfonium salt 3 by the sequence of Wittig olefination (via
ylide 4)-sulfur ylide cyclopropanation (via ylide 6), as shown
Scheme 1, with a controllable cis:trans steroselectivity.
This is particularly the case for aldehydes, which undergo
Wittig olefination more slowly than an α-keto aldehyde.
Among sulfur ylides, dimethylsulfonium phenacylid has been
reported not to give an epoxide when it was treated with
an aldehyde or a ketone but it did react with α,β-unsaturated
carbonyl compounds to give cyclopropane derivatives.23
Therefore, we chose benzaldehyde 1a, phenacyltriphenylphos-
phonium bromide 2, and S-phenacylthiolanium bromide 3
as model compounds to explore the Wittig-sulfur ylide cyclo-
propanation sequence.
When equal moles of 1a, 2, and 3 were stirred in CH3CN in
the presence of DBU (2 equiv.) at room temperature for two
days, we observed the formation of cyclopropane 7a with a
high cis:trans ratio of 95:5, albeit in a low yield (Table 1,
entry1). The stereochemistry of 7a was assigned by comparing
1
1
its H NMR with the literature data.24 The H NMR spectra
of cis-7a exhibited two peaks at 3.42 (d, J = 6.2 Hz, 2H), and
3.58 (t, J = 6.2 Hz, 1H), which corresponded to the protons on
the cyclopropane ring and are in agreement with those
reported:24 3.31 (d, J = 6.0 Hz, 2H), and 3.47 (t, J = 6.0 Hz,
1H). The cyclopropane ring protons of trans-7a appeared as
three double doublets at 3.59, 3.81 and 4.28, respectively, with
coupling constants being 4.8, 6.2, and 10.0 Hz, also in good
agreement with those reported:24 3.47 (dd, J = 6.0, 10 Hz, 1H),
3.69 (dd, J = 5.0, 10.0 Hz, 1H), 4.17 (dd, J = 5.0, 6.0, 1H). The
low yield of 7a might be due to the slow rate of Wittig olefina-
tion, which would lead to the deterioration of the sulfonium
salt 3 and a termination of the following cyclopropanation.
Bergdahl and co-workers have reported25 that water or metha-
nol can promote Wittig olefination. This encouraged us to add
some water to our reaction system. We found that by using a
9:1 mixture of CH3CN/water as the solvent, the yield of cyclo-
propane 7a dramatically increased to 62% with the almost
same cis:trans ratio (Table 1, entry 2). On increasing the
amount of DBU that was used to 2.5 equiv, the yield of 7a
increased slightly to 68% but the stereoselectivity was inverted
to a cis:trans ratio of 26:74 (Table 1, entry 3). On further
increasing the amount of DBU to 3 equiv., both the yield of 7a
and the cis:trans stereoselectivity remained almost the same
(Table 1, entry 4). Screening other bases showed that K2CO3
gave 7a in 71% yield with a high stereoselectiviy in favour of
cis-isomer but DABCO gave 7a in a low yield and a slightly
lower stereoselectivity (Table, entries 5 and 6). Using Cs2CO3
as the base, the yield of 7a slightly increased to 74%; reducing
the quantity of solvent that was used and further increasing the
quantity of water and reaction time increased the yield of 7a to
86% with the same cis:trans ratio of 89:11 (Table, entries
7–10). Because the cis:trans stereoselectivity was inverted in
case of DBU as base, we tried to further enhance this inverted
stereoselectivity. We found that the cis:trans ratio approached
10:90 and the yield of 7a also increased to 76% when using
MeOH to replace CH3CN/water as solvent (Table, entry 11 vs
To make the Wittig-sulfur ylide cyclopropanation sequence
viable, the obstacle that sulfur ylides are known to react with
aldehydes to form epoxides18–22 must be overcome. Epoxida-
tion via a sulfur ylide would compete with Wittig olefination to
terminate the Wittig-sulfur ylide cyclopropanation sequence.
Scheme 1
* Correspondent. E-mail: huangwh@tju.edu.cn

JOURNAL OF CHEMICAL RESEARCH 2013 381
Table 1 Optimisation of reaction conditionsa
Entry
Base/equiv.
Solvent
Time/days
Yield/%b
cis:transc
1
2
DBU (2)
DBU (2)
CH3CN
2
2
2
2
2
2
2
2
2
3
2
2
3
35
62
68
67
71
32
74
73
79
86
76
84
89
95:5
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)
CH3CN/water (9:1, v/v)d
CH3CN/water (8:2, v/v)d
CH3CN/water (8:2, v/v)d
CH3OH
93:7
3
DBU (2.5)
DBU (3.0)
K2CO3 (2.5)
DABCO (2.5)
Cs2CO3 (2.5)
Cs2CO3 (2.5)
Cs2CO3 (2.5)
Cs2CO3 (2.5)
DBU (2.5)
DBU (2.5)
DBU (2.5)
26:74
22:78
92:8
4
5
6
87:13
89:11
89:11
89:11
89:11
10:90
8:92
7
8
9
10
11
12
13
CH3OHd
CH3OHd
7:93
a Reaction condition: 1a (0.47 mmol), 2 (0.47 mmol), 3 (0.47 mmol), base, solvent (5 mL), rt. b The total yield of cis-7a and trans-7a.
c cis and trans refer to the configuration of the two benzoyl groups. d Total volume: 2 mL.
entry 3). By reducing the quantity of MeOH to 2 mL, and
performing the reaction for 2 days and 3 days gave 7a in 84%
and 89% yields, respectively, with the high stereoselectivities
in favour of trans-isomer (Table 1, entries 12 and 13).
After screening, we obtained two sets of optimised reaction
conditions with inverse stereoselectivities: (a) Cs2CO3 (2.5
equiv.), CH3CN/water (8:2, v/v), 3 days, affording the cis-
isomer, and (b) DBU (2.5 equiv.), MeOH, 3 days, affording the
trans-isomer.
At first, we applied the condition a to a range of aldehydes,
whose structures are shown in Scheme 2. As shown in Table 2,
for benzaldehydes with an electron-withdrawing group at the
para position gave the desired cyclopropane products in good
to excellent yields, with cis:trans ratios in the range of 78:22 to
88:12 (entries 2, and 4–6). For ortho-chlorobenzaldehyde 1c,
the corresponding cyclopropane product 7c was obtained in a
lower yield (entry 3) but the ortho nitro and the meta nitro
benzaldehydes still gave cyclopropanes 7g and 7h in high yield
and stereoselectivity (entries 7 and 8). Introducing a methyl
group at the para position of benzaldehyde still gave the cyclo-
propane product in good yield, but introducing one methoxy
group or two methoxy groups dramatically reduced the yield
of the cyclopropane product, though the cis:trans ratio in case
of 3,4-dimethoxybenzaldehyde 1l increased to 92:8 (entries
9–12). For 1-naphthaldehyde 1m, and the heteroaromatic
aldehydes 1n and 1o, the cyclopropane products were obtained
in good yields (entries 13–15), with the highest cis:trans ratio
in case of 1m. For α-keto aldehyde 1p, the corresponding
cyclopropane product was obtained in 66% yield. Furthermore,
in 10 examples, the major isomer (cis-7) precipitated from
the mixture after the reaction, and so it could be isolated as a
pure product by simple filtration. The filtration yield ranges
from 44 to 79%, just slightly lower, in most cases, than the
corresponding total yield of cis-7.
Then we applied the optimised conditon b to the same set
of aldehydes, and the results are summarised in Table 3. For
benzaldehydes with an electron-withdrawing group, the yields
of 7 were good to excellent but the stereoselectivity was
inverted in favour of trans-isomer with the cis:trans ratios
being 7:93 to 0:100, except for 1g, which gave 7g in a moder-
ate yield (entries 1–8). For benzaldehydes with one or two
electron-donating groups, 4-methylbenzaldehyde 1i gave 7i in
good yield and high stereoselectivity (entry 9), but others gave
7 in lower yields (entries 10–12). Aldehyde 1k gave 7k only
in 41% yield, and the stereoselectivity was partially inverted
but still favouring the cis-isomer (entry 11). Other aromatic
Table 2 One-pot synthesis of cyclopropanes using Cs2CO3
Entry
1
7
Yield/%a
cis-7b
cis:trans
7c
1
2
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
1p
7a
7b
7c
7d
7e
7f
7g
7h
7i
7j
7k
7l
7m
7n
7o
7p
76
86
99
66
92d
94
89
88
96
80
49
38
54
85
86
83
65
89:11
88:12
79:21
79:21
88:12
78:22
85:15
90:10
89:11
88:12
87:13
92:8
87 (79)
52 (44)
73 (72)
83 (71)
70 (54)
75 (52)
86 (55)
71 (64)
43
3
4
5
6
7
8
9
10
11
12
13
14
15
16
33
49
81 (58)
68
96:4
79:21
66e
79:21e
f
65 (62)
-
a Isolated yield except that specified. Reaction conditions:1
(0.47 mmol), 2 (0.47 mmol), 3 (0.47 mmol), Cs2CO3 (1.18 mmol),
CH3CN/water (8:2, v/v, 2 mL), rt, 3 d. b The number in parenthe-
sis is the yield by filtration after reaction. c The total yield of
cis-7 and trans-7. d The reaction was run for one day. e The NMR
yield and ratio. f Only one isomer was obtained.
Scheme 2 Stuctures of aldehydes used.

382 JOURNAL OF CHEMICAL RESEARCH 2013
Table 3 One-pot synthesis of cyclopropanes using DBU
Experimental
1H NMR spectra were recorded on a Mercury Plus 400 NMR spec-
trometer. IR spectra were recorded on a Thermo Nicolet Avatar 360 IR
spectrometer. Electrospray ionisation mass spectra were obtained on
an LCQ Advantage MAX (Finnigan) instrument. All melting points
were measured on a melting apparatus with microscope and hot stage
and were uncorrected. All reactions were carried out under N2. Phena-
cyltriphenylphosphonium bromide 2 was prepared using the reported
method.26 Other reagents were purchased from a local company
and used as received. S-Phenacylthiolanium bromide 3 is a known
compound.27 The stereochemistry of the product 7 was evaluated by
1H NMR and those of 7a, 7b, 7d, 7i, and 7j are in agreement with
those reported.24 PE = petroleum ether (b.p. 60–90 °C).
Entry
1
7
Yield/%a
trans-7b
cis:trans
7c
1
2
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
1p
7a
7b
7c
7d
7e
7f
7g
7h
7i
7j
7k
7l
7m
7n
7o
7p
82 (67)
88 (81)
89 (73)
91 (86)
87 (66)
89 (83)
54
89
90
91
94
93
89
54
83
85
72
41
75
87
76
84
30
7:93
2:98
3
3:97
4
3:97
6:94
0:100
1:99
3:97
2:98
5
6
Synthesis of S-phenacylthiolanium bromide (3)
7
8
81 (71)
83 (75)
62
2-Bromoacetophenone (11.3 g, 57 mmol) was added to a solution of
tetrahydrothiophene (5.0 g, 57 mmol) in acetone (20 mL). The mix-
ture was stirred at room temperature for 3h, and the white solids were
collected by filtration, washed with acetone (3 × 5 mL), and dried
under reduced pressure to give the product 3 (14.0 g, 85% yield). 1H
NMR (400 MHz, DMSO-d6) δ 2.19–2.25 (m, 2H), 2.28–2.34 (m,
2H), 3.60–3.68 (m, 4H), 5.58 (s, 2H), 7.59–7.64 (m, 2H), 7.74–7.79
(m, 1H), 8.04 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, DMSO-d6)
δ 28.8, 43.2, 52.9, 129.2, 129.5, 134.5, 135.3, 192.6.
9
10
11
12
13
14
15
16
14:86
63:37
15:85
27:73
17:83
75:25d
15
63
63
63
63d
e
30 (30)
–
a Isolated yield except that specified. Reaction conditions: 1
(0.47 mmol), 2 (0.47 mmol), 3 (0.47 mmol), DBU (1.18 mmol),
MeOH (2 mL), rt, 3 d. b The number in parenthesis is the yield by
filtration after reaction. c The total yield of cis-7 and trans-7.
d The NMR yield and ratio. e Only one isomer was obtained.
Synthesis of cyclopropane derivatives using Cs2CO3 as base; general
procedure
The aldehyde 1 (0.47 mmol), phosphonium salt 2 (0.47 mmol), sulfo-
nium salt 3 (0.47 mmol), Cs2CO3 (1.18 mmol), CH3CN (1.6 mL) and
water (0.4 mL) was sequentially added to a round-bottom flask
(50 mL). The mixture was then stirred at room temperature for 3 days
and the precipitate was collected by filtration, washed with cold meth-
anol (3 × 1 mL), and dried under reduced pressure to give most of
the major product. The filtrate and washes were evaporated, and the
residue was purified by preparative TLC to give the minor product and
the rest of the major product. In the case where there was no or little
precipitate, the reaction mixture was evaporated, and the residue was
purified by preparative TLC to give the major and minor products.
aldehydes, including 1-nathpthaldehyde 1m, and 2-furfural
1n, and 2-pyridinealdehyde 1o also gave good yields of
the desired cyclopropanes but with lower stereoselectivities
(entries 13–15). For the α-keto aldehyde 1p, the cyclopropane
product 7p was obtained in a low yield (entry 16). In nine
examples, the cyclopropane products, most of which were
from aldehydes with an electron-withdrawing group, precipi-
tated from the reaction mixture and could be isolated by simple
filtration. Attempts to expand this reaction sequence to
aliphatic aldehydes or by using a combination of other phos-
phonium salts and other sulfonium salts were unsuccessful,
whether using the optimised condition a or b. As for the altered
cis:trans stereoselectivity when using the optimised condition
b, we reasoned that the initially formed cyclopropane product
was a cis-isomer, and in the presence of an excess of DBU it
was isomerised to the trans-isomer. In order to confirm this
explanation, we carried out a control experiment by mixing
cis-7a with 0.5 equiv of DBU, and stirred it at room tempera-
ture for 3 days. We found that 70% of the cis-7a was inverted
to the thermodynamically more stable trans-7a probably due
to deprotonation by DBU followed by the reconfiguration, as
shown in Scheme 3. Although Cs2CO3 is also in excess in the
optimised condition a, the product cis-7a was not inverted
to trans-7a probably due to the weaker basicity of Cs2CO3
compared to that of DBU.
Synthesis of cyclopropane derivatives using DBU as base; general
procedure
The aldehyde 1 (0.47 mmol), phosphonium salt 2 (0.47 mmol), sulfo-
nium salt 3 (0.47 mmol), DBU (1.20 mmol), and methanol (2 mL) was
sequentially added to a round-bottom flask (50 mL). The mixture was
stirred at room temperature for 3 days. The reaction was then worked
up according to the same procedure as described above.
(3-Phenylcyclopropane-1,2-diyl)bis(phenylmethanone) (7a): cis-
7a: white solid, m.p. 148–150 °C (lit.24 148–150 °C). IR (KBr) 1652
(C=O), 1684 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.42 (d, J =
6.2 Hz, 2H), 3.58 (t, J = 6.2 Hz, 1H), 7.30–7.36 (m, 3H), 7.38–7.41
(m, 2H), 7.43–7.48 (m, 4H), 7.54–7.58 (m, 2H), 8.01–8.04 (m, 4H).
13C NMR (100 MHz, CDCl3) δ 31.3, 36.9, 126.6, 127.3, 128.4, 128.6,
128.9, 133.2, 137.2, 138.5, 194.3. ESI-HRMS (positive): calcd for
C23H18NaO2+ [M+Na]+ 349.1199; found, 349.1196. Anal. Calcd for
C23H18O2: C, 84.64; H, 5.56. Found: C, 84.64; H, 5.72%. trans-7a:
White solid, m.p. 120–122 °C (lit.24 115–117 °C). IR (KBr) 1655
1
(C=O) cm−1. H NMR (400 MHz, CDCl3) δ 3.59 (dd, J1 = 6.2 Hz,
J2 = 10.0 Hz, 1H), 3.81 (dd, J1 = 4.8 Hz, J2 = 10.0 Hz, 1H), 4.28 (dd,
J1 = 4.8 Hz, J2 = 6.2 Hz, 1H), 7.19–7.30 (m, 5H), 7.45–7.50 (m, 2H),
7.54–7.60 (m, 3H), 7.63–7.68 (m, 1H), 8.02 (d, J = 7.6 Hz, 2H), 8.19
(d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 29.8, 37.5, 38.0,
127.3, 128.29, 128.34, 128.5, 128.6, 128.77, 128.81, 133.2, 133.6,
134.4, 137.1, 137.5, 193.7, 197.4. ESI-HRMS (positive): calcd for
C23H18NaO2+ [M+Na]+ 349.1199; found, 349.1198. Anal. Calcd for
C23H18O2: C, 84.64; H, 5.56. Found: C, 84.75; H, 5.47%.
(3-(4-Chlorophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7b): cis-7b: White solid, m.p. 169–174 °C (lit.24 158–160 °C). IR
(KBr) 1657 (C=O), 1681 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ
3.39 (d, J = 6.2 Hz, 2H), 3.55 (t, J = 6.2 Hz, 1H), 7.25–7.29 (m, 2H),
7.35–7.38 (m, 2H), 7.43–7.47 (m, 4H), 7.54–7.59 (m, 2H), 7.99–8.02
(m, 4H). 13C NMR (100 MHz, DMSO-d6) δ 30.3, 37.7, 128.6, 128.9,
129.07, 129.11, 131.9, 133.8, 137.1, 138.4, 194.3. ESI-HRMS (posi-
tive): calcd for C23H17ClNaO2+ [M+Na]+ 383.0809; found, 383.0812.
trans-7b: White solid, m.p. 143–144 °C (lit.24 140–141 °C). IR (KBr)
1659 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.55 (dd, J1 = 6.4 Hz,
J2 = 10.0 Hz, 1H), 3.80 (dd, J1 = 5.0 Hz, J2 = 10.0 Hz, 1H), 4.23 (dd,
In conclusion, we have demonstrated a tandem reaction of
Wittig olefination-sulfur ylide cyclopropanation starting from
aromatic aldehydes can efficiently afford cyclopropane deriva-
tives in one pot. By choosing a different base and solvent, the
stereoselectivity of this reaction can be controlled. Our proto-
col is performed at room temperature, and some cyclopropane
products can even be isolated by simple filtration, so providing
a facile and efficient access to cyclopropane derivatives.
Scheme 3

JOURNAL OF CHEMICAL RESEARCH 2013 383
J1 = 5.0 Hz, J2 = 6.4 Hz, 1H), 7.20–7.23 (m, 4H), 7.46–7.51 (m, 2H),
7.54–7.61 (m, 3H), 7.63–7.68 (m, 1H), 8.01 (d, J = 7.2 Hz, 2H), 8.17
(d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 29.9, 37.0, 37.3,
128.3, 128.5 (overlap, 2C), 128.7, 128.9, 130.1, 132.9, 133.2, 133.4,
133.7, 137.0, 137.4, 193.5, 197.0. ESI-HRMS (positive): calcd for
C23H17ClNaO2+ [M+Na]+ 383.0809; found, 383.0808.
(3-(2-Nitrophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7g): cis-7g: White solid, m.p. 176–177 °C. IR (KBr) 1678 (C=O)
1
cm−1. H NMR (400 MHz, CDCl3) δ 3.44 (d, J = 6.4 Hz, 2H), 4.02
(t, J = 6.4 Hz, 1H), 7.39–7.44 (m, 4H), 7.47–7.56 (m, 4H), 7.61–7.66
(m, 1H), 7.96–8.02 (m, 5H). 13C NMR (100 MHz, CDCl3) δ 28.9,
35.2, 125.0, 128.3, 128.5, 128.6, 129.5, 133.2, 133.3, 133.4, 137.0,
150.4, 193.5. ESI-HRMS (positive): calcd for C23H17NNaO4+ [M+Na]+
394.1050; found, 394.1056. trans-7g: White solid, m.p. 123–124 °C.
IR (KBr) 1658 (C=O), 1678 (C=O) cm−1. 1H NMR (400 MHz, CDCl3)
δ 3.95 (dd, J1 = 6.4 Hz, J2 = 10.0 Hz, 1H), 3.99 (dd, J1 = 5.0 Hz,
J2 = 10.0 Hz, 1H), 4.21 (dd, J1 = 5.0 Hz, J2 = 6.4 Hz, 1H), 7.40–7.51
(m, 3H), 7.54–7.63 (m, 5H), 7.64–7.69 (m, 1H), 7.94 (d, J = 8.0 Hz,
1H), 8.03 (d, J = 7.2 Hz, 2H), 8.16 (d, J = 8.4 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 31.7, 35.8, 36.4, 124.8, 128.4 (overlap, 2C),
128.5, 128.7, 128.9, 130.2, 132.0, 132.9, 133.6, 133.8, 136.8, 136.9,
149.8, 194.2, 196.2. ESI-HRMS (positive): calcd for C23H17NNaO4+
[M+Na]+ 394.1050; found, 394.1054.
(3-(2-Chlorophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7c): cis-7c: White solid, m.p. 159–162 °C. IR (KBr) 1655 (C=O),
1678 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.41 (d, J = 6.4 Hz,
2H), 3.81 (t, J = 6.4 Hz, 1H), 7.27–7.30 (m, 3H), 7.42–7.47 (m, 5H),
7.53–7.58 (m, 2H), 8.03 (d, J = 7.6 Hz, 4H). 1 H NMR (400 MHz,
CDCl3). 13C NMR (100 MHz, CDCl3) δ 29.8, 35.5, 127.0, 127.7,
128.4, 128.6, 128.7, 129.8, 133.2, 135.9, 136.2, 137.2, 194.1. MALDI-
HRMS (positive): calcd for C23H17ClNaO2+ [M+Na]+ 383.0809; found,
383.0812. trans-7c: White solid, m.p. 110–112 °C. IR (KBr) 1659
1
(C=O) cm−1. H NMR (400 MHz, CDCl3) δ 3.67 (dd, J1 = 6.6 Hz,
J2 = 9.6 Hz, 1H), 3.95 (dd, J1 = 4.6 Hz, J2 = 9.6 Hz, 1H), 4.25 (dd,
J1 = 4.6 Hz, J2 = 9.6 Hz, 1H), 7.16–7.21 (m, 1H), 7.23–7.31 (m, 1H),
7.29 (d, J = 8.0 Hz, 1H), 7.37 (d, J = 7.6 Hz, 1H), 7.45–7.50 (m, 2H),
7.54–7.60 (m, 3H), 7.63–7.68 (m, 1H), 8.07 (d, J = 7.2Hz, 2H), 8.19
(d, J = 7.2 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 30.7, 36.4, 36.5,
126.4, 128.50, 128.54, 128.57, 128.65, 128.8, 129.3, 130.5, 132.3,
133.3, 133.6, 135.6, 137.0, 137.3, 193.8, 196.9. ESI-HRMS (posi-
tive): calcd for C23H17ClNaO2+ [M+Na]+ 383.0809; found, 383.0809.
(3-(4-Bromophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7d): cis-7d: White solid, m.p. 174–176 °C (lit.24 170–172 °C). IR
(KBr) 1656 (C=O), 1680 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ
3.39 (d, J = 6.0 Hz, 2H), 3.53 (t, J = 6.0 Hz, 1H), 7.21 (d, J = 8.2 Hz,
2H), 7.43–7.47 (m, 4H), 7.52 (d, J = 8.2 Hz, 2H), 7.54–7.59 (m, 2H),
8.00 (d, J = 7.6 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ 30.4, 36.8,
121.0, 128.29, 128.34, 128.6, 132.0, 133.3, 137.0, 137.6, 193.9. ESI-
HRMS (positive): calcd for C23H17BrNaO2+ [M+Na]+ 427.0304; found,
427.0308. trans-7d: White solid, m.p. 163–165 °C (lit.24 161–163 °C).
IR (KBr) 1655 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.53 (dd,
J1 = 6.4 Hz, J2 = 9.6 Hz, 1H), 3.80 (dd, J1 = 5.0 Hz, J2 = 9.6 Hz, 1H),
4.23 (dd, J1 = 5.0 Hz, J2 = 6.4 Hz, 1H), 7.15 (d, J = 8.2 Hz, 2H), 7.37
(d, J = 8.2 Hz, 2H), 7.46–7.51 (m, 2H), 7.54–7.61 (m, 3H), 7.64–7.68
(m, 1H), 8.01 (d, J = 7.2 Hz, 2H), 8.17 (d, J = 7.2 Hz, 2H). 13C NMR
(100 MHz, DMSO-d6) δ 29.3, 36.0, 37.5, 120.7, 128.66, 128.74,
129.3, 129.4, 131.3, 131.5, 134.0, 134.2, 134.4, 137.0, 137.4, 193.5,
196.5. ESI-HRMS (positive): calcd for C23H17BrNaO2+ [M+Na]+
427.0304; found, 427.0306.
(3-(3-Nitrophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7h): cis-7h: White solid, m.p. 169–172 °C. IR (KBr) 1682 (C=O)
1
cm−1. H NMR (400 MHz, CDCl3) δ 3.52 (d, J = 6.0 Hz, 2H), 3.70
(t, J = 6.0 Hz, 1H), 7.43–7.48 (m, 4H), 7.55–7.60 (m, 3H), 7.74 (d,
J = 7.6 Hz, 1H), 8.01 (d, J = 7.6 Hz, 4H), 8.14 (s, 1H), 8.18 (d, J =
8.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 29.9, 37.0, 120.6, 122.2,
128.4, 128.7, 129.8, 133.5, 133.7, 136.8, 140.9, 148.7, 193.3. ESI-
HRMS (positive): calcd for C23H17NNaO4+ [M+Na]+ 394.1050; found,
394.1055. trans-7h: White solid, m.p. 137–139 °C. IR (KBr) 1659
1
(C=O) cm−1. H NMR (400 MHz, CDCl3) δ 3.67 (dd, J1 = 6.4 Hz,
J2 = 9.8 Hz, 1H), 3.85 (dd, J1 = 4.8 Hz, J2 = 9.8 Hz, 1H), 4.31 (dd,
J1 = 4.8 Hz, J2 = 6.4 Hz, 1H), 7.40–7.45 (m, 1H), 7.46–7.51 (m, 2H),
7.55–7.62 (m, 4H), 7.65–7.69 (m, 1H), 8.00 (d, J = 7.6 Hz, 2H), 8.06
(d, J = 8.4 Hz, 1H), 8.18 (d, J = 6.8 Hz, 2H), 8.18 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ 30.0, 36.4, 37.0, 122.4, 124.0, 128.3, 128.5,
128.8, 128.9, 129.2, 133.7, 133.9, 134.9, 136.6, 136.7, 137.2, 148.1,
193.3, 196.4. ESI-HRMS (positive): calcd for C23H17NNaO4+ [M+Na]+
394.1050; found, 394.1053.
(3-(p-Tolyl)cyclopropane-1,2-diyl)bis(phenylmethanone) (7i): cis-
7i: White solid, m.p. 156–158 °C (lit.24 153–155 °C). IR (KBr) 1656
(C=O), 1682 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 2.39 (s, 3H),
3.38 (d, J = 6.2 Hz, 2H), 3.54 (t, J = 6.2 Hz, 1H), 7.19–7.25 (m, 4H),
7.42–7.47 (m, 4H), 7.53–7.58 (m, 2H), 8.01–8.04 (m, 4H). 13C NMR
(100 MHz, CDCl3) δ 21.1, 31.1, 36.9, 126.5, 128.4, 128.6, 129.6,
133.1, 135.5, 137.0, 137.3, 194.5. ESI-HRMS (positive): calcd for
C24H20NaO2+ [M+Na]+ 363.1356; found, 363.1361. trans-7i: White
solid, m.p. 139–141 °C (lit.24 135–136 °C). IR (KBr) 1660 (C=O) cm−1.
1H NMR (400 MHz, CDCl3) δ 2.28 (s, 3H), 3.57 (dd, J1 = 6.2 Hz,
J2 = 9.8 Hz, 1H), 3.81 (dd, J1 = 5.0 Hz, J2 = 9.8 Hz, 1H), 4.27 (dd,
J1 = 5.0 Hz, J2 = 6.2 Hz, 1H), 7.06 (d, J = 8.0 Hz, 2H), 7.19 (d, J =
8.0 Hz, 2H), 7.45–7.50 (m, 2H), 7.53–7.59 (m, 3H), 7.62–7.67 (m,
1H), 8.04 (d, J = 7.6 Hz, 2H), 8.20 (d, J = 7.6 Hz, 2H). 13C (100 MHz,
CDCl3) δ 21.1, 30.0, 37.5, 38.0, 128.4, 128.5, 128.6 (overlap, 2C),
128.8, 129.0, 131.3, 133.2, 133.5, 136.9, 137.2, 137.6, 193.8, 197.5.
ESI-HRMS (positive): calcd for C24H20NaO2+ [M+Na]+ 363.1356;
found, 363.1360.
(3-(4-Fluorophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7e): cis-7e: White solid, m.p. 151–154 °C. IR (KBr) 1657 (C=O),
1681 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.50 (d, J = 6.0 Hz,
2H), 3.67 (t, J = 6.0 Hz, 1H), 7.44–7.51 (m, 6H), 7.56–7.60 (m, 2H),
8.00 (d, J = 7.6 Hz, 4H), 8.27 (d, J = 8.8 Hz, 2H). 13C NMR
(100 MHz, DMSO-d6) δ 30.3, 37.6, 115.8 (d, JC-F = 21.2 Hz), 128.6,
129.1, 129.2, 133.8, 135.4 (d, JC-F = 2.8 Hz), 137.1, 161.7 (d, JF-C
=
241.0 Hz), 194.4. ESI-HRMS (positive): calcd for C23H17FNaO2+
[M+Na]+ 367.1105; found, 367.1107. trans-7e: White solid, m.p.
131–132 °C. IR (KBr) 1656 (C=O) cm−1. 1H NMR(400 MHz, CDCl3)
δ 3.56 (dd, J1 = 6.2 Hz, J2 = 9.8 Hz, 1H), 3.79 (dd, J1 = 5.0 Hz, J2 = 9.8
Hz, 1H), 4.24 (dd, J1 = 5.0 Hz, J2 = 6.2 Hz, 1H), 6.91–6.96 (m, 2H),
7.23–7.29 (m, 2H), 7.46–7.51 (m, 2H), 7.54–7.61 (m, 3H), 7.63–7.68
(m, 1H), 8.02 (d, J = 7.6 Hz, 2H), 8.18 (d, J = 7.6 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 30.0, 37.1, 37.3, 115.2 (d, JC-F = 21.5 Hz), 128.3,
128.5, 128.7, 128.8, 130.1 (d, JF-C = 3.1 Hz), 130.4 (d, JF-C = 8.1 Hz),
133.4, 133.6, 137.0, 137.4, 162.0 (d, JF-C = 244.8 Hz), 193.6, 197.1.
ESI-HRMS (positive): calcd for C23H17FNaO2+ [M+Na]+ 367.1105;
found, 367.1106.
(3-(4-Methoxylphenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7j): cis-7j: White solid, m.p. 128–130 °C. IR (KBr) 1658 (C=O),
1682 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.37 (d, J = 6.2 Hz,
2H), 3.54 (t, J = 6.2 Hz, 1H), 3.84 (s, 3H), 6.94 (d, J = 8.6 Hz, 2H),
7.26 (d, J = 8.6 Hz, 2H), 7.42–7.46 (m, 4H), 7.53–7.57 (m, 2H), 8.01–
8.04 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 30.9, 36.9, 55.4, 114.3,
127.7, 128.4, 128.6, 130.5, 133.1, 137.3, 158.9, 194.5. ESI-HRMS
(positive): calcd for C24H20NaO3+ [M+Na]+ 379.1305; found, 379.1304.
trans-7j: Pale yellow solids, m.p. 98–101 °C. IR (KBr) 1656 (C=O)
(3-(4-Nitrophenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7f): cis-7f: White solid, m.p. 195–197 °C. IR (KBr) 1686 (C=O) cm−1.
1H NMR (400 MHz, CDCl3) δ 3.54 (d, J = 6.0 Hz, 2H), 3.67 (t,
J = 6.0 Hz, 1H), 7.42–7.50 (m, 6H), 7.54–7.59 (m, 2H), 8.00 (d,
J = 7.5 Hz, 4H), 8.23 (d, J = 7.5 Hz, 2H). 13C NMR (100 MHz, CDCl3)
δ 30.2, 37.3, 124.1, 127.4, 128.4, 128.7, 133.5, 136.8, 146.4, 147.0,
193.3. ESI-HRMS (positive): calcd for C23H17NNaO4+ [M+Na]+
394.1050; found, 394.1054. trans-7f: White solid, m.p. 155–156 °C.
IR (KBr) 1657 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.65 (dd,
J1 = 6.4 Hz, J2 = 10.0 Hz, 1H), 3.86 (dd, J1 = 4.8 Hz, J2 = 10.0 Hz, 1H),
4.30 (dd, J1 = 4.8 Hz, J2 = 6.4 Hz, 1H), 7.43–7.51 (m, 4H), 7.55–7.62
(m, 3H), 7.65–7.70 (m, 1H), 7.98–8.01 (m, 2H), 8.11 (d, J = 8.4 Hz,
2H), 8.16–8.19 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 30.1, 36.6,
37.3, 123.5, 128.3, 128.5, 128.8, 128.9, 129.7, 133.8, 133.9, 136.7,
137.0, 142.1, 147.1, 193.2, 196.4. ESI-HRMS (positive): calcd for
C23H17NNaO4+ [M+Na]+ 394.1050; found, 394.1056.
1
cm−1. H NMR (400 MHz, CDCl3) δ 3.54 (dd, J1 = 6.2 Hz, J2 =
10.0 Hz, 1H), 3.75 (s, 3H), 3.78 (dd, J1 = 4.8 Hz, J2 = 10.0 Hz, 1H),
4.24 (dd, J1 = 4.8 Hz, J2 = 6.2 Hz, 1H), 6.78 (d, J = 8.6 Hz, 2H), 7.21
(d, J = 8.6 Hz, 2H), 7.46–7.50 (m, 2H), 7.53–7.60 (m, 3H), 7.62–7.67
(m, 1H), 8.02 (d, J = 7.2 Hz, 2H), 8.18 (d, J = 7.6 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 30.1, 37.6, 37.7, 55.1, 113.7, 126.3, 128.3, 128.5,
128.6, 128.8, 129.8, 133.2, 133.5, 137.2, 137.6, 158.8, 193.8, 197.4.
ESI-HRMS (positive): calcd for C24H20NaO3+ [M+Na]+ 379.1305;
found, 379.1302.
(3-(2,4-Dimethoxyphenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7k): cis-7k: White solid, m.p. 176–178 °C. IR (KBr) 1675 (C=O)
cm−1. 1H NMR (400 MHz, CDCl3) δ 3.39 (d, J = 6.4 Hz, 2H), 3.59 (t,
J = 6.4 Hz, 1H), 3.79 (s, 3H), 3.85 (s, 3H), 6.48–6.52 (m, 2H), 7.12 (d,
J = 8.0 Hz, 1H), 7.42–7.46 (m, 4H), 7.52–7.57 (m, 2H), 8.04 (d,
J = 7.6 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ 27.9, 35.5, 55.4,

384 JOURNAL OF CHEMICAL RESEARCH 2013
55.5, 98.7, 104.1, 119.2, 127.9, 128.37, 128.44, 132.9, 137.6, 159.5,
160.2, 195.3. ESI-HRMS (positive): calcd for C25H22NaO4+ [M+Na]+
409.1410; found, 409.1408. trans-7k: yellow oil. IR (KBr) 1663
yields were determined by 1H NMR respectively. cis-7o: White solid,
m.p. 136–138 C. IR (KBr) 1654 (C=O), 1681 (C=O) cm−1. 1H NMR
(400 MHz, CDCl3) δ 3.63 (t, J = 5.6 Hz, 1H), 3.83 (d, J = 5.6 Hz, 2H),
7.19 (dd, J1 = 1.6 Hz, J2 = 5.2 Hz, 1H), 7.39–7.44 (m, 4H), 7.46 (d,
J = 7.6 Hz, 1H), 7.50–7.55 (m, 2H), 7.66 (ddd, J1 = 1.0 Hz, J2 =
7.6 Hz, J3 = 7.6 Hz, 1H), 8.04 (d, J = 7.6 Hz, 4H), 8.56 (d, J = 4.4 Hz,
1H). 13C NMR (100 MHz, CDCl3) δ 31.5, 37.3, 122.0, 123.7, 128.4,
128.5, 133.1, 136.5, 137.1, 149.6, 157.2, 194.3. ESI-HRMS (posi-
tive): calcd for C22H17NNaO2+ [M+Na]+ 350.1151; found, 350.1151.
trans-7o: Pale yellow solids, m.p. 94–96 °C. IR (KBr) 1659 (C=O)
1
(C=O) cm−1. H NMR (400 MHz, CDCl3) δ 3.47 (dd, J1 = 6.4 Hz,
J2 = 9.8 Hz, 1H), 3.49 (s, 3H), 3.77 (s, 3H), 3.83 (dd, J1 = 4.8 Hz,
J2 = 9.8 Hz, 1H), 4.13 (dd, J1 = 4.8 Hz, J2 = 6.4 Hz, 1H), 6.30 (d,
J = 2.0 Hz, 1H), 6.44 (dd, J1 = 2.0 Hz, J2 = 8.4 Hz, 1H), 7.18 (d,
J = 8.4 Hz, 1H), 7.45–7.50 (m, 2H), 7.53–7.58 (m, 3H), 7.62–7.66
(m, 1H), 8.07 (d, J = 7.2 Hz, 2H), 8.19 (d, J = 7.6 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 30.2, 34.0, 36.5, 54.7, 55.2, 98.2, 103.7,
115.3, 128.3, 128.4 (overlap, 2C), 128.7, 130.4, 132.8, 133.4, 137.3,
137.7, 159.0, 160.2, 194.1, 197.7. ESI-HRMS (positive): calcd for
C25H22NaO4+ [M+Na]+ 409.1410; found, 409.1416.
(3-(3,4-Dimethoxyphenyl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7l): cis-7l: White solid, m.p. 156–157 °C. IR (KBr) 1675 (C=O) cm−1.
1H NMR (400 MHz, CDCl3) δ 3.39 (d, J = 6.2 Hz, 2H), 3.54 (t,
J = 6.2 Hz, 1H), 3.90 (s, 3H), 3.91 (s, 3H), 6.84–6.90 (m, 3H),
7.41–7.46 (m, 4H), 7.52–7.57 (m, 2H), 8.01–8.04 (m, 4H). 13C NMR
(100 MHz, CDCl3) δ 31.1, 36.9, 56.0, 56.0, 110.8, 111.6, 118.1, 128.4,
128.6, 131.0, 133.1, 137.2, 148.4, 149.3, 194.4. ESI-HRMS (posi-
tive): calcd for C25H22NaO4+ [M+Na]+ 409.1410; found, 409.1413.
trans-7l: Pale yellow solids, m.p. 102–103 °C. IR (KBr) 1663 (C=O),
1686 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.55 (dd, J1 = 6.2 Hz,
J2 = 10.0 Hz, 1H), 3.73 (s, 3H), 3.76 (dd, J1 = 4.8 Hz, J2 = 10.0 Hz,
1H), 3.82 (s, 3H), 4.22 (dd, J1 = 4.8 Hz, J2 = 6.2 Hz, 1H), 6.73 (d,
J =1.4 Hz, 1H), 6.74 (d, J = 8.4 Hz, 1H), 6.85 (dd, J1 = 1.4 Hz,
J2 = 8.4 Hz, 1H), 7.45–7.50 (m, 2H), 7.53–7.60 (m, 3H), 7.62–7.67
(m, 1H), 8.04 (d, J = 7.2 Hz, 2H), 8.18 (d, J = 7.2 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 30.0, 37.6 (overlap, 2 C), 55.71, 55.75, 110.9,
112.0, 121.0, 126.9, 128.35, 128.45, 128.6, 128.8, 133.3, 133.5, 137.1,
137.5, 148.3, 148.5, 193.8, 197.4. ESI-HRMS (positive): calcd for
C25H22NaO4+ [M+Na]+ 409.1410; found, 409.1414.
1
cm−1. H NMR (400 MHz, CDCl3) δ 3.66 (dd, J1 = 5.6 Hz, J2 =
10.0 Hz, 1H), 3.75 (dd, J1 = 5.2 Hz, J2 = 10.0 Hz, 1H), 4.41 (dd, J1 =
5.2 Hz, J2 = 5.6 Hz, 1H), 7.05–7.09 (m, 1H), 7.29 (d, J = 7.6 Hz, 1H),
7.41–7,46 (m, 2H), 7.51–7.58 (m, 4H), 7.60–7.65 (m, 1H), 8.01 (d,
J = 7.2 Hz, 2H), 8.22 (d, J = 7.2 Hz, 2H), 8.44 (d, J = 4.8 Hz, 1H). 13
C
NMR (100 MHz, CDCl3) δ 30.1, 37.0, 38.2, 122.1, 123.3, 128.4,
128.55, 128.63, 128.7, 133.2, 133.5, 136.1, 137.1, 137.4, 149.2, 154.6,
193.9, 197.2. ESI-HRMS (positive): calcd for C22H17NNaO2+ [M+Na]+
350.1151; found, 350.1150.
Cyclopropane-1,2,3-trityltris(phenylmethanone) (7p): Only one isomer
was obtained: White solid, m.p. 214–217 °C (lit.28 216–217 °C). IR
1
(KBr) 1663 (C=O), 1685 (C=O) cm−1. H NMR (400 MHz, CDCl3)
δ 3.79 (d, J = 5.6 Hz, 2H), 4.26 (t, J = 5.6 Hz, 1H), 7.43–7.48 (m, 4H),
7.53–7.59 (m, 4H), 7.63–7.68 (m, 1H), 8.02–8.05 (m, 4H), 8.21–8.23
(m, 2H). 13C NMR (100 MHz, CDCl3) δ 30.4, 36.4, 128.5, 128.7,
128.8, 128.9, 133.5 (overlap, 2C), 133.9, 136.5, 193.0, 196.0. ESI-
HRMS (positive): calcd for C24H18NaO3+ [M+Na]+ 377.1148; found,
377.1151.
We thank the National Natural Science Foundation of China
(Grant No. 21272170) for financial support of our program.
(3-(Naphthalen-1-yl)cyclopropane-1,2-diyl)bis(phenylmethanone)
(7m): cis-7m: White solid, m.p. 166–167 °C. IR (KBr) 1656 (C=O),
1681 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.53 (d, J = 6.4 Hz,
2H), 4.17 (t, J = 6.4 Hz, 1H), 7.43–7.50 (m, 6H), 7.51–7.58 (m, 4H),
7.84–7.87 (m, 1H), 7.90–7.93 (m, 1H), 8.07–8.09 (m, 4H), 8.36–8.39
(m, 1H). 13C NMR (100 MHz, CDCl3) δ 29.1, 35.5, 123.7, 124.4,
125.3, 126.3, 126.7, 128.2, 128.4, 128.5, 128.6, 133.0, 133.3, 133.7,
134.6, 137.2, 194.5. ESI-HRMS (positive): calcd for C27H20NaO2+
[M+Na]+ 399.1356; found, 399.1362. trans-7m: White solid, m.p.
121–122 °C. IR (KBr) 1658 (C=O) cm−1. 1H NMR (400 MHz, CDCl3)
δ 3.99 (dd, J1 = 6.4 Hz, J2 = 9.4 Hz, 1H), 4.11 (dd, J1 = 4.8 Hz, J2 = 9.6
Hz, 1H), 4.42 (dd, J1 = 4.8 Hz, J2 = 6.4 Hz, 1H), 7.34–7.46 (m, 5H),
7.49–7.56 (m, 2H), 7.56–7.61 (m, 2H), 7.66–7.70 (m, 1H), 7.76 (d, J
= 8.0 Hz, 1H), 7.81 (d, J = 7.6 Hz, 1H), 7.99 (d, J = 7.2 Hz, 2H), 8.19
(d, J = 8.4 Hz, 1H), 8.25 (d, J = 7.2 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 30.8, 36.5, 36.6, 123.7, 125.1, 125.7, 126.1, 126.9, 128.2,
128.4, 128.5, 128.6, 128.7, 128.9, 130.2, 132.7, 133.1, 133.6, 133.7,
137.1, 137.3, 193.5, 197.5. ESI-HRMS (positive): calcd for
C27H20NaO2+ [M+Na]+ 399.1356; found, 399.1357.
(3-(Furan-2-yl)cyclopropane-1,2-diyl)bis(phenylmethanone) (7n):
cis-7n: Pale yellow solids, m.p. 136–138 °C. IR (KBr) 1655 (C=O),
1678 (C=O) cm−1. 1H NMR (400 MHz, CDCl3) δ 3.53–3.58 (m, 3H),
6.34 (d, J = 3.0 Hz, 1H), 6.39–6.41 (m, 1H), 7.36–7.39 (m, 1H),
7.43–7.48 (m, 4H), 7.54–7.59 (m, 2H), 8.01–8.04 (m, 4H). 13C NMR
(100 MHz, CDCl3) δ 24.5, 34.9, 107.0, 110.9, 128.4, 128.6, 133.2,
137.1, 141.5, 151.6, 193.8. ESI-HRMS (positive): calcd for
C21H16NaO3+ [M+Na]+ 339.0992; found, 339.0993. trans-7n: Pale
yellow solids, m.p. 85–88 °C. IR (KBr) 1662 (C=O), 1682 (C=O)
cm−1. 1H NMR (400 MHz, CDCl3) δ 3.46 (dd, J1 = 6.0 Hz, J2 = 9.6 Hz,
1H), 3.71 (dd, J1 = 5.2 Hz, J2 = 9.6 Hz, 1H), 4.17 (dd, J1 = 5.2 Hz,
J2 = 6.0 Hz, 1H), 6.18 (d, J = 3.0 Hz, 1H), 6.25 (dd, J1 = 2.0 Hz,
J2 = 3.0 Hz, 1H), 7.25 (d, J = 2.0 Hz, 1H), 7.48–7.51 (m, 2H), 7.52–
7.61 (m, 3H), 7.61–7.66 (m, 1H), 8.06 (d, J = 7.2 Hz, 2H), 8.17 (d,
J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 29.4, 29.5,
35.9, 108.0, 110.4, 128.4, 128.5, 128.7, 128.8, 133.3, 133.6, 136.9,
137.2, 142.1, 149.0, 193.2, 196.5. ESI-HRMS (positive): calcd for
C21H16NaO3+ [M+Na]+ 339.0992; found, 339.0987.
Received 17 March 2013; accepted 12 April 2013
Paper 1301841 doi: 10.3184/174751913X13692098347208
Published online: 12 June 2013
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