AsPh3-catalyzed ylide cyclopropanation for the synthesis of trisubstituted vinylcyclopropane derivatives

Article abstract of DOI:10.1016/j.tet.2008.03.076

Under mild conditions, the reaction of alkylidene, arylidene, and heteroarylidene malonates with tosylhydrazone salts in the presence of catalytic amount of Rh₂(OAc)₄ and triphenylarsine affords trans-2,3-disubstituted cyclopropane 1

Full text of DOI:10.1016/j.tet.2008.03.076

Tetrahedron 64 (2008) 5032–5035
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AsPh3-catalyzed ylide cyclopropanation for the synthesis
of trisubstituted vinylcyclopropane derivatives
*
Hong Jiang, Xiu-Li Sun, Chun-Ying Zhu, Li-Xin Dai, Yong Tang
The State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 354 Fenglin Lu, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Under mild conditions, the reaction of alkylidene, arylidene, and heteroarylidene malonates with
tosylhydrazone salts in the presence of catalytic amount of Rh2(OAc)4 and triphenylarsine affords trans-
2,3-disubstituted cyclopropane 1,1-dicarboxylic esters in high yields and high diastereoselectivities.
Ó 2008 Elsevier Ltd. All rights reserved.
Received 27 February 2008
Received in revised form 21 March 2008
Accepted 21 March 2008
Available online 28 March 2008
1. Introduction
Br
CO2Et
CO2Et
CO2Et
Dioxane, 60 °C
Ph
Vinylcyclopropane 1,1-dicarboxylic esters are very useful syn-
thetic intermediates in the creation of cyclopentane skeleton and
heterocyclic compounds.1–4 In our study on ylide chemistry,5 we
recently developed a reaction of telluronium ylide with arylidene
malonates for the preparation of such compounds.6 Later on, we
extended the substrate scope and found both arylidene malonates
and alkylidene malonates were good for this cyclopropanation by
employing arsonium ylides (Scheme 1).7 However, stoichiometric
amount of ylides are required in both aforementioned reactions.
Attempts to develop the catalytic reaction of ethylidene malonate
with cinnamylbromide in the presence of substoichiometric tri-
phenylarsine8 failed (Scheme 2). In this case, only a trace amount of
the desired product was observed and propylidene malonate was
+
CO2Et
trace
20 mol% AsPh3
150 mol% Cs2CO3
Et
Ph
150 mol%
Et
Ts
Na+
Ph
Ph
N-
CO2Me
CO2Me
N
CO2Me
CO2Me
1 mol% Rh2(OAc)4
AsPh3
(1)
Ph
1
3a
2a
Ph
Scheme 2. Attempts on catalytic ylide cyclopropanation.
decomposed when the reaction time was prolonged probably be-
cause the reaction of triphenylarsine with cinnamylbromide was
sluggish. Aggarwal et al. developed an elegant strategy to generate
ylide by employing tosylhydrazone salt and successfully applied it
to ylide reactions.9 We envisioned that 2-phenylvinyl tosylhy-
drazone salt can be used for the formation of arsonium cinnamylide
in the presence of metal catalyst, which allows to realize a catalytic
version of the ylide cyclopropanation as shown in Eq. 1 (Scheme 2).
In this paper, we wish to report our efforts on this subject.
CO2Et
CO2Et
+Br-
i-Bu2Te
R1
CO2Et
CO2Et
toluene
+
-78 °C to r.t.
KHMDS
R2
R2 = Ar
R2
R1
Yields: 74-93%; trans/cis = 71/29-98/2
Ph3As+Br-
CO2Et
R1
CO2Et
CO2Et
THF
-78 °C to r.t.
KHMDS
R2
+
CO2Et
R2
2. Result and discussion
R1
R1 = Ph, SiMe3, H
R2 = Aryl, Alkyl
Initially, a mixture of tosylhydrazone salt 1 and dimethyl
2-benzylidenemalonate 2a in dioxane was stirred at 40 ꢀC in the
presence of catalytic amounts of Rh2(OAc)4 (1 mol %), AsPh3
(20 mol %), and benzyltriethylammonium chloride (20 mol %) for
8 h, affording the desired cyclopropane 3a in 46% yield. Encouraged
by this result, we screened several solvents and found that solvents
strongly influenced the yield of the desired product. As shown in
Table 1, both ether solvents such as THF, dioxane and arene solvents
Yields: 83-94%
trans/cis up to 43/1
Scheme 1. Ylide cyclopropanation for the synthesis of cyclopropanes.
* Corresponding author. Tel.: þ86 21 54925156; fax: þ86 21 54925078.
E-mail address: tangy@mail.sioc.ac.cn (Y. Tang).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.03.076

H. Jiang et al. / Tetrahedron 64 (2008) 5032–5035
5033
Table 1
Ph
HN
Ph
Ph
MeO2C
COOMe
Effects of reaction conditions for catalytic cyclopropanationa
N
N
E
E
Ph
N
Ph
N
N
H
N
E
N
N
Ph
Ph
2a
CO2Me
CO2Me
1 mol% Rh2(OAc)4
E
AsPh3
6
E
3a
4
+
1
+
Et3BnN+Cl-
40 °C dioxane
N
Ph
Ph
E
Path A
2a
4
Ph
Ph
Na+
N-
E = CO2Me
40 °C
PTC
Ph
N
Ph
N
Ts
N
5
Entry
Solvent (mL)b
Ph3As (mol %)
PTC (mol %)
Conversion (%, 3a/4)c
1
[Rh]
1
2
3
4
5
6
7
8
Toluene (6)
BTF (6)
THF (6)
CH3CN (6)
DCE (6)
CHCl2CHCl2 (6)
CHCl3 (6)
Dioxane (6)
Dioxane (1)
Dioxane (1)
Dioxane (1)
Dioxane (1)
Dioxane (1)
Dioxane (0.8)
Dioxane (0.5)
20
20
20
20
20
20
20
20
20
d
20
20
20
20
20
20
20
20
20
20
20
20
10
10
10
41(14:27)
55(35:20)
73(30:43)
68(18:50)
10(7:3)
Path B
N2
Ph
[Rh]
AsPh3
CO2Me
CO2Me
d
12(12:0)
77(46:31)
72(60:12)
40(0:40)
100(100:0)
100(100:0)
78(74:4)
80(78:2)
100(100:0)
3a
[Rh] Ph3As
Ph
Ph
AsPh3
7
8
Ph
9
10d
11
12
13
14
15e
Scheme 3. A possible mechanism for the formation of byproduct 4.
100
50
20
20
20
According to this mechanistic insight and the aforementioned
observation, we envisioned that the loading reduction of the phase-
transfer catalyst and increasing the concentration of the reactants
might inhibit partially the formation of compound 4 and improve
the yield of the desired cyclopropane. As shown in Table 1, de-
creasing the amount of PTC from 20 to 10 mol % reduced the
byproduct yield from 12% to 4% (Table 1, entry 13). Under this
condition, increasing the concentration of reactants and As3Ph by
reduction of dioxane from 1.0 to 0.8 mL and furthermore to 0.5 mL
resulted in a clean reaction (Table 1, entries 14 and 15). In the case
of 0.5 mL of dioxane used, cyclopropane 3a could be obtained in
86% isolated yield and no byproduct 4 was isolated.
Under the optimized conditions, the scope and limitation of the
current cyclopropanation was investigated by employing various
alkylidene, arylidene, and heteroarylidene malonate derivatives as
substrates. The results were summarized in Table 2. The ester
groups of the Michael acceptors had almost no effects on the dia-
stereoselectivity. For example, both methyl and ethyl benzylidene-
malonates gave the corresponding vinylcyclopropanes with the
same diastereoselectivity (entries 1 and 2, Table 2). In the case of
arylidene malonates, both electron-donating and electron-with-
drawing substituents on the benzene ring were well tolerated and
a
Reactions were performed at 40 ꢀC in dioxane with tosylhydrazone salt 1
(150 mg, 0.45 mmol).
b
Volume of solvent.
c
Conversion based on 2a by 1H NMR.
d
In the absence of Rh2(OAc)4 and stirring for 24 h.
Isolated yield was 86%.
e
gave good conversions (entries 1–3 and 8). In halogenated solvents,
this reaction did not proceed well (entries 5–7). The optimal one
was dioxane (Table 1, entries 1–8). In all cases screened, byproduct
4 was isolated and was confirmed by X-ray crystallographic analysis
(Fig. 1). It is envisaged that 4 was formed by a rearrangement of
cinnamyl diazo compound generated from tosylhydrazone salt 1,
followed by a Michael addition to dimethyl 2-benzylidenemalonate
(Scheme 3).10 Further study showed that increasing the loading of
AsPh3 from 20 to 50 mol % or to 100 mol % led to a complete con-
version of 2a into the desired cyclopropanation product 3a and
byproduct 4 was not formed (entries 9, 11, and 12).
Table 2
Catalytic cyclopropanation of alkylidene and arylidene malonatesa
1 mol% Rh2(OAc)4
CO2R'
CO2R'
R'O2C
R1
20 mol% AsPh3
1 +
10 mol% Et3BnN+Cl-
40 °C 0.5 mL Dioxane
CO2R'
2a-2m
R1
Ph
3a-3m
Entry
Substrate
R1
R0
3 (yield, %)b
(trans/cis)c
1
2
3
4
5
6
7
8
2a
2b
2c
2d
2e
2f
2g
2h
2i
Ph
Ph
Me
Et
Et
3a (86)
3b (79)
3c (91)
3d (86)
3e (78)
3f (87)
3g (98)
3h (85)
3i (90)
3j (89)
3k (42)
3l (63)
3m (76)
88:12
88:12
89:11
86:14
89:11
89:11
88:12
92:8
88:11
95:5
90:10
75:25
84:16
p-Br-C6H4
o-Br-C6H4
2,4-Cl2-C6H3
p-NO2-C6H4
p-Me-C6H4
1-Naphthyl
2-Furyl
2-Pyridyl
Et
i-Pr
Et
Me
Me
Me
Et
Me
Me
Et
9
10
11
12
13
2j
2k
2l
Et
Me
Figure 1. Molecular structure of compound 4.
2m
i-Bu
a
Ph3As (18 mg, 0.06 mmol), 2a–2m (0.30 mmol), dioxane (0.5 mL), Rh2(OAc)4
(1.5 mg, 0.003 mmol), benzyltriethylammonium chloride (7 mg, 0.03 mmol), and
tosylhydrazone salt 1 (145 mg, 0.45 mmol).
In the absence of triphenylarsine, no desired product was pro-
duced. This observation is consistent with the mechanism as shown
in Scheme 3, since the arrangement of diazo compound 5 to 6 is
a competing reaction with the generation of metal carbene 7.
b
Isolated yield.
c
Determined by 1H NMR.

5034
H. Jiang et al. / Tetrahedron 64 (2008) 5032–5035
all gave the desired products in high yields with good selectivities
(entries 3–7), suggesting that the electronic effects only influenced
slightly the reaction. Heteroarylidene malonates 2i and 2j were also
examined and high yields were obtained with high diaster-
eoselectivities (entries 9 and 10). Alkylidene malonates gave
moderate to good diastereoselectivities but the yields strongly
depended on structure of the alkyl group (entries 11–13). For ex-
ample, propylene malonate only afforded the desired product in
42% yield. However, iso-butylene and iso-pentylene malonates
were used, the yields were increased to 63% and 76%, respectively
(entries 12 and 13). Thus, this method provided a convenient way to
the synthesis of vinylcyclopropane 1,1-dicarboxylic esters.
4.4. Diethyl trans-2-phenyl-3-styrylcyclopropane-1,1-
dicarboxylate (3b)6
1H NMR (300 MHz, CDCl3): 7.40–7.19 (m, 10H), 6.78 (d,
J¼15.9 Hz, 1H), 6.04 (dd, J¼15.9, 8.7 Hz, 1H), 4.30–4.16 (m, 2H),
4.00–3.82 (m, 2H), 3.49 (d, J¼7.8 Hz, 1H), 3.32 (t, J¼9.0 Hz, 1H), 1.24
(t, J¼7.2 Hz, 3H), 0.92 (t, J¼7.2 Hz, 3H).
4.5. Diethyl trans-2-(4-bromophenyl)-3-styrylcyclopropane-
1,1-dicarboxylate (3c)7
Mp 71–72 ꢀC; 1H NMR (300 MHz, CDCl3): 7.41 (d, J¼8.7 Hz, 2H),
7.34–7.25 (m, 5H), 7.15 (d, J¼8.7 Hz, 2H), 6.79 (d, J¼15.9 Hz, 1H),
6.01 (dd, J¼15.9, 8.7 Hz, 1H), 4.36–4.10 (m, 2H), 4.04–3.84 (m, 2H),
3.42 (d, J¼8.1 Hz, 1H), 3.28 (t, J¼8.1 Hz, 1H), 1.25 (t, J¼7.2 Hz, 3H),
1.00 (t, J¼6.9 Hz, 3H).
3. Conclusion
In summary, a mild catalytic ylide cyclopropanation for the
preparation of vinylcyclopropane 1,1-dicarboxylic esters from
arylidene and alkylidene malonates has been developed. Compared
with our previous report, the loading of AsPh3 was reduced from
stoichiometric amount to 20 mol % for the first time. The readily
available starting material, good selectivities, and high yields make
this protocol potentially useful in organic synthesis. Current
investigations are focused upon asymmetric variants of this
reaction, and results will be reported in due course.
4.6. Diethyl trans-2-(2-bromophenyl)-3-styrylcyclopropane-
1,1-dicarboxylate (3d)
1H NMR (300 MHz, CDCl3): 7.55 (d, J¼7.5 Hz, 1H), 7.37–7.09 (m,
8H), 6.80 (d, J¼16.2 Hz, 1H), 6.05 (dd, J¼15.6, 8.7 Hz, 1H), 4.33–4.20
(m, 2H), 3.97–3.89 (m, 2H), 3.57 (d, J¼8.1 Hz, 1H), 3.37 (t, J¼8.7 Hz,
1H), 1.25 (t, J¼7.2 Hz, 3H), 0.94 (t, J¼7.2 Hz, 3H); 13C NMR (75 MHz,
CDCl3): 207.4, 166.9, 166.3, 136.5, 134.2, 132.5, 129.8, 128.9, 128.5,
127.6, 126.9, 126.3, 126.1, 123.6, 61.7, 61.4, 44.0, 37.8, 33.9, 14.2, 13.7;
IR (thin film)/cmꢁ1: 2980 (m), 1724 (s), 1369 (m), 1288 (m), 1210
(m), 1097 (m), 1026 (m), 963 (m), 749 (m), 693 (m); HRMS (ESI)
calcd for C23H23O4BrNa (MþNa)þ 465.0672; found 465.0672.
4. Experimental
4.1. General procedure for the catalytic cyclopropanation
(2a as a substrate)
4.7. Dimethyl trans-2-(2,4-dichlorophenyl)-3-
styrylcyclopropane-1,1-dicarboxylate (3e)
A mixture of triphenylarsine (18 mg, 0.06 mmol), rhodium(II)
acetate dimer (1.5 mg, 0.003 mmol), benzyltriethylammonium
chloride (7 mg, 0.03 mmol), dimethyl 2-benzylidenemalonate 2a
(66 mg, 0.30 mmol), and tosylhydrazone sodium salt 1 (145 mg,
0.45 mmol) in anhydrous dioxane (0.5 mL) was stirred vigorously at
room temperature for 10 min, then heated at 40 ꢀC for 8–24 h (turn
to orange). After the reaction was complete, it was quenched by
addition of ethyl acetate (10 mL) and filtered rapidly through a glass
funnel with a thin layer of silica gel (ethyl acetate as a eluent,
50 mL). The filtrate was concentrated and the residue was sub-
jected to 1H NMR analysis to determine the ratio of isomers. The
pure product 3a was obtained by flash chromatography on silica
gel.
1H NMR (300 MHz, CDCl3): 7.39–7.13 (m, 8H), 6.80 (d, J¼15.9 Hz,
1H), 5.99 (dd, J¼15.9, 8.4 Hz,1H), 3.80 (s, 3H), 3.54 (d, J¼8.7 Hz, 4H),
3.52 (s, 3H), 3.32 (dd, J¼16.5, 8.7 Hz, 1H); 13C NMR (75 MHz, CDCl3):
167.3, 166.7, 136.5, 136.3, 134.6, 133.9, 131.1, 130.4, 129.1, 128.6, 127.8,
126.7, 126.2, 123.0, 52.9, 52.6, 43.6, 35.1, 34.2; IR (thin film)/cmꢁ1
:
2947 (m), 1731 (s), 1436 (m), 1294 (m), 1221 (m), 1098 (m), 753 (m),
694 (m), 563 (m); HRMS (ESI) calcd for C21H18O4Cl2Na (MþNa)þ
427.0479; found 427.0474.
4.8. Dimethyl trans-2-(4-nitrophenyl)-3-styrylcyclopropane-
1,1-dicarboxylate (3f)
1H NMR (300 MHz, CDCl3): 8.16 (d, J¼8.4 Hz, 2H), 7.45–7.24 (m,
7H), 6.82 (d, J¼16.5 Hz, 1H), 6.00 (dd, J¼15.9, 8.7 Hz, 1H), 3.80 (s,
3H), 3.55 (d, J¼8.1 Hz, 1H), 3.49 (s, 3H), 3.37 (t, J¼8.4 Hz, 1H); 13C
NMR (75 MHz, CDCl3): 167.2, 166.2, 147.1, 142.1, 136.2, 134.8, 129.4,
128.6, 127.9, 126.2, 123.4, 122.6, 53.1, 52.8, 44.7, 36.1, 34.2; IR (thin
film)/cmꢁ1: 2949 (m), 1731 (s), 1522 (m), 1347 (m), 1293 (m), 858
(m), 740 (m), 694 (m); HRMS (ESI) calcd for C21H19NO6Na (MþNa)þ
404.1119; found 404.1105.
4.2. Dimethyl 2-(phenyl(3-phenyl-1H-pyrazol-1-yl)methyl)
malonate (4)
Mp (hexane) 99–101 ꢀC; 1H NMR (300 MHz, CDCl3): 7.84–7.80
(m, 2H), 7.51–7.25 (m, 9H), 6.50 (d, J¼2.4 Hz, 1H), 5.93 (d, J¼11.1 Hz,
1H), 4.91 (d, J¼11.1 Hz, 1H), 3.66 (s, 3H), 3.51 (s, 3H); 13C NMR
(75 MHz, CDCl3): 167.1, 166.8, 151.1, 137.0, 133.5, 131.0, 128.7, 128.6,
128.5,127.7,127.5,125.5,103.0, 64.3, 57.2, 52.9, 52.7; MS (EI) m/z (rel
intensity) 364 (Mþ, 4), 57 (100), 43 (76), 71 (66), 85 (48), 55 (48), 41
(45), 69 (44), 83 (27); IR (thin film)/cmꢁ1: 2953 (m), 1756 (s), 1741
(s), 1500 (m), 1457 (m), 1435 (m), 1317 (m), 1265 (m), 753 (m), 696
(m). Anal. Calcd for C21H20N2O4: C, 69.22; H, 5.53; N, 7.69. Found: C,
69.11; H, 5.51; N, 7.49.
4.9. Dimethyl trans-2-styryl-3-p-tolylcyclopropane-1,1-
dicarboxylate (3g)7
Mp 84–85 ꢀC; 1H NMR (300 MHz, CDCl3): 7.39–7.19 (m, 5H), 7.13
(d, J¼9.0 Hz, 2H), 7.08 (d, J¼9.0 Hz, 2H), 6.78 (d, J¼15.9 Hz, 1H), 6.02
(dd, J¼15.9, 9.0 Hz, 1H), 3.77 (s, 3H), 3.49–3.42 (m, 4H), 3.33 (t,
J¼8.1 Hz, 1H), 2.31 (s, 3H).
4.3. Dimethyl trans-2-phenyl-3-styrylclopropane-1,1-
dicarboxylate (3a)7
4.10. Diethyl trans-2-(naphthalen-1-yl)-3-styryl-
cyclopropane-1,1-dicarboxylate (3h)
1H NMR (300 MHz, CDCl3): 7.40–7.18 (m, 10H), 6.79 (d,
J¼15.9 Hz, 1H), 6.03 (dd, J¼15.6, 8.4 Hz, 1H), 3.78 (s, 3H), 3.50 (d,
J¼8.4 Hz, 1H), 3.44 (s, 3H), 3.34 (t, J¼8.4 Hz, 1H).
1H NMR (300 MHz, CDCl3): 8.27 (d, J¼8.1 Hz, 1H), 7.84–7.74 (m,
2H), 7.60–7.20 (m, 9H), 6.87 (d, J¼16.2 Hz, 1H), 6.11 (dd, J¼16.2,

H. Jiang et al. / Tetrahedron 64 (2008) 5032–5035
5035
8.7 Hz, 1H), 4.37–4.28 (m, 2H), 3.88 (d, J¼8.1 Hz, 1H), 3.67–3.58 (m,
2H), 3.53 (t, J¼8.4 Hz, 1H), 1.27 (t, J¼7.2 Hz, 3H), 0.47 (t, J¼7.2 Hz,
3H); 13C NMR (75 MHz, CDCl3): 167.7, 166.3, 136.6, 134.0, 133.3,
132.8, 130.6, 128.6, 128.2, 128.1, 127.6, 126.1, 126.0, 125.8, 125.0,
124.5, 124.1, 61.8, 61.0, 44.2, 34.9, 33.3, 14.2, 13.2; IR (thin film)/
cmꢁ1: 2976 (m), 1721 (s), 1289 (m), 1198 (m), 793 (m), 776 (m), 752
(m), 735 (m), 689 (m), 694 (m), 640 (m); HRMS (ESI) calcd for
Development Program (Grant No. 2006CB806105), The Chinese
Academy of Sciences, and The Science and Technology Commission
of Shanghai Municipality.
Supplementary data
C
27H26O4Na (MþNa)þ 437.1712; found 437.1723.
General synthetic procedures, characterization, and spectral
data for new compounds, CIF for compound 4. Supplementary data
associated with this article can be found in the online version, at
doi:10.1016/j.tet.2008.03.076.
4.11. Dimethyl trans-2-(furan-2-yl)-3-styrylcyclopropane-1,1-
dicarboxylate (3i)
1H NMR (300 MHz, CDCl3): 7.36–7.22 (m, 6H), 6.77 (d, J¼15.6 Hz,
1H), 6.30 (dd, J¼3.3, 2.1 Hz, 1H), 6.19 (d, J¼3.3 Hz, 1H), 6.02 (dd,
J¼15.9, 8.7 Hz, 1H), 3.77 (s, 3H), 3.60 (s, 3H), 3.38 (d, J¼7.8 Hz, 1H),
3.25 (t, J¼8.1 Hz, 1H); 13C NMR (75 MHz, CDCl3): 167.3, 166.7, 148.8,
142.1, 136.5, 134.5, 128.5, 127.7, 126.2, 122.8, 110.5, 107.8, 53.0, 52.8,
43.4, 33.9, 30.0; IR (thin film)/cmꢁ1: 2967 (m), 1732 (s), 1436 (m),
1289 (m),1231 (m), 793 (m), 752 (m), 735 (m); HRMS (ESI) calcd for
References and notes
1. (a) Kang, Y.-B.; Sun, X.-L.; Tang, Y. Angew. Chem., Int. Ed. 2007, 46, 3918; (b)
Korotkov, V. S.; Larionov, O. V.; Hofmeister, A.; Magull, J.; de Meijere, A.
J. Org. Chem. 2007, 72, 7504; (c) Korotkov, V. S.; Larionov, O. V.; de Meijere,
A. Synthesis 2006, 21, 3542; (d) Kang, Y.-B.; Tang, Y.; Sun, X.-L. Org. Biomol.
Chem. 2006, 4, 299; (e) Cardona, F.; Goti, A. Angew. Chem. 2005, 117, 8042;
Angew. Chem., Int. Ed. 2005, 44, 7832; (f) Carson, C. A.; Kerr, M. A. J. Org.
Chem. 2005, 70, 8242; (g) Pohlhaus, P. D.; Johnson, J. S. J. Am. Chem. Soc.
2005, 127, 16014; (h) Wurz, R. P.; Charette, A. B. Org. Lett. 2005, 7, 2313; (i)
Sibi, M. P.; Ma, Z.; Jasperse, C. P. J. Am. Chem. Soc. 2005, 127, 5764; (j)
Pohlhaus, P. D.; Johnson, J. S. J. Org. Chem. 2005, 70, 1057; (k) Young, I. S.;
Kerr, M. A. Org. Lett. 2004, 6, 139; (l) Ganton, M. D.; Kerr, M. A. J. Org. Chem.
2004, 69, 8554; (m) Young, I. S.; Kerr, M. A. Angew. Chem., Int. Ed. 2003, 42,
C
19H18O5Na (MþNa)þ 349.1042; found 349.1047.
4.12. Dimethyl trans-2-(pyridin-2-yl)-3-styrylcyclopropane-
1,1-dicarboxylate (3j)
1H NMR (300 MHz, CDCl3): 8.46 (d, J¼4.5 Hz, 1H), 7.64–7.56 (m,
1H), 7.37–7.09 (m, 7H), 6.80 (d, J¼15.9 Hz, 1H), 6.17 (dd, J¼16.2,
9.3 Hz,1H), 3.77 (s, 3H), 3.57 (s, 3H), 3.50 (dd, J¼16.2, 9 Hz, 1H), 3.41
(d, J¼7.2 Hz, 1H); 13C NMR (75 MHz, CDCl3): 167.8, 167.0, 154.9,
149.0, 136.7, 136.2, 134.2, 128.5, 127.5, 126.1, 123.9, 123.6, 121.9, 52.9,
52.5, 44.6, 37.9, 35.8; IR (thin film)/cmꢁ1: 2940 (m), 1732 (s), 1591
(m), 1435 (m), 1280 (m), 1231 (m), 1206 (m), 1111 (m), 755 (m), 694
(m), 563 (m); HRMS (ESI) calcd for C20H20NO4 (MþH)þ 338.1395;
found 338.1387.
3023; For
a review on the ring-opening reactions of donor/acceptor-
substituted cyclopropanes, see: (n) Reissig, H. U.; Zimmer, R. Chem. Rev.
2003, 103, 1151.
2. For the preparation of vinylcyclopropane 1,1-dicarboxylic esters by intra-
molecular substitution, please see: (a) Gnamm, C.; Fo¨rster, S.; Miller, N.;
Bro¨dner, K.; Helmchen, G. Synlett 2007, 790; (b) Miura, K.; Fujisawa, N.; Toyo-
hara, S.; Hosomi, A. Synlett 2006, 1883; (c) Ma, S.; Jiao, N.; Yang, Q.; Zheng, Z.
J. Org. Chem. 2004, 69, 6463; (d) Ma, S.; Jiao, N.; Zhao, S.; Hou, H. J. Org. Chem.
2002, 67, 2837; (e) Trost, B. M.; Tanimori, S.; Dunn, P. T. J. Am. Chem. Soc. 1997,
119, 2735.
3. For the preparation of vinylcyclopropane 1,1-dicarboxylic esters by metal
decomposition of diazoalkanes with olefins, please see: (a) Mueller, P.;
Allenbach, Y.; Robert, E. Tetrahedron: Asymmetry 2003, 779; (b) Yang, M.;
Webb, T. R.; Livant, P. J. Org. Chem. 2001, 66, 4945; For other methods, please
see: (c) Georgakopoulou, G.; Kalogiros, C.; Hadjiarapoglou, L. P. Synlett 2001,
1843.
4. For reviews on the preparation of cyclopropane 1,1-dicarboxylic esters, please
see: Lebel, H.; Marcoux, J.-F.; Molinaro, C.; Charette, A. B. Chem. Rev. 2003, 103,
977.
4.13. Diethyl trans-2-ethyl-3-styrylcyclopropane-1,1-
dicarboxylate (3k)7
1H NMR (300 MHz, CDCl3): 7.32–7.19 (m, 5H), 6.63 (d, J¼15.9 Hz,
1H), 5.89 (dd, J¼15.9, 9.0 Hz, 1H), 4.29–4.10 (m, 4H), 2.58 (t,
J¼8.1 Hz, 1H), 2.13 (q, J¼7.8 Hz, 1H), 1.51–1.40 (m, 2H), 1.28 (t,
J¼7.2 Hz, 3H), 1.21 (t, J¼7.2 Hz, 3H), 1.00 (t, J¼7.2 Hz, 3H).
5. (a) Li, C.-Y.; Wang, X.-B.; Sun, X.-L.; Tang, Y.; Zheng, J.-C.; Xu, Z.-H.; Zhou,
Y.-G.; Dai, L.-X. J. Am. Chem. Soc. 2007, 129, 1494; (b) Li, C.-Y.; Sun, X.-L.; Jing,
Q.; Tang, Y. Chem. Commun. 2006, 2980; (c) Ye, L.-W.; Sun, X.-L.; Li, C.-Y.; Tang,
Y. J. Org. Chem. 2007, 72, 1335; (d) Zheng, J.-C.; Liao, W.-W.; Tang, Y.; Sun,
X.-L.; Dai, L.-X. J. Am. Chem. Soc. 2005, 127, 12222; (e) Liao, W.-W.; Li, K.; Tang,
Y. J. Am. Chem. Soc. 2003, 125, 13030; (f) Ye, S.; Huang, Z. Z.; Xia, C. A.; Tang,
Y.; Dai, L.-X. J. Am. Chem. Soc. 2002, 124, 2432; (g) Ye, S.; Yuan, L.; Huang, Z. Z.;
Tang, Y.; Dai, L.-X. J. Org. Chem. 2000, 65, 6257; (h) Ye, S.; Tang, Y.; Dai, L.-X.
J. Org. Chem. 2001, 66, 5717.
6. Tang, Y.; Chi, Z.-F.; Huang, Y.-Z.; Dai, L.-X.; Yu, Y.-H. Tetrahedron 1996, 8747.
7. Jiang, H.; Deng, X.; Sun, X.; Tang, Y.; Dai, L.-X. J. Org. Chem. 2005, 70, 10202.
8. For arsonium ylide in organic synthesis, please see: (a) Cao, P.; Li, C.-Y.; Kang,
Y.-B.; Xie, Z.; Sun, X.-L.; Tang, Y. J. Org. Chem. 2007, 72, 6628; (b) Habrant, D.;
Stengel, B.; Meunier, S.; Mioskowski, C. Chem.dEur. J. 2007, 13, 5433; (c) Dai,
W.-M.; Wu, A.-X.; Wu, H.-F. Tetrahedron: Asymmetry 2002, 2187; (d) Chen, Y.-L.;
Ding, W.-Y.; Cao, W.-G.; Lu, C. Synth. Commun. 2002, 1953; (e) Dai, W.-M.; Lau,
C. W. Tetrahedron Lett. 2001, 42, 2541; (f) Shen, Y.-C.; Wang, T.-L. J. Fluorine
Chem. 1997, 82, 139; (g) Moorhoff, C. M. J. Chem. Res., Synop. 1997, 130; (h) Dai,
W.-M.; Wu, J.; Huang, X. Tetrahedron: Asymmetry 1997, 8, 1979; For reviews,
see: (i) He, H. S.; Chung, C. W. Y.; But, T. Y. S.; Toy, P. H. Tetrahedron 2005,
1385; (j) Huang, Y.-Z.; Shi, L.-L.; Zhou, Z.-L. Triphenylarsine. In Encyclopedia
of Reagents for Organic Synthesis; Paquette, L. A., Ed.; Wiley: New York, NY,
1995; p 5339.
4.14. Diethyl trans-2-isopropyl-3-styrylcyclopropane-1,1-
dicarboxylate(3l)7
1H NMR (300 MHz, CDCl3): 7.34–7.14 (m, 5H), 6.63 (d, J¼15.9 Hz,
1H), 5.86 (dd, J¼15.9, 9 Hz, 1H), 4.34–4.06 (m, 4H), 2.62 (t, J¼
7.8 Hz, 1H), 1.95 (dd, J¼10.5, 7.8 Hz, 1H), 1.40–1.18 (m, 7H), 1.05 (d,
J¼6.6 Hz, 3H), 0.98 (d, J¼6.9 Hz, 3H).
4.15. Dimethyl trans-2-isobutyl-3-styrylcyclopropane-1,1-
dicarboxylate (3m)7
1H NMR (300 MHz, CDCl3): 7.40–7.08 (m, 5H), 6.63 (d, J¼15.9 Hz,
1H), 5.86 (dd, J¼15.9, 9.0 Hz, 1H), 3.76 (s, 3H), 3.72 (s, 3H), 2.60 (t,
J¼8.1 Hz, 1H), 2.22–2.12 (m, 1H), 1.78–1.62 (m, 1H), 1.58–1.40 (m,
1H), 1.20–1.06 (m, 1H), 0.94 (t, J¼6.9 Hz, 6H).
9. Ph3As-catalyzed ylide reactions through decomposition of diazocompound: (a)
Zhu, S. F.; Liao, Y. X.; Zhu, S. Z. Org. Lett. 2004, 6, 377; (b) Aggarwal, V. K.; Patel,
M.; Studley, J. Chem. Commun. 2002, 1514; For a recent review see: (c) Fulton,
J. R.; Aggarwal, V. K.; de Vincente, J. Eur. J. Org. Chem. 2005, 1479.
10. Doyle, M. P.; Yan, M. J. Org. Chem. 2002, 67, 602.
Acknowledgements
We are grateful for the financial support from the Natural
Sciences Foundation of China, the Major State Basic Research