Triphenylarsine-catalyzed cyclopropanation: Highly stereoselective synthesis of trans-2,3-dihydro-spiro[cyclopropane-1,2′-indan-1′, 3′-dione] from alkene and phenacyl bromide

Article abstract of DOI:10.1080/00397910802029406

The triphenylarsine-catalyzed approach for the highly stereoselective synthesis of trans-2,3-dihydro-spiro[cyclopropane-1,2′-indan-1′, 3′-dione] with alkenes and phenacyl bromide in organic solvent is described. The triphenylarsine-catalyzed cyclopropanat

Full text of DOI:10.1080/00397910802029406

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Triphenylarsine-Catalyzed
Cyclopropanation: Highly
Stereoselective Synthesis
of Trans -2,3-Dihydro-
Spiro[Cyclopropane-1,2′-
Indan-1′,3′-dione] from Alkene
and Phenacyl Bromide
Zhongjiao Ren a , Weiguo Cao a b , Weiqi Tong a , Jie
Chen a , Hongmei Deng c & Danyi Wu a
a Department of Chemistry, Shanghai University,
Shanghai, China
b State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai, China
c Instrumental Analysis and Research Center of
Shanghai University, Shanghai, China
Version of record first published: 18 Aug 2008.
To cite this article: Zhongjiao Ren , Weiguo Cao , Weiqi Tong , Jie Chen , Hongmei
Deng & Danyi Wu (2008): Triphenylarsine-Catalyzed Cyclopropanation: Highly
Stereoselective Synthesis of Trans -2,3-Dihydro-Spiro[Cyclopropane-1,2′-Indan-1′,3′-
dione] from Alkene and Phenacyl Bromide, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:13,
2200-2214

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Synthetic Communications1, 38: 2200–2214, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910802029406
Triphenylarsine-Catalyzed Cyclopropanation:
Highly Stereoselective Synthesis of Trans-2,3-
Dihydro-Spiro[Cyclopropane-1,20-Indan-10,30-
dione] from Alkene and Phenacyl Bromide
Zhongjiao Ren,1 Weiguo Cao,1,2 Weiqi Tong,1 Jie Chen,1
Hongmei Deng,3 and Danyi Wu1
1Department of Chemistry, Shanghai University, Shanghai, China
2State Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai, China
3Instrumental Analysis and Research Center of Shanghai University,
Shanghai, China
Abstract: The triphenylarsine-catalyzed approach for the highly stereoselective
synthesis of trans-2,3-dihydro-spiro[cyclopropane-1,20-indan-10,30-dione] with
alkenes and phenacyl bromide in organic solvent is described. The triphenylar-
sine-catalyzed cyclopropanation in water was investigated. The mixture of cis=
trans isomers is provided with water as a solvent. The cis isomer is formed using
water as a solvent. The reactivity of the reaction in water is higher than that in the
organic solvent.
Keywords: Cyclopropanation; Spirocyclopropyl compound; Stereoselective
synthesis; Triphenylarsine-catalyzed; Water
INTRODUCTION
Recently, the spirocyclopropyl compounds have attracted much attention
because of their occurrence in numerous natural products,[1] their wide
range of biological activities,[2] and their utility as versatile intermediates
for synthesis of natural and synthetic products.[3] Thus, the development
Received January 18, 2008
Address correspondence to Zhongjiao Ren, Department of Chemistry,
Shanghai University, Shanghai 200444, China. E-mail: zjren@shu.edu.cn
2200

Triphenylarsine-Catalyzed Cyclopropanation
2201
Scheme 1. Triphenylarsine-catalyzed cyclopropanation of alkenes with phenacyl
bromide.
of methodologies for synthesis of a spirocyclopropyl moiety has become
a subject of great interest and intense effort for synthetic chemists.
Some synthetic approaches for this class of compounds have been
reported in recent years, such as transition metal–catalyzed cyclopropa-
nation of alkene with diazo compound or reductive cyclization, but these
methods are often not highly stereoselective, and a mixture of cis=trans
isomers is generally obtained.[4,5] The cyclopropanation reaction of
alkene with arsonium ylide has been reported.[6] We are interested in tri-
phenylarsine-catalyzed cyclopropanation of alkene with halide. Here we
report a new approach for highly stereoselective synthesis of trans-2,3-
hydro-spiro[cyclopropane-1,20-indan-10,30-dione] via triphenylarsine-cat-
alyzed cyclopropanation of alkenes with phenacyl bromide, and the same
reaction in water was studied (Scheme 1).
Our initial studies focused on screening the optimum reaction con-
ditions. We tested a number of solvents. In the model experiment, a mix-
ture of 2-(4-chlorobenzylidene)-2H-indan-1,3-dinone 1a (1 equiv),
phenacyl bromide 2 (1 equiv), and NaHCO3 (3 equiv) in solvent was
stirred under reflux in the presence of 10 mol% Ph3As, and the com-
pound 3a was obtained. As summarized in Table 1, it is clear that the suc-
cess of this reaction depended on the solvent and temperature. The
nonpolar solvent, such as benzene, gave a poor yield (Table 1, entry 3),
whereas the polar solvents such as chloroform, tetrahydrofuran (THF),
or acetonitrile gave higher yields (Table 1, entries 1, 2, and 4). At a higher
refluxing temperature such as in dioxane (101 ꢀC), the reaction solvent
became a deep color and the unidentified mixture was formed. No cor-
responding cyclopropane was obtained, which suggested that the higher
temperature was unfavorable for the reaction. The best yield was
afforded by CH3CN as solvent (Table 1, entry 4).

2202
Z. Ren et al.
Table 1. Optimization of condition for Ph3As-catalyzed cyclopropanation
Entry
Solvent
Temperature (ꢀC)
Time (h)
Yielda 3a (%)
1
2
3
4
6
chloroform
THF
benzene
acetonitrile
dioxane
61
65
80
82
50
48
90
24
16
60
62
32
67
0b
101
aIsolated yield by silica-gel chromatography.
bNo corresponding cyclopropane was obtained from an unidentified mixture.
To determine the scope of this approach for the construction of spir-
ocyclopropyl indene-1,3-dione, a number of arylidene-indene-1.3-diones
were tested. According to the literature, the arylidene-2H-indan-1,3-
diones were readily prepared through Knoevenagel condensation of aro-
matic aldehydes with indan-1,3-dione in the presence of piperidine in
organic solvent.[7] As shown in Table 2, the desired spirocyclopropanes
3a–j were obtained. In all cases, the trans-2,3-dihydrospirocyclopropane
3 was obtained as the sole product and no cis isomer was observed.
1
The structures of compounds 3a–j were confirmed by H NMR, 13C
NMR, MS, IR, elemental analysis, and X-ray.
In recent years, there has been increasing interest in the investigation
of the possibility of using water as a solvent for organic reactions,
because some reactions have brought surprising and unforeseen results.[8]
Table 2. Triphenylarsine-catalyzed highly stereoselective cyclopropanationa
Entry
Ar
Product
Yieldb (%)
1
2
3
4
5
6
7
8
9
10
4-ClC6H4
2-ClC6H4
3-ClC6H4
2,4-Cl2C6H3
4-FC6H4
3-BrC6H4
3a
3b
3c
3d
3e
3f
67
72
55
85
45
35
62
52
63
26
C6H5
3g
3h
3i
4-CH3C6H4
4-CH3OC6H4
3,4-(CH3O)2C6H3
3j
aTypical reaction condition: A mixture of alkene 1 (5 mmol), bromide 2
(5 mmol), and NaHCO3 (15 mmol) in CH3CN (5 mL) in the presence of 10 mol%
Ph3As was stirred under reflux for 24 h.
bIsolated yield by silica-gel chromatography.

Triphenylarsine-Catalyzed Cyclopropanation
2203
Figure 1. X-ray crystal structure of 3a.
Encouraged by the success of the Ph3 As-catalyzed cyclopropanation
reaction, we focused on the investigation of the possibility that this reac-
tion might be performed in water. The second part of our studies is
devoted to the triphenylarsin-catalyzed cyclopropanation reaction with
water as solvent.
The surfactant plays an important role in solving the problem of
solubility of organic compounds in water. Our initial studies started
with the screening of a suitable surfactant. As can be seen from Table
3, this reaction proceeded smoothly in water to give the corresponding
spirocyclopropyl compounds (3+4)a (cis=trans ¼ 1:2.5). No reaction
occurred in the absence of surfactant (Table 3, entry 6). It indictes that
the surfactant in this reaction is indispensable. Cetyltrimethylammo-
nium bromide (CTMAB) is the most effective of these surfactants
(Table 3, entry 5).
Further the investigation of optimization of the reaction conditions
showed that this reaction depended on the reaction temperature. The
highest yield was afforded by performing the reaction at 40 ꢀC in the
presence of CTMAB (Table 3, entry 5). At higher temperature
(60 ꢀC), some deep-color complex mixtures appeared, and the yield of
(3+4)a decreased to 75% (Table 3 entry 10). Under a lower tempera-
ture (30 ꢀC), (3+4)a was obtained in 74% yield after 72 h (Table 3,
entry 8).

2204
Z. Ren et al.
Table 3. Optimization of conditions for Ph3 As-catalyzed cyclopropanation in
watera
Temp. Time Yield
(ꢀC)
Entry
Surfactant
(h)
(%)b
1
2
3
4
5
6
7
8
9
Tetrabutylammonium bromide
Tetrabutylammonium iodide
Benyltriethylammonium chloride
Benyldimethyltetradecylammonium chloride
Cetyltrimethylammonium bromide (CTMAB)
None
CTMAB
CTMAB
CTMAB
40
40
40
40
40
40
30
30
60
48
48
48
48
48
48
48
72
48
63
57
80
83
86
0
58
74
75
aUnless otherwise specified, the reaction was carried out with triphenylarsine
(0.1 equiv), phenacyl bromide (1.0 equiv), 2-(4-chlorobenzylidene)-2H-indene-
1,3-dinone (1.0 equiv), NaHCO3 (3.0 equiv), and surfactant (0.1 equiv) in water
(5 mL).
To determine the scope of this reaction, a variety of alkenes were
examined. As shown in Table 4, the reaction proceeded smoothly to give
the corresponding spirocyclopropanes in moderate to excellent yields.
1
The structures of compounds (3+4)a–g were confirmed by H NMR,
elemental analysis, and X-ray.
In comparison with the reaction in water (Table, 4 entry 1), the same
reaction using CH3CN as a solvent was performed at 40 ꢀC for 48 h, and
Table 4. Ph3 As-catalyzed cyclopropanation reaction in water in the presence of
CTMABa
Entry
Ar
Time (h)
Yieldb (3+4)(%)
cis=trans ratioc
1
2
3
4
5
6
7
4-ClC6H4
2-ClC6H4
3-ClC6H4
2,4-Cl2C6H3
4-FC6H4
C6H5
48
48
48
48
48
48
48
(a) 83
(b) 84
(c) 75
(d) 95
(e) 65
(f) 91
(g) 85
1 : 2.5
1: 1.9
1 : 2
1 : 1.7
1 : 1
1.8 : 1
1 : 1
4-CH3C6H4
aTypical reaction condition: the reaction was carried out with triphenylarsine
(0.1 equiv), phenacyl bromide (1.0 equiv), 2-(arylidene)-2H-indene-1,3-dinone
(1.0 equiv), NaHCO3 (3.0 equiv), and surfactant (0.1 equiv) in water (5 mL) at
40ꢀC.
bThe combined yield of a mixture of cis=trans isomer.
1
cDetermine by H NMR.

Triphenylarsine-Catalyzed Cyclopropanation
2205
Figure 2. X-ray crystal structure of 3g (cis isomer) (cis-2,3-dihydrospirocyclopro-
pane).
the compound 3a was obtained in only 35 % yield. It is suggested that the
reactivity in water is higher than that in the organic solvent. To the best
of our knowledge, this is the first example of Ph3As-catalyzed cyclopro-
panation reaction in water.
Additional confirmation for the stereochemical assignments of these
cis=trans isomers came from the examination of the coupling constants
for the cyclopropyl ring protons. In general, cyclopropyl protons with
a cis relationship give rise to larger couplings when compared to those
with atrans relationship.[9] The 1H NMR spectrum of compounds
(3+4)a–g showed that the chemical shifts and coupling constants of pro-
tons on cis=trans cyclopropyl are very distinct. In the cis isomers, the
chemical shifts of 2-H are d 3.71–3.80 and ones of 3-H are d 3.87–3.90,
Figure 3. X-ray crystal structure of 4g (trans isomer) (trans-2,3-dihydrospirocy-
clopropane).

2206
Z. Ren et al.
whereas in the trans isomers, the chemical shifts of 2-H are d 4.12–4.20
and ones of 3-H are d 4.24–4.29. The coupling constants of 2-H and
3-H on cis cyclopropyl are in the range of 10.2–10.4 Hz, whereas the
coupling constants of 2-H and 3-H on trans isomer are in the range of
8.8–9.1 Hz.
The hypothetical mechanisms for these processes are proposed,
which involve path A (in the organic solvent) and path B (in water)
Scheme 3.
Path A
(1) The arsonium salt A is formed from triphenylarsine and bromide fol-
lowed by the deprotoantion ofarsonium salt A to afford the arsonium
ylide B in the presence of NaHCO3. (2) The ylide B nucleophilically
attacks the alkene C to result in either two of transition states (TS-D)
or(TS-E). Apparently the TS-E should be favored over TS-D, with the lat-
ter being higher energy given the steric repulsion between bulky COR and
Ar groups in the conformation of TS-D. (3) The trans-disubstituted spir-
ocyclopropane F is produced via trans-elimination of TS-E. In this step,
triphenylarsin is regenerated, and the catalytic cycle is completed.
Path B
(1) The arsonium salt A and arsonium ylide B can be afforded as in path A.
(2) Besides the conformation of TS-H as shown in path A, the new fixed
Scheme 2. Proposed mechanism for stereoselective cyclopropanation in organic
solvent.

Triphenylarsine-Catalyzed Cyclopropanation
2207
conformation of TS-I is formed, in which arsonium cation is coordinated by
the oxygen of the water molecule and an internal hydrogen bond is formed
between this water molecule and enlate of the indene-1,3-dione. The cis iso-
mer G is afforded through cis-elimination of TS-I. Sometimes the fixed TS-I
can be transformed into the more stable TS-H. The driven force of the trans-
formation results from the steric repulsion between the bulky COPh and Ar
groups in the conformation of TS-I. In these cases, the major product is
trans-disubstituted spirocyclopropane F.
We have developed a triphenylarsine-catalyzed approach for the pre-
paration of trans-dihydro-spiro[cyclopropane-1,20-indene-10,30-dione] with
alkenes and phenacyl bromide in CH3CN in the presence of NaHCO3.
The success of this method depends on the choice of solvent and tempera-
ture. The triphenylarsine-catalyzed cyclopropanation in water was also
investigated. We found that water had a strong effect on both the yield
and stereoselectivity in this reaction. The total yields of the spiro[cyclopro-
pane-1,20-indene-10,30-dione] compounds obtained in water are higher than
that obtained in the organic solvent. Moreover, water is not only acting as
a solvent but is also required to provide cis-isomer. The surfactant is neces-
sary for the triphenylarsine-catalyzed cyclopropanation in water.
EXPERIMENTAL
All reagents and solvents were obtained from commercial sources and
used without purification. All melting points were uncorrected. Melting
points were determined on a WRS-1 digital melting-point apparatus
made by Shanghai physical instrument factory (SPOIF), China. IR
1
spectra were measured in KBr on a PE-580B spectrometer. H NMR
Scheme 3. A plausible reaction mechanism for cyclopropanation in water.

2208
Z. Ren et al.
spectra were recorded at a Bruker AM-300, using CDCl3 as solvent and
TMS as internal reference. Mass spectra were taken with a HP5989A
mass spectrometer at an ionizing voltage of 70 eV. Elemental analyses
were measured on the Elemental Vario EL III. X-ray crystal data were
collected with Smart Apex CCD or Bruker Smart Apex2 CCD.
General Procedure for Preparing trans-2,3-Dihydro-spiro[cyclopropane-
1,20-indan-10,30-dione]
The general process for synthesis of trans-spiro[cyclopropane-1,20-
indene-10,30-dione] (3a–j) is as follows: a mixture of alkene (1) (1 mmol),
phenacyl bromide (2) (0.199 g, 1 mmol), NaHCO3 (0.240 g, 3 mmol), and
triphenylarsine (0.03 g, 0.1 mmol) was stirred in the refluxing CH3CN
(5 mL) for 24 h. The CH3CN was removed off under reduced pressure,
and the residue was run on a silica-gel chromatographic column (eluant:
petroleum ether=ethyl acetate 8=1). The desired products (3) can be
obtained and triphenylarsine recovered respectively.
General Procedure for Preparing Spiro[cyclopropane-1,20-
indan-10,30-dione]
The general process for synthesis of trans-spiro[cyclopropane-1,20-
indene-10,30-dione] (3+4)a–g is as follows: a mixture of alkene (1)
(1 mmol), phenacyl bromide (2) (0.199 g, 1 mmol), NaHCO3 (0.240 g,
3 mmol), cetyltrimethylammoniumbromide (CTMAB) (0.334g, 0.1 mmol),
and triphenylarsine (0.03 g, 0.1 mmol) was stirred at 40 ꢀC in H2O (5 mL)
for 48 h. The H2O was removed off under reduced pressure, and the resi-
due was run on a silica-gel chromatographic column (eluant: petroleum
ether=ethyl acetate 8=1). The desired products (3+4) can be obtained
and triphenylarsine recovered.
Data
trans-2,3-Dihydrospiro[2-benzoyl-3-(4-chlorophenyl)-cyclopropane]-1,20-
indan-10,30-dione (3a)
Colorless solid, mp 184–185 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.18 (d, J ¼ 8.8 Hz, 1 H, CH), 4.24 (d, J ¼ 8.8 Hz,
Hz, 1 H, CH), 7.31 (s, 4H), 7.36–7.43 (m, 2 H), 7.52–7.57 (m, 1 H), 7.78–

Triphenylarsine-Catalyzed Cyclopropanation
2209
7.81 (m, 2 H), 7.88–7.94 (m, 4 H). 13C NMR (75 MHz, CDCl3) d: 40.6,
41.2, 47.1, 76.6, 77.0, 77.4, 122.8, 123.0, 128,3, 128.5, 128.8, 130.8,
133.8, 134.0, 135.2, 135.3, 135.9, 141.8, 141.9, 190.1, 193.9. IR (KBr)
1734, 1704, 1683, 1596 cmꢁ1 .MS (EI) (m=z) (%): 105 (100) [PhCO]þ ,
77 (29.1) [Ph]þ , 106 (7.0) [PhCO þ 1]þ , 76 (6.4) [Ph-1]þ , 51 (5.4),
189 (2.2), 50 (2.1), 7.8 (2.0). Anal. calcd. for C24H15ClO3:C, 74.52; H,
3.91. Found: C, 74.66; H, 3.62.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(2-Chlorophenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3b)
Colorless solid, mp 160–161 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.16 (s, 2 H, CH), 7.26–7.38 (m, 4 H), 7.40–7.56
(m, 4 H), 7.77–7.80 (m, 2 H), 7.88–7.96 (m, 3H). 13C NMR (75 MHz,
CDCl3) d: 39.2, 40.5, 46.2, 76.6, 77.0, 77.4, 122.7, 123.0, 126.7, 128.3,
128.8, 129.2, 129.5, 130.5, 131.3, 133.8, 135.1, 135.2, 135.8, 141.6,
141.9, 190.3, 193.8. IR (KBr) 1737, 1706, 1684, 1595 cmꢁ1 MS (EI)
(m=z) (%): 105 (100) [PhCO]þ , 77 (36.3) [Ph]þ , 76 (7.5) [Ph ꢁ 1]þ ,
106 (6.6) [PhCO þ 1]þ , 51 (6.0), 281 (5.4), 189 (3.8), 50 (3.6), 7.8 (2.0).
Anal. calcd. for C24H15ClO3:C, 74.52; H, 3.91. Found: C, 74.66; H, 3.62.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(3-Chlorophenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3C)
Colorless solid, mp 157–158 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.17 (d, J ¼ 8.8 Hz, 1 H, CH), 4.24 (d, J ¼ 8.8 Hz,
Hz, 1 H, CH), 7.25–7.28 (s, 4 H), 7.36–7.43 (m, 2 H), 7.52–7.54 (m, 1 H),
7.79–7.82 (m, 2 H), 7.88–7.94 (m, 4 H). 13C NMR (75 MHz, CDCl3) d:
40.4, 40.9, 47.0, 76.6, 77.0, 77.4, 122.9, 123.1, 127.3, 128.3, 128.8,
129.3, 129.5, 133.8, 134.2, 134.4, 135.2, 135.9, 141.8, 141.9,190.1, 193.8.
IR (KBr) 1737, 1704, 1675, 1596 cmꢁ1. MS (EI) (m=z) (%): 57 (100),
71 (93.3), 105 (93.2) [PhCO]þ , 43 (77.5), 85 (55.5), 55 (46.4), 41 (39.6),
69 (39.3). Anal. calcd. for C24H15ClO3:C, 74.52; H, 3.91. Found: C,
74.64; H, 3.68.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(2,4-Dichlorophenyl)-Cyclopro-
pane]-1,20-Indan-10,30-Dione (3d)
Colorless solid, mp 172–173 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.12 (s, 2 H, CH), 7.26–7.32 (m, 2 H), 7.37–7.42
(m, 3 H), 7.52–7.54 (m, 1 H), 7.80–7.82 (m, 2 H), 7.89–7.92 (m, 4 H).

2210
Z. Ren et al.
13C NMR (75 MHz, CDCl3) d: 38.2, 40.7, 46.0, 76.6, 77.0, 77.4, 122.8,
123.1, 126.7, 127.1, 128.2, 128.3, 128.8, 129.0, 130.1, 131.3, 133.9,
134.7, 135.3, 135.5, 135.9, 136.4, 190.1, 193.7, 193.8. IR (KBr) 1736,
1708, 1685, 1593 cmꢁ1. MS (EI) (m=z) (%): 105 (100) [PhCO]þ ,
77 (28.1) [Ph]þ , 106 (9.0) [PhCO þ 1]þ , 76 (6.3) [Ph ꢁ 1]þ , 51 (4.7), 57
(4.3), 44 (4.0), 43 (2.7). Anal. calcd. for C24H14Cl2O3:C, 68.43; H, 3.35.
Found: C, 68.51; H, 3.03.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(4-Fluorophenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3e)
Colorless solid, mp 207–208 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.20 (d, J ¼ 8.8 Hz, 1 H, CH), 4.25 (d, J ¼ 8.8 Hz,
1 H, CH), 7.00–7.06 (m, 2 H), 7.26–7.39 (m, 4 H), 7.52–7.57 (m, 1 H),
7.78–7.83 (m, 2 H), 7.87–7.96 (m, 4 H). 13C NMR (75 MHz, CDCl3) d:
40.7, 41.3, 76.6, 77.0, 77.4, 115.2, 115.4, 122.8, 123.0, 128.3, 128.8,
130.7, 130.8, 133.8, 135.2, 135.3, 135.9, 141.9, 190.3, 194.1. IR (KBr)
1737, 1706, 1675, 1595 cmꢁ1. MS (EI) (m=z) (%): 105 (100) [PhCO]þ ,
77 (30.8) [Ph]þ , 106 (7.7) [PhCO þ 1]þ , 363 (6.5), 44 (4.8), 51 (4.6), 76
(4.6) [Ph ꢁ 1]þ , 220 (4.3). Anal. calcd. for C24H15FO3: C, 77.83; H,
4.08. Found: C, 77.83; H, 3.97.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(3-Bromophenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3f)
Colorless solid, mp 167–168 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.18 (d, J ¼ 8.8 Hz, 1 H, CH), 4.24 (d, J ¼ 8.8 Hz,
Hz, 1 H, CH), 7.16–7.30 (m, 3 H), 7.40–7.46 (m, 2 H), 7.51–7.57 (m, 2 H),
7.79–7.84 (m, 2 H), 7.88–7.94 (m, 4 H). 13C NMR (75 MHz, CDCl3) d:
40.4, 40.8, 47.0, 76.6, 77.0, 77.4, 122.3, 122.9, 123.1, 127.7, 128.3,
128.8, 129.8, 131.2 132.2, 133.8, 134.6, 135.3, 135.4, 135.9, 141.8, 141.9,
190.1, 193.9. IR (KBr) 1705, 1685, 1596 cmꢁ1. MS (EI) (m=z) (%):105
(100) [PhCO]þ , 77 (30.6) [Ph]þ , 106 (7.4) [PhCO þ 1]þ , 246 (5.3), 76
(5.1) [Ph ꢁ 1]þ , 51 (3.5), 189 (3.1), 326 (2.6). Anal. calcd. for C24H15BrO3:C,
66.84; H, 3.51. Found: C, 67.00; H, 3.40.
trans-2,3-Dihydrospiro[2-Benzoyl-3-Phenyl-Cyclopropane]-1,20-Indan-
10,30-Dione (3g)
Colorless solid, mp 175–176 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 4.23 (d, J ¼ 8.8 Hz, 1 H, CH), 4.29 (d, J ¼ 8.8 Hz,
1 H, CH), 7.30–7.43 (m, 6 H), 7.50–7.56 (m, 2 H), 7.76–7.80 (m, 2 H),
7.87–7.90 (m, 2 H), 7.93–7.96 (m, 2 H). 13C NMR (75 MHz, CDCl3) d:

Triphenylarsine-Catalyzed Cyclopropanation
2211
40.8, 42.4, 47.4, 76.6, 77.0, 77.4, 122.8, 123.0, 128.1, 128.3, 128.4, 128.8,
129.2, 132.4, 133.7, 135.1, 135.2, 136.2, 141.9, 142.0, 190.5, 194.0, 194.3.
IR (KBr) 1737, 1706, 1676, 1595 cmꢁ1. MS (EI) (m=z) (%): 105 (100)
[PhCO]þ , 77 (31.8) [Ph]þ , 106 (6.6) [PhCO þ 1]þ , 76 (5.3) [Ph ꢁ 1]þ ,
44 (5.3), 51 (4.4), 247 (4.3), 50 (2.6). Anal. calcd. for C24H16O3:C,
81.80; H, 4.58. Found: C, 82.11; H, 4.35.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(4-Methoxyphenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3h)
Colorless solid, mp 147–148 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 3.80 (s, 3 H, CH3), 4.18 (d, J ¼ 8.8 Hz, 1 H, CH),
4.26 (d, J ¼ 8.8 Hz, 1 H, CH), 6.87 (d, J ¼ 8.6 Hz, 2 H), 7.30 (d, J ¼
8.6 Hz, 2 H), 7.38–7.43 (m, 2 H), 7.51–7.53 (m, 1 H), 7.76–7.78 (m, 2 H),
7.86–7.96 (m, 4 H). 13C NMR (75 MHz, CDCl3) d: 41.0, 42,6, 47.7,
55.2, 76.6, 77.0, 77.4, 113.8, 122.7, 122.9, 124.2, 128.4, 128.8, 130.3,
133.7, 135.0, 135.1, 136.2, 141.9, 142.1, 159.5, 190.6, 194.2, 194.3. IR
(KBr) 1734, 1706, 1680, 1609, 1596 cmꢁ1. MS (EI) (m=z) (%): 105
(100) [PhCO]þ , 77 (22.6) [Ph]þ , 106 (6.8) [PhCO þ 1]þ , 51 (4.1), 76
(4.1) [Ph ꢁ 1]þ , 277 (2.5), 50 (2.1), 78 (1.8). Anal. calcd. for
C25H18O4:C, 78.52; H, 4.74. Found: C, 78.83; H, 4.58.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(4-Methylphenyl)-Cyclopropane]-
1,20-Indan-10,30-Dione (3i)
Colorless solid, mp 158–159 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 2.34 (s, 3 H, CH3), 4.20 (d, J ¼ 9.1 Hz, 1 H, CH),
4.28 (d, J ¼ 9.1 Hz, 1 H, CH), 7.14 (d, J ¼ 8.0 Hz, 2 H), 7.25 (d, J ¼
8.0 Hz, 2 H), 7.38–7.43 (m, 2 H), 7.51–7.53 (m, 1 H), 7.76–7.80 (m, 2 H),
7.86–7.90 (m, 2 H), 7.93–7.97 (m, 2 H). 13C NMR (75 MHz, CDCl3) d:
21.2, 40.9, 42.6, 47.5, 76.6, 77.0, 77.4, 122.8, 122.9, 128.4, 128.8, 129.0,
129.1, 129.3, 133.7, 135.0, 135.1, 136.2, 138.0, 142.0, 142.1, 190.7,
194.2, 194.4. IR (KBr) 1748, 1735, 1705, 1689, 1595 cmꢁ1. MS (EI)
(m=z) (%): 105 (100) [PhCO]þ , 77 (27.2) [Ph]þ , 106 (8.7) [PhCO þ 1]þ ,
, 76 (5.8) [Ph ꢁ 1]þ , 51 (5.7), 91 (5.1), 291 (4.6), 41 (4.0). Anal. calcd. for
C25H18O3:C, 81.95; H, 4.95. Found: C, 81.96; H, 4.81.
trans-2,3-Dihydrospiro[2-Benzoyl-3-(3,4-Dimethoxyphenyl)-Cyclopro-
pane]-1,20-Indan-10,30-Dione (3j)
Colorless solid, mp 168–169 ꢀC (CH2Cl2=petroleum ether). 1H NMR
(300 MHz, CDCl3) d: 3.80 (s, 3 H, CH3), 3.88 (s, 3 H, CH3), 4.17 (d,

2212
Z. Ren et al.
J ¼ 8.8 Hz, 1 H, CH), 4.27 (d, J ¼ 8.8 Hz, 1 H, CH), 6.82–6.97 (m, 3 H),
7.38–7.43 (m, 2 H), 7.52–7.54 (m, 1 H), 7.77–7.80 (m, 2 H), 7.88–7.96 (m,
4 H). 13C NMR (75 MHz, CDCl3) d: 41.2, 43.0, 47.8, 55.8, 55.9, 76.6,
77.0, 77.4, 110.8, 112.3, 121.5, 122.7, 122.9, 124.7, 128.4, 128.8, 133.7,
135.0, 135.1, 136.1, 141.9, 148.7, 149.0, 190.5, 194.1, 194.3. IR (KBr)
1736, 1704, 1672, 1594 cmꢁ1. MS (EI) (m=z) (%): 105 (100) [PhCO]þ ,
77 (26.7) [Ph]þ , 106 (8.0) [PhCO þ 1]þ , 307 (6.4), 76 (3.9), 44 (3.5), 51
(3.1), 78 (2.3). Anal. calcd. for C26H20O5:C, 75.72; H, 4.89. Found: C,
75.84; H, 4.84.
Spiro[2-Benzoyl-3-(4-Chlorophenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)a
cis=trans (1:2.5). cis-Isomer 1H NMR (300 MHz, CDCl3) d: 3.76 (d,
1
J ¼ 10.2 Hz, 1 H, CH), 3.88 (d, J ¼ 10.2 Hz, 1 H, CH). trans-Isomer H
NMR (300 MHz, CDCl3) d: 4.19 (d, J ¼ 8.8 Hz, 1 H, CH), 4.25 (d,
J ¼ 8.8 Hz, 1 H, CH). Anal. calcd. for C24H15ClO3: C, 74.52; H, 3.91.
Found: C, 74.43; H, 3.64.
Spiro[2-Benzoyl-3-(2-Chlorophenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)b
1
cis=trans (1:1.9). cis-Isomer H NMR (300 MHz, CDCl3) d: 3.80 (d, J ¼
10.2 Hz, 1 H, CH), 3.98 (d, J ¼ 10.2 Hz, 1 H, CH). trans-Isomer 1H
NMR (300 MHz, CDCl3) d: 4.19 (s, 2 H, CH). Anal. calcd. for
C24H15ClO3:C, 74.52; H, 3.91. Found: C, 74.50; H, 3.92.
Spiro[2-Benzoyl-3-(3-Chlorophenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)c
1
cis=trans (1:2). cis-Isomer H NMR (300 MHz, CDCl3) d: 3.73 (d, J ¼
10.4 Hz, 1 H, CH), 3.87 (d, J ¼ 10.4 Hz, 1 H, CH). trans-Isomer 1H
NMR (300 MHz, CDCl3) d: 4.19 (d, J ¼ 8.8 Hz, 1 H, CH), 4.26 (d,
J ¼ 8.8 Hz, 1 H, CH). Anal. calcd. for C24H15ClO3:C, 74.52; H, 3.91.
Found: C, 74.36; H, 3.92.
Spiro[2-Benzoyl-3-(2,4-Dichlorophenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)d
cis=trans (1:1.7). cis-Isomer 1H NMR (300 MHz, CDCl3) d: 3.71 (d,
1
J ¼ 10.2 Hz, 1 H, CH), 3.96 (d, J ¼ 10.2 Hz, 1 H, CH). trans-Isomer H
NMR (300 MHz, CDCl3) d: 4.12 (d, J ¼ 8.8 Hz, 1 H, CH), 4.15 (d,

Triphenylarsine-Catalyzed Cyclopropanation
2213
J ¼ 8.8 Hz, 1 H, CH).Anal. calcd. for C24H14Cl2O3: C, 68.43; H, 3.35.
Found: C, 68.69; H, 3.11.
Spiro[2-Benzoyl-3-(4-Fluorophenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)e
cis=trans (1:1). cis-Isomer 1H NMR (300 MHz, CDCl3) d: 3.78 (d,
1
J ¼ 10.4 Hz, 1 H, CH), 3.88 (d, J ¼ 10.4 Hz, 1 H, CH). trans-Isomer H
NMR (300 MHz, CDCl3) d: 4.20 (d, J ¼ 8.8 Hz, 1 H, CH), 4.25 (d,
J ¼ 8.8 Hz, 1 H, CH). Anal. calcd. for C24H15FO3: C, 77.83; H, 4.08.
Found: C, 77.72; H, 3.93.
Spiro[2-Benzoyl-3-Phenyl-Cyclopropane]-1,20-Indan-10,30-Dione (3+4)f
cis=trans (1.8:1). cis-Isomer 1H NMR (300 MHz, CDCl3) d: 3.82 (d,
1
J ¼ 10.4 Hz, 1 H, CH), 3.84 (d, J ¼ 10.4 Hz, 1 H, CH). trans-Isomer H
NMR (300 MHz, CDCl3) d: 4.24 (d, J ¼ 8.8 Hz, 1 H, CH), 4.30 (d,
J ¼ 8.8 Hz, 1 H, CH). Anal. calcd. for C24H16O3: C, 81.80; H, 4.58.
Found: C, 81.53; H, 4.23.
Spiro[2-Benzoyl-3-(4-Methylphenyl)-Cyclopropane]-1,20-Indan-10,30-
Dione (3+4)g
1
cis=trans (1:1). cis-Isomer H NMR (300 MHz, CDCl3) d: 2.25 (s, 3 H,
CH3), 3.80 (d, J ¼ 10.4 Hz, 1 H, CH), 3.88 (d, J ¼ 10.4 Hz, 1 H, CH).
1
trans-Isomer H NMR (300 MHz, CDCl3) d: 2.34 (s, 3 H, CH3), 4.21
(d, J ¼ 9.1 Hz, 1 H, CH), 4.29 (d, J ¼ 9.1 Hz, 1 H, CH). Anal. calcd.
for C25H18O3:C, 81.95; H, 4.95. Found: C, 81.81; H, 4.93.
ACKNOWLEDGMENT
Thanks are due to the National Natural Science Foundation of China
(No. 20472047).
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