Synthesis of polyfunctionalized vinyl cyclopropanes via the NaI-catalyzed ring-opening cyclization of doubly activated cyclopropenes with 1,1-bis(phenylsulfonyl)ethylene

Article abstract of DOI:10.1016/j.tetlet.2009.01.097

A NaI-catalyzed reaction of 3,3-bis(alkoxycarbonyl)cyclopropenes in the presence of 1,1-bis(phenylsulfonyl)ethylene providing an efficient route to a series of polyfunctionalized vinyl cyclopropanes is described. The reaction is general for a range of dif

Full text of DOI:10.1016/j.tetlet.2009.01.097

Tetrahedron Letters 50 (2009) 3175–3177
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Tetrahedron Letters
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Synthesis of polyfunctionalized vinyl cyclopropanes via the NaI-catalyzed
ring-opening cyclization of doubly activated cyclopropenes with
1,1-bis(phenylsulfonyl)ethylene
Jie Chen a, Ning Xin b, Shengming Ma a,b,
*
a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, PR China
b Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road,
Shanghai 200062, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A NaI-catalyzed reaction of 3,3-bis(alkoxycarbonyl)cyclopropenes in the presence of 1,1-bis(phenylsulfo-
nyl)ethylene providing an efficient route to a series of polyfunctionalized vinyl cyclopropanes is
described. The reaction is general for a range of different 3,3-bis(alkoxycarbonyl)cyclopropenes affording
the products in moderate to high yields. A plausible rationale for this transformation is discussed.
Ó 2009 Elsevier Ltd. All rights reserved.
Received 27 December 2008
Revised 15 January 2009
Accepted 15 January 2009
Available online 23 January 2009
Cyclopropenes, which are highly strained but readily accessible
carbocyclic molecules, have been shown to possess interesting
reactivities in organic synthesis.1–3 Functionalized cyclopropanes
are important synthetic targets and common structural compo-
nents in numerous biologically active natural products and phar-
maceuticals.4 Compounds containing cyclopropane fragments are
valuable synthetic intermediates.5,6 For example, functionalized vi-
nyl cyclopropanes as a useful synthetic unit have been successfully
used to prepare the core of yuremamine.6 Some synthetic methods
of functionalized cyclopropanes have been developed.7,8 One of the
most common methods is the transition metal-catalyzed cyclo-
propanation reaction of diazo compounds with olefins.7
In 2003, we described a regioselective cycloisomerization of
cyclopropenyl ketones leading to 2,3,4-trisubstituted furans or
2,3,5-trisubstituted furans by using CuI or PdCl2(CH3CN)2 as the
catalysts, respectively.9 In the same year, we noticed an XÀ (X = I,
Br)-triggered ring-opening coupling reaction of cyclopropenyl car-
boxylates with organic halides providing an efficient and highly re-
gio- and stereoselective route to a series of polyfunctionalized
1(E)-alkenyl halides.10 However, in the presence of imines, the
NaI-catalyzed reaction of cyclopropenyl carboxylates provided a
highly regio- and stereoselective route to a series of polyfunction-
alized vinyl aziridines.11 Herein, we wish to further report a NaI-
catalyzed reaction of cyclopropenyl carboxylates in the presence
of 1,1-bis(phenylsulfonyl)ethylene providing a convenient route
to a series of polysubstituted vinyl cyclopropanes.
in THF under reflux was studied. To our delight, the reaction took
place smoothly to afford dimethyl 2-(1-(2,2-bis(phenylsulfo-
nyl)cyclopropyl)pentylidene)malonate 3a in 75% yield (Table 1,
entry 1), the structure of which was established by its X-ray dif-
fraction study (Fig. 1).12 No reaction was observed in the absence
of NaI (Table 1, entry 4). The reaction occurred smoothly with a
catalytic amount of NaI (0.2 equiv). Control experiment indicated
that the addition of Na2CO3 is not necessary in this case (Table 1,
entry 6). Concerning the solvent, THF is the best for this transfor-
mation (Table 1, compare entries 7–15 with entry 6).
With the optimized reaction conditions in hand, the scope of
the reaction was studied with some of the typical results being
summarized in Table 2. With R1 being alkyl, aryl, Bn, PhCH2CH2,
protected alcohol, such as TBSOCH2CH2CH2 or THPOCH2CH2CH2
and R2 being CO2Me or CO2Bn, the reactions proceeded smoothly
to afford the corresponding vinyl cyclopropanes in fairly good
yields (Table 2, entries 1–9). However, for substrates with R1 being
t-Bu and R2 being CO2Me, no reaction occurred, and the starting
material was recovered. Unfortunately, for substrates with R1
being Ph or n-C4H9 and R2 or R3 being acyl, no expected product
was formed. With R1 being unprotected alcohol and R2 being
CO2Me, the reactions were complicated.
A plausible mechanism for this transformation is depicted in
Scheme 1. The regioselective nucleophilic attack of IÀ at the less
substituted sp2 carbon atom of cyclopropenes 1a affords carbanion
4a, which attacks the 1,1-bis(phenylsulfonyl)ethylene directly to
afford 5a. Subsequent intramolecular nucleophilic substitution
leads to the formation of the three-membered compound 3a.
In conclusion, we have developed a NaI-catalyzed ring-opening
cyclization reaction of 3,3-bis(alkoxycarbonyl)cyclopropenes in
As an initial trial, the reaction of dimethyl 2-butylcycloprop-2-
ene-1,1-dicarboxylate 1a, 1.0 equiv of 1,1-bis(phenylsulfonyl)eth-
ylene 2, and 1.0 equiv of NaI in the presence of 1.0 equiv of Na2CO3
the presence of 1,1-bis(phenylsulfonyl)ethylene providing
method for the synthesis of a series of polyfunctionalized vinyl
a
* Corresponding author. Tel.: +86 21 62237360; fax: +86 21 62609305.
E-mail address: masm@mail.sioc.ac.cn (S. Ma).
0040-4039/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2009.01.097

3176
J. Chen et al. / Tetrahedron Letters 50 (2009) 3175–3177
Table 1
Reaction of 1a with 2 under different reaction conditions
MeO2C
n-C4H9
CO2Me
CO2Me
MeO2C
NaI (0.2 equiv)
PhO2S
SO2Ph
n-C4H9
1.0 equiv
SO2Ph
SO2Ph
1a
3a
2
Entry
Solvent
Additive (X equiv Na2CO3)
Temp (°C)
Time (h)
Yield of 3aa (%)
1b
2b,c
3
4
5
6
7
8
9
10
11
12
13
14
15
THF
THF
THF
THF
THF
THF
Acetone
NMP
DCE
CH3CN
Toluene
DMF
CH3NO2
DME
1.0
1.0
1.0
1.0
0.5
—
—
—
—
—
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
60
60–80
60–80
60-reflux
60
1
1
1
17.6
1
1
11
10
24
24
24
24
11
11
26
75
81
77
0d
78
81
70
67
52
46
45
32
0e
—
—
—
—
60
60
60-reflux
0e
Dioxane
—
0f
a
Isolated yield.
b
c
d
e
f
1.0 equiv of NaI was added.
1.2 equiv of 2 was added.
The reaction was conducted in the absence of NaI, and 88% of 1a was recovered after workup.
The reaction was complicated.
69% of 1a was recovered.
MeO2C
n-C4H9
CO2Me
MeO2C
CO2Me
I-
n-C4H9
I
H
SO2Ph
SO2Ph
1a
MeO2C
4a
CO2Me
n-C4H9
MeO2C
n-C4H9
SO2Ph
SO2Ph
CO2Me
CO2Me
n-C4H9
3a
CO2Me
SO2Ph
I
SO2Ph
SO2Ph
H
SO2Ph
3a
5a
Figure 1. ORTEP representation of 3a.
Scheme 1. Plausible mechanism of NaI-catalyzed ring-opening cyclization.
Acknowledgments
cyclopropanes. This reaction may be extended to other doubly
activated or monoactivated alkenes, and further studies in this area
are now being carried out in our laboratory.
Financial support from the Major State Basic Research Develop-
ment Program (2009CB825300) is greatly appreciated. We thank
Mr. Ping Lu in this group for reproducing the results presented in
entries 3 and 9 in Table 2.
Table 2
The reaction of cyclopropene 1 with 2
Supplementary data
R2
R1
R2
R2
R2
R1
NaI (0.2 equiv)
THF, reflux
PhO2S
SO2Ph
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tetlet.2009.01.097.
SO2Ph
SO2Ph
1.0 equiv
2
1
3
References and notes
Entry
R1
Ph
R2
Time (h)
Yield of 3a (%)
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n-C8H17
Bn
PhCH2CH2
p-NO2C6H4
n-C4H9
a
Isolated yield.

J. Chen et al. / Tetrahedron Letters 50 (2009) 3175–3177
3177
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12. X-ray data for compound 3a: C25H28O8S2, Mw = 520.59, monoclinic, space group
P2(1)/c, Mo K
(all data), R1 = 0.0842, wR2 = 0.1662, a = 22.0886 (19) Å, b = 7.1012 (6) Å,
c = 16.2013 (14) Å, = 90°, b = 94.577 (2)°,
= 90°, V = 2533.2(4) Å3, T = 293
(2) K, Z = 4, reflections collected/unique: 14,261/5505 (Rint = 0.0618), number
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a
c
r
data have been deposited at the Cambridge Crystallographic Data Center.
CCDC: 712641.