Reactions of methylenecyclopropanes and vinylidenecyclopropanes with N-fluorodibenzenesulfonimide

Article abstract of DOI:10.1016/j.tet.2009.04.075

Methylenecyclopropanes and vinylidenecyclopropanes undergo ring-opening reactions with N-fluorodibenzenesulfonimide (NFSI) upon heating at 60 °C in tetrahydrofuran to give the corresponding fluorinated derivatives 2 and 6 in good to excellent yields. A pl

Full text of DOI:10.1016/j.tet.2009.04.075

Tetrahedron 65 (2009) 5222–5227
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Reactions of methylenecyclopropanes and vinylidenecyclopropanes
with N-fluorodibenzenesulfonimide
*
Min Jiang, Min Shi
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 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:
Methylenecyclopropanes and vinylidenecyclopropanes undergo ring-opening reactions with N-fluo-
rodibenzenesulfonimide (NFSI) upon heating at 60 ꢀC in tetrahydrofuran to give the corresponding
fluorinated derivatives 2 and 6 in good to excellent yields. A plausible reaction mechanism has been
discussed on the basis of previous literature.
Received 16 March 2009
Received in revised form 22 April 2009
Accepted 24 April 2009
Available online 3 May 2009
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Methylenecyclopropanes
Vinylidenecyclopropanes
N-Fluorodibenzenesulfonimide
Fluorinated derivatives
1. Introduction
to various fluorinated compounds.7,8 Therefore, as the ongoing
studies on the chemistry of highly strained small ring, we in-
Methylenecyclopropanes (MCPs) and vinylidenecyclopropanes
(VDCPs) are highly strained but readily accessible molecules that
have served as useful building blocks in organic synthesis.1–4 Thus
far, many novel transformations of these interesting small molecules
have been disclosed by organic chemists. For example, we and others
have recently been investigating the Lewis acid/transition metal-
mediated/catalyzed ring-opening reactions of MCPs 1 and VDCPs 5
with a variety of nucleophiles such as alcohols and aromatic amines
as well as other reactants under mild conditions to produce a variety
of interesting compounds.5 However, to the best of our knowledge,
the investigation on the fluorine-containing transformation of MCPs
1 and VDCPs 5 is rare. For example, although thermal and photo-
chemical skeletal conversions of VDCPs 5 as well as their Lewis acid-
catalyzed transformations with electrophiles had been made great
progress from mechanistic, theoretical, spectroscopic, and synthetic
viewpoints in past decades,3,4 no example on the reaction of VDCPs 5
with fluorinating agents has been disclosed thus far. The specific
properties of fluorine as a substituent in organic compounds have
resulted in a steadily growing interest in organofluorine chemistry,
which has proved to be a research area with numerous applications
in agrochemistry and pharmaceutical chemistry.6 In addition, the
commercialization of safe and efficient fluorinating agents has paved
the way for the development of a wide scope of synthetic pathways
vestigated the reactions of MCPs 1 and VDCPs 5 with fluorinating
agent such as N-fluorodibenzenesulfonimide (NFSI) under various
reaction conditions. In this paper, we wish to report the full details.
2. Results and discussion
Initial examinations using methylenecyclopropane 1a as the
substrate to react with NFSI under a variety of reaction conditions
were aimed at determining the reaction outcome and the optimal
reaction conditions. The results of these experiments are summa-
rized in Table 1. Using 1a (1.0 equiv) with NFSI (1.0 equiv) in DCE at
60 ꢀC, the ring-opened products 2a and 3a were produced in 73%
and 18% yields, respectively, after 12 h under ambient atmosphere
(Table 1, entry 1). Changing the ratio of 1a/NFSI to 1/2 or 1/1.5 also
provided 2a and 3a in similar yields, respectively (Table 1, entries 2
and 3). Thus, we chose the ratio of 1a/NFSI¼1/1 as the best com-
bination to further optimize the reaction conditions. When the
reaction temperature was changed to room temperature (20 ꢀC), 2a
and 3a were obtained in 69% and 12% yields, respectively, after 38 h
(Table 1, entry 4). Adding a variety of Lewis acids such as Sc(OTf)3,
Sn(OTf)2, Yb(OTf)3, Nd(OTf)3, and Sm(OTf)2 to the reaction system
did not significantly improve the yields of 2a and 3a, although the
reactions could complete within 3–10 h (Table 1, entries 5–9).
Further examination of solvent effects revealed that in tetrahy-
drofuran (THF), the product 2a was obtained in 83% yield as a sole
product without compound 3a within 15 h (Table 1, entry 10). In
toluene, the yields of 2a and 3a were 52% and 26%, respectively,
* Corresponding author.
E-mail address: mshi@mail.sioc.ac.cn (M. Shi).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.04.075

M. Jiang, M. Shi / Tetrahedron 65 (2009) 5222–5227
5223
Table 1
Table 2
Optimization of the reaction conditions between 1a and NFSI
Scope and limitations of the reaction of MCPs 1 with NFSI
R1
Ph
R1
R2
Ph
Ph
THF
60 °C
LA, solvent
temp
N(SO2Ph)2
Ph
N(SO2Ph)2
+
(PhSO2)2NF
NFSI
R2
(PhSO2)2NF
NFSI
+
Ph
F
2
F
1
2a
1a
Ph
Entrya
1 (R1/R2)
Time (h)
Yieldb (%)
+
O
2
N
Ph
S
1
2
3
4
5
6
7
8
9
10
1b (p-MeC6H4/p-MeC6H4)
1c (p-MeOC6H4/p-MeOC6H4)
1d (m,p-Me2C6H3/C6H5)
1e (p-ClC6H4/p-ClC6H4)
1f (p-ClC6H4/C6H5)
1g (p-FC6H4/C6H5)
1h (m,p-(MeO)2C6H3/H)
1i (p-MeC6H4/H)
1j (C4H9/C4H9)
12
10
12
24
24
24
3
11
8
30
2b, 86
2c, 91
F
O
SO2Ph
3a
2d,c 85 (1.1:1)
Entrya
1a/NFSI
LA
Solvent
Temp (ꢀC)
Time (h)
Yieldb (%)
2e, 62
2f,d 78 (13:7)
2g,d 71 (1:1)
2h,c 90 (>99:1)
2i,c 84 (4:1)
complex
2a
3a
1
2
3
4
5
6
7
8
1/1
1/2
1/1.5
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
1/1
d
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
THF
Toluene
Et2O
CH2Cl2
CH3CN
60
60
60
rt
12
12
12
38
3
73
72
73
69
66
65
68
66
67
83
52
54
61
52
13
12
11
12
14
19
21
17
18
Trace
26
25
25
9
d
d
d
1k (C4H9/H)
NR
Sc(OTf)3
Sn(OTf)2
Yb(OTf)3
Nd(OTf)3
Sm(OTf)2
d
60
60
60
60
60
60
60
30
30
60
a
Reaction conditions: 1 (0.2 mmol), NFSI (0.2 mmol), solvent (2.0 mL) and the
7
8
reactions were carried out at various temperatures.
b
Isolated yields.
10
10
15
24
42
40
18
c
The ratios were determined by 1H NMR spectroscopic data.
9
d
The ratios were determined by 19F NMR spectroscopic data.
10
11
12
13
14
d
d
If using vinylidenecyclopropanes 5 as substrates to react with
NFSI under the standard reaction conditions, we found that the
products are compounds 6. The results are summarized in Table 3.
We also found the electronic nature of the substituents on the
benzene rings is significant on the reaction outcomes. Using
vinylidenecyclopropane 5a as the substrate, the corresponding
product 6a was obtained in 82% yield after 24 h (Table 3, entry 1).
As for the substrates 5b–5d having electron-donating substituents
on the benzene rings, the yields of 6b–6d could reach 91–95%, re-
spectively (Table 3, entries 2–4). However, as for VDCPs 5e and 5f
with electron-poor substituents on the benzene rings, the corre-
sponding products 6e and 6f were obtained in lower yields (76–
79%) after 24 h under the standard conditions (Table 3, entries 5
and 6). For unsymmetrical VDCPs 5d and 5f, the corresponding
products 6d and 6f were obtained as isomeric mixtures in which
the ratios were determined by 1H NMR spectroscopic data (Table 3,
entries 4 and 6) (Supplementary data).
The reaction mechanism of MCPs with NFSI is outlined in
Schemes 1 and 2, respectively. Initially, the fluoric cation Fþ and the
anionic intermediate A (ꢁN(SO2Ph)2) are generated from NFSI un-
der the standard reaction conditions,9 in which the anionic in-
termediate A can be transformed to another anionic intermediate B
(ꢁOS(O)(Ph)SO2Ph). The MCP 1 is added by Fþ to form intermediate
C.10 Then, the anionic intermediates A and B attack intermediate C
d
d
a
Reaction conditions: 1a (0.2 mmol), NFSI (x mmol), solvent (2.0 mL) and the
reactions were carried out at various temperatures.
b
Isolated yields.
Ph
NHCOCH3
Ph
F
4 (24% yield)
within 24 h (Table 1, entry 11). When the reaction was carried out at
30 ꢀC, 2a and 3a were formed in 54% and 25% yields in ether and
61% and 25% yields in dichloromethane, respectively (Table 1, en-
tries 12 and 13). Using acetonitrile as the solvent, the unexpected
product 4 was obtained in 24% yield along with the production of
2a and 3a in 52% and 9% yields (Table 1, entry 14). Therefore, the
best conditions are to carry out the reaction in THF at 60 ꢀC using
1.0 equiv of 1a and 1.0 equiv NFSI as the starting materials.
Under these optimal reaction conditions, we next carried out
this ring-opening reaction of a variety of methylenecyclopropanes
1 with NFSI. The results of these experiments are summarized in
Table 2. We found that the electronic nature of the substituents on
the benzene rings of 1 is very significant. As can be seen from Table
2, in the presence of an electron-donating substituent at the para or
meta positions of the benzene rings led to 2a in higher yields within
less reaction time than those with electron-withdrawing
substituents (Table 2, entries 1, 2, and 4). For unsymmetrical MCPs
1d, 1f, and 1g, the corresponding products 2d, 2f, and 2g were
obtained as mixtures of E- and Z-isomers on the basis of 1H or 19F
NMR spectroscopic data (Table 2, entries 3 and 5 and 6) (Supple-
mentary data). As for unsymmetrical MCPs 1h and 1i with electron-
donating substituent on the benzene rings, the corresponding
products 2h and 2i were also obtained as isomeric mixtures in
which the ratios were determined by 1H NMR spectroscopic data
and the products E-2h and E-2i were the major ones, perhaps due
to that the aromatic group is more sterical than a hydrogen atom
(Table 2, entries 7 and 8) (Supplementary data). As for aliphatic
MCP 1j, the complicated reaction products were formed without
the isolation of the expected product 2j (Table 2, entry 9). Using
unsymmetrical aliphatic MCP 1k as the substrate, no reaction
occurred (Table 2, entry 10).
Table 3
Scope and limitations of the reaction of VDCPs with NFSI
R3
R3
THF
24 h, 60 °C
R4
+ (PhSO2)2NF
NFSI
R4
F
5
6
Entrya
5 (R3/R4)
Yieldb (%)
6
1
2
3
4
5
6
5a (C6H5/C6H5)
6a, 82
6b, 91
6c, 95
5b (p-MeC6H4/p-MeC6H4)
5c (p-MeOC6H4/p-MeOC6H4)
5d (p-MeOC6H4/C6H5)
5e (p-ClC6H4/p-ClC6H4)
5f (p-ClC6H4/C6H5)
6d,c 94 (1:1)
6e, 76
6f,c 79 (17:3)
a
Reaction conditions: 5 (0.2 mmol), NFSI (0.2 mmol), THF (2.0 mL) and the re-
actions were carried out at various temperatures.
b
Isolated yields.
c
The ratios were determined by 1H NMR spectroscopic data.

5224
M. Jiang, M. Shi / Tetrahedron 65 (2009) 5222–5227
-O N(SO2Ph)
-N(SO2Ph)2
F+
S
F-N(SO2Ph)2
NFSI
+
Ph
O
A
B
R1
N(SO2Ph)2
Ph
Nu = A
R2
R2
R2
F
2
1 F+
R1
R1
R2
R
F+
Nu = B
N
O
S
SO2Ph
R2
1
F
O
C
3
Nu
R1
Nu = CH3C
N
N
+
F
D
H2O
R1
R1
NHCOCH3
R2
N
R2
F
F
OH2
H+
E
4
Scheme 1. Proposed mechanism for the reaction of MCPs with NFSI.
F
F+
+
R3
R4
F+
R3
R4
R3
R4
F
5
G
R3
R4
F
F
-H+
+
R3
R4
H
6
Scheme 2. Proposed mechanism for the reaction of VDCPs with NFSI.
to produce the products 2 and 3, respectively. When the reaction is
carried out in acetonitrile, the solvent also can act as a nucleophile
to attack intermediate C, affording intermediate D. Intermediate D
undergoes hydrolysis with water to give intermediate E, which
produces the product 4 via deprotonation (Scheme 1).
4. Experimental procedures
4.1. General methods
1H and 13C NMR spectra were recorded on a Bruker AM-400
spectrometer for solution in CDCl3 with tetramethylsilane (TMS) as
an internal standard; J values are in hertz. Mass spectra were
recorded by EI methods, and HRMS was measured on a Finnigan
MAþ mass spectrometer. CHN microanalyses were recorded on
a Carlo-Erba 1106 analyzer. Solvents were used without further
drying up. Commercially obtained reagents were used without fur-
ther purification. All reactions were monitored by TLC with Huan-
ghai GF254 silica gel coated plates. Flash column chromatography was
carried out using 300–400 mesh silica gel at increased pressure.
In the case of VDCPs 5, fluoric cation Fþ adds to a double bond of
5 to give cationic intermediate G via intermediate F. Intermediate G
can give the cyclopropane opened cationic intermediate H rapidly
under the standard conditions, which produces the product 6 via
depronotation.11
3. Conclusion
In summary, we have disclosed the reactions of methyl-
enecyclopropanes (MCPs) and vinylidenecyclopropanes (VDCPs)
with NFSI at 60 ꢀC in tetrahydrofuran (THF) to give the corre-
sponding fluorinated derivatives 2 and 6 in moderate to excellent
yields. A plausible reaction mechanism has been discussed on the
basis of previous literature. The particular highly strained three-
membered cyclopropane plays a key role for this transformation.
The corresponding fluorinated products 2 and 6 may be useful in-
termediates in organic synthesis. Efforts are in progress to further
elucidate the mechanistic details of this reaction and to determine
its scope and limitations.
4.2. General procedure
General procedure for the reactions of MCPs 1 or VDCPs 5 with
NFSI. Under ambient atmosphere, methylenecyclopropanes (MCPs)
1
or vinylidenecyclopropanes (VDCPs) 2 (0.2 mmol), NFSI
(0.2 mmol) were added into a Schlenk tube. The reaction mixture
was stirred at 60 ꢀC until the reaction completed. Then, the solvent
was removed under reduced pressure and the residue was purified
by a flash column chromatography (SiO2) to give the corresponding
products 2 or 6 in moderate to good yields.

M. Jiang, M. Shi / Tetrahedron 65 (2009) 5222–5227
5225
4.2.1. Compound 2a
CH2), 3.92–3.99 (2H, m, CH2), 7.08 (2H, d, J¼7.5 Hz, ArH), 7.14 (2H, d,
J¼8.4 Hz, ArH), 7.24–7.30 (3H, m, ArH), 7.37 (2H, d, J¼8.4 Hz, ArH),
7.42–7.52 (4H, m, ArH), 7.64 (2H, t, J¼7.5 Hz, ArH), 7.91 (3H, d,
A white solid, mp 98–100 ꢀC; IR (CH2Cl2):
n 3061, 3024, 2925,
1664, 1494, 1447, 1379, 1168, 1085, 1071, 910, 850, 807, 720,
686 cmꢁ1 1H NMR (300 MHz, CDCl3, TMS):
;
d
2.65–2.74 (2H, m,
J¼8.4 Hz, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d 31.8 (d,
CH2), 3.95–3.99 (2H, m, CH2), 7.20–7.28 (7H, m, ArH), 7.35–7.47 (7H,
JC–F¼26.0 Hz), 46.3, 122.8 (d, JC–F¼13.4 Hz), 127.2, 127.6, 128.0, 128.1,
m, ArH), 7.59 (2H, t, J¼7.6 Hz, ArH), 7.95 (4H, d, J¼7.6 Hz, ArH); 13C
128.6,129.1,129.4,129.5,130.0,130.1,133.9,136.7,138.0,138.1,139.6,
NMR (75 MHz, CDCl3, TMS):
d
31.8 (d, JC–F¼26.7 Hz), 46.3, 122.8 (d,
153.7 (d, JC–F¼259.1 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
ꢁ105.6
d
JC–F¼13.4 Hz), 127.2, 127.6, 128.0, 128.1, 128.6, 129.1, 129.4, 129.5,
(t, JH–F¼15.5 Hz); MS (ESI) m/z (%): 612 (100.00) [Mþþ23]; HRMS
(MALDI) calcd for C28H22NO4FCl2S2Naþ (Mþþ23) requires 612.0243,
found: 612.0241.
130.0,130.1,133.9,136.7,138.0,138.1,139.6,153.7 (d, JC–F¼259.5 Hz);
19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ107.6 (t, JH–F¼13.4 Hz); MS
(ESI) m/z (%): 544 (100.00) [Mþþ23]. Anal. Calcd for C28H24NO4FS2
requires C, 64.47; H, 4.64; N, 2.69%. Found: C, 64.43; H, 4.77;
N, 2.64%.
4.2.6. Compound 2f
A yellow oil; IR (CH2Cl2):
1448, 1378, 1169, 1090, 1016, 930, 850, 752, 686 cmꢁ1
(300 MHz, CDCl3, TMS): 2.64–2.72 (2H, m, CH2), 3.96–3.99 (2H, m,
n
3064, 2924, 2854, 1664, 1585, 1492,
;
1H NMR
4.2.2. Compound 2b
d
A yellow oil; IR (CH2Cl2):
1479, 1448, 1378, 1179, 1068, 929, 702, 685 cmꢁ1
(300 MHz, CDCl3, TMS): 2.31 (3H, s, CH3), 2.40 (3H, s, CH3), 2.63–
2.76 (2H, m, CH2), 3.95–4.00 (2H, m, CH2), 7.05–7.16 (6H, m, ArH),
7.20 (2H, d, J¼8.7 Hz, ArH), 7.45 (4H, t, J¼7.8 Hz, ArH), 7.60 (2H, t,
J¼7.8 Hz, ArH), 7.91 (4H, d, J¼8.7 Hz, ArH); 13C NMR (75 MHz,
n
3064, 3025, 2921, 2867, 1910, 1660,
CH2),7.10(1H, d,J¼8.8 Hz, ArH), 7.15–7.31(6H,m, ArH), 7.35–7.42(2H,
;
1H NMR
m, ArH), 7.44–7.51 (4H, m, ArH), 7.58–7.64 (2H, m, ArH), 7.88–7.93
d
(4H, m, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d
31.9 (d, JC–F¼25.8 Hz),
46.3, 121.7 (d, JC–F¼14.4 Hz), 127.2, 127.7, 127.8, 127.9, 128.6, 128.7,
128.9, 129.2, 129.3, 129.8, 130.5, 130.6, 131.2, 131.3, 132.8, 133.5, 133.7,
134.9, 136.1, 136.2, 136.3, 137.4, 139.3, 153.0 (d, JC–F¼258.7 Hz), 153.8
CDCl3, TMS):
d
21.1, 21.2, 31.7 (d, JC–F¼27.3 Hz), 46.4, 122.5 (d,
(d, JC–F¼249.4 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
ꢁ107.4 (0.35F,
d
JC–F¼13.3 Hz), 128.1, 128.6, 129.0, 129.2, 129.3, 129.4, 129.9, 133.8,
t, JH–F¼18.9 Hz), ꢁ107.5 (0.65F, t, JH–F¼21.4 Hz); MS (ESI) m/z (%): 578
(100.00) [Mþþ23]; HRMS (MALDI) calcd for C28H23NO4FS2ClNaþ
(Mþþ23) requires 578.0633, found: 578.0638.
134.0, 135.1, 135.3, 136.9, 137.2, 139.6, 153.1 (d, JC–F¼258.4 Hz); 19F
NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ108.4 (t, JH–F¼13.8 Hz); MS (ESI)
m/z (%): 572 (100.00) [Mþþ23]; HRMS (MALDI) calcd for
C30H28NO4FS2Naþ (Mþþ23) requires 572.1336, found: 572.1330.
4.2.7. Compound 2g
A colorless oil; IR (CH2Cl2):
1448, 1373, 1168, 1085, 1064, 999, 929, 848, 736 cmꢁ1
(300 MHz, CDCl3, TMS): 2.64–2.73 (2H, m, CH2), 3.95–3.99 (2H, m,
n
3066, 3921, 1907, 1666, 1603, 1506,
4.2.3. Compound 2c
;
1H NMR
A yellow oil; IR (CH2Cl2):
1463, 1381, 1169, 1032, 999, 927, 852, 720, 685 cmꢁ1
(300 MHz, CDCl3, TMS): 2.67–2.79 (2H, m, CH2), 3.78 (3H, s,
n
3065, 2956, 2935, 2837, 1660, 1573,
d
;
1H NMR
CH2), 6.96 (1H, t, J¼8.8 Hz, ArH), 7.06–7.28 (6H, m, ArH), 7.38–7.49
d
(6H, m, ArH), 7.58–7.63 (2H, m, ArH), 7.90 (4H, t, J¼9.6 Hz, ArH); 13C
OCH3), 3.84 (3H, s, OCH3), 3.98–4.03 (2H, m, CH2), 6.84 (2H, d,
J¼8.4 Hz, ArH), 6.96 (2H, d, J¼9.0 Hz, ArH), 7.12 (2H, d, J¼8.1 Hz,
ArH), 7.22 (2H, d, J¼8.1 Hz, ArH), 7.48 (4H, t, J¼7.2 Hz, ArH), 7.61
(2H, t, J¼7.5 Hz, ArH), 7.94 (4H, d, J¼7.8 Hz, ArH); 13C NMR (75 MHz,
NMR (75 MHz, CDCl3, TMS):
d
31.5, 31.7 (d, JC–F¼26.8 Hz), 46.1, 46.2,
114.8 (d, JC–F¼20.8 Hz), 115.6 (d, JC–F¼20.8 Hz), 121.80, 121.83, 121.93,
121.98, 127.0, 127.3, 127.8, 128.01, 128.06, 128.7, 129.1, 129.3, 129.4,
129.9, 130.0, 131.13, 131.18, 131.20, 131.26, 131.6, 131.72, 131.77,
132.7, 133.90, 133.93, 136.5, 137.7, 137.8, 139.50, 139.51, 153.6 (d,
JC–F¼268.0 Hz), 153.7 (d, JC–F¼259.6 Hz), 161.7 (d, JC–F¼246.9 Hz),
CDCl3, TMS):
d
31.7 (d, JC–F¼27.7 Hz), 46.3, 55.1, 55.2, 113.2, 113.6,
113.9, 121.8, 128.0, 128.4, 129.0, 129.4, 130.3, 130.4, 130.6, 130.7,
131.1, 133.7, 133.8, 139.5, 152.7 (d, JC–F¼257.3 Hz), 158.5, 158.9; 19F
162.2 (d, JC–F¼246.1 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
ꢁ116.8
d
NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ109.4 (t, JH–F¼14.1 Hz); MS (ESI)
(0.5F, s), ꢁ116.4 (0.5F, s), ꢁ110.1 (0.5F, t, JH–F¼17.2 Hz), ꢁ109.4 (0.5F, t,
JH–F¼16.1 Hz); MS (EI) m/z (%): 539 (6.32) [Mþ], 310 (29.43), 242
(98.64), 209 (24.23), 183 (6.49), 141 (100.00), 77 (83.56), 51 (13.74);
HRMS (EI) calcd for C28H23NO4F2S2 (Mþ) requires 539.1037, found:
539.1038.
m/z (%): 604 (100.00) [Mþþ23]; HRMS (MALDI) calcd for
C30H28NO6FS2Naþ (Mþþ23) requires 604.1234, found: 604.1218.
4.2.4. Compound 2d
A yellow oil; IR (CH2Cl2):
1378, 1169, 1090, 1070, 1016, 930, 850, 752, 721, 686 cmꢁ1; 1H NMR
(300 MHz, CDCl3, TMS): 2.19 (1.65H, s, CH3), 2.22 (1.65H, s, CH3),
2.27 (1.35H, s, CH3), 2.31 (1.35H, s, CH3), 2.61–2.74 (2H, m, CH2),
3.93–4.01 (2H, m, CH2), 6.89–6.97 (2H, m, ArH), 7.03–7.06 (1H, m,
ArH), 7.15–7.28 (4H, m, ArH), 7.36–7.49 (5H, m, ArH), 7.61 (2H, t,
J¼10.0 Hz, ArH), 7.88–7.92 (4H, m, ArH); 13C NMR (75 MHz,
n 3064, 2924, 1664, 1585, 1492, 1448,
4.2.8. Compound 2h
d
A colorless oil; IR (CH2Cl2):
1581, 1449, 1208, 1035, 835, 752, 686 cmꢁ1
CDCl3, TMS): 2.67–2.75 (2H, m, CH2), 3.79 (3H, s, OCH3), 3.81 (3H,
n
3068, 3003, 2938, 2838, 1689, 1610,
;
1H NMR (300 MHz,
d
s, OCH3), 3.94–3.99 (2H, m, CH2), 5.81 (1H, d, J¼40.8 Hz, CH), 7.53
(5H, t, J¼8.0 Hz, ArH), 7.63–7.67 (4H, m, ArH), 8.05 (4H, d, J¼7.8 Hz,
CDCl3, TMS):
d
19.4, 19.5, 19.7, 19.8, 31.7 (d, JC–F¼26.8 Hz), 31.8 (d,
ArH); 13C NMR (75 MHz, CDCl3, TMS):
d
34.5 (d, JC–F¼27.1 Hz), 46.4,
JC–F¼26.4 Hz), 46.3, 46.4, 122.7 (d, JC–F¼12.5 Hz), 122.8 (d,
JC–F¼13.7 Hz), 126.9, 127.0, 127.1, 127.4, 127.5, 127.9, 128.1, 128.3,
128.6, 128.9, 129.0, 129.1, 129.2, 129.4, 129.5, 129.8, 130.0, 130.5,
130.6, 131.1, 133.8, 134.2, 135.4, 135.5, 135.7, 135.9, 136.1, 136.9, 137.0,
138.2, 138.3, 139.6, 139.7, 153.1 (d, JC–F¼257.7 Hz), 153.4 (d,
55.3, 55.4, 98.1, 101.5, 104.5, 114.6, 127.7, 128.2, 129.1, 130.3, 130.4,
133.9, 139.6, 155.6 (d, JC–F¼257.8 Hz), 157.1, 159.9; MS (EI) m/z (%):
505 (30.39) [Mþ], 208 (27.06), 195 (100.00), 177 (11.56), 164 (9.71),
141 (24.48), 77 (35.70), 51 (9.34); 19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ108.5 (dt, J¼30.2, 13.2 Hz); HRMS (EI) calcd for C24H24NO6FS2
JC–F¼258.4 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ109.3 (t,
(Mþ) requires 505.1029, found: 505.1039.
JH–F¼16.6 Hz); MS (ESI) m/z (%): 572 (100.00) [Mþþ23]; HRMS
(MALDI) calcd for C30H28NO4FS2Naþ (Mþþ23) requires 572.1336,
found: 572.1337.
4.2.9. Compound 2i
A colorless oil; IR (CH2Cl2):
1513, 1448, 1377, 1169, 1085, 926, 854, 752, 686 cmꢁ1
(300 MHz, CDCl3, TMS): 2.31 (0.6H, s, CH3), 2.33 (2.4H, s, CH3),
2.66–2.75 (2H, m, CH2), 3.95–3.99 (2H, m, CH2), 5.41 (0.8H, d,
J¼39.2 Hz, CH), 6.23 (0.2H, d, J¼22.0 Hz, CH), 6.80 (0.5H, d,
J¼8.0 Hz, ArH), 6.95 (1H, s, ArH), 7.11–7.18 (2H, m, ArH), 7.31 (2H, d,
n
3065, 3005, 2923, 1727, 1690, 1610,
;
1H NMR
4.2.5. Compound 2e
d
A white solid, mp 105–107 ꢀC; IR (CH2Cl2):
n
3066, 3049, 2921,
2854, 1967, 1666, 1603, 1507, 1448, 1373, 1168, 1085, 1064, 929, 853,
811, 685 cmꢁ1; 1H NMR (300 MHz, CDCl3, TMS):
2.62–2.72 (2H, m,
d

5226
M. Jiang, M. Shi / Tetrahedron 65 (2009) 5222–5227
J¼8.0 Hz, ArH), 7.49–7.56 (5H, m, ArH), 7.61–7.68 (3H, m, ArH),
7.98–8.05 (5.5H, m, ArH); 13C NMR (75 MHz, CDCl3, TMS):
21.2,
4.2.14. Compound 6c
d
A colorless oil; IR (CH2Cl2):
n
3301, 2926, 1652, 1494, 1446, 1376,
21.4, 34.3 (d, JC–F¼26.4 Hz), 46.3, 108.4, 108.5, 127.2, 127.4, 128.1,
128.2, 128.32, 128.34, 128.4, 128.5, 128.9, 129.1, 129.2, 129.3, 129.7,
130.0, 130.10, 130.14, 131.9, 133.9, 134.0, 134.1, 134.8, 137.0, 139.0,
139.5, 139.7, 155.6 (d, JC–F¼264.0 Hz); MS (EI) m/z (%): 459 (8.59)
[Mþ], 310 (26.36), 298 (30.47), 234 (22.04), 162 (56.71), 141 (96.15),
1275, 1262, 1092, 1027, 764, 701 cmꢁ1 1H NMR (300 MHz, CDCl3,
;
TMS):
d
1.67 (3H, d, J¼3.6 Hz, CH3), 1.72 (3H, d, J¼3.6 Hz, CH3), 1.82
(3H, s, CH3), 3.77 (3H, s, CH3), 3.78 (3H, s, CH3), 4.52–4.53 (1H, m,
CH2), 4.92–4.93 (1H, m, CH2), 6.76 (2H, d, J¼8.8 Hz, ArH), 6.84 (2H,
d, J¼8.8 Hz, ArH), 7.06 (2H, d, J¼8.8 Hz, ArH), 7.24 (2H, d, J¼8.8 Hz,
77 (100.00), 51 (14.49); 19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ108.3
ArH); 13C NMR (75 MHz, CDCl3, TMS):
d 21.6, 22.7, 22.8, 55.0, 55.1,
to ꢁ108.1 (m); HRMS (EI) calcd for C23H22NO4S2F (Mþ) requires
113.1, 113.2, 113.3, 113.6, 116.3, 122.4 (d, JC–F¼19.3 Hz), 130.1, 130.7,
130.8, 130.9, 131.0, 131.1, 131.2, 131.4, 131.5, 137.5, 137.6, 142.0, 153.2
(d, JC–F¼255.1 Hz), 158.4, 158.5; 19F NMR (CDCl3, 282 MHz, CFCl3):
459.0974, found: 459.0970.
4.2.10. Compound 3a
d
ꢁ90.1; MS (EI) m/z (%): 352 (45.22) [Mþ], 337 (52.39), 291 (8.41),
A white solid, mp 102–104 ꢀC; IR (CH2Cl2):
n
3169, 3059, 3029,
2920, 1663, 1494, 1448, 1375, 1169, 1085, 1072, 852, 1000, 934, 852,
700 cmꢁ1 1H NMR (300 MHz, CDCl3, TMS):
267 (100.00), 135 (56.65), 121 (16.89), 91 (4.58), 77 (7.66); HRMS
(EI) calcd for C23H25O2F (Mþ) requires 352.1839, found: 352.1835.
;
d
2.70 (2H, dt, J¼15.3,
4.5 Hz, CH2), 4.39–4.49 (2H, m, CH2), 7.07–7.11 (2H, m, ArH), 7.20–7.32
(8H, m, ArH), 7.41–7.53(5H, m, ArH), 7.61–7.65 (1H, m, ArH), 7.89–7.91
(2H, m, ArH), 7.95–7.97 (2H, m, ArH); 13C NMR (75 MHz, CDCl3, TMS):
4.2.15. Compound 6d
A colorless oil; IR (CH2Cl2):
1443, 1289, 1284, 1170, 1036, 900, 834, 699 cmꢁ1
(300 MHz, CDCl3, TMS):
1.67 (1.5H, d, J¼4.4 Hz, CH3), 1.69 (1.5H, d,
n
3080, 2933, 2836, 2854, 1630, 1511,
;
1H NMR
d
30.3 (d, JC–F¼27.4 Hz), 67.7, 126.7, 127.3, 127.7, 127.9, 128.6, 128.7,
d
129.3, 1294, 130.0, 130.1, 132.4, 134.6, 135.4, 136.6, 142.6, 153.5 (d,
J¼4.4 Hz, CH3), 1.71 (1.5H, d, J¼5.2 Hz, CH3), 1.73 (1.5H, d, J¼5.2 Hz,
CH3), 1.81 (1.5H, s, CH3), 1.83 (1.5H, s, CH3), 3.76 (1.5H, s, OCH3), 3.78
(1.5H, s, OCH3), 4.48 (0.5H, d, J¼1.2 Hz, CH2), 4.55 (0.5H, d, J¼1.6 Hz,
CH2), 4.90–4.91 (0.5H, m, ]CH2), 4.94–4.95 (0.5H, m, ]CH2), 6.76
(1H, d, J¼8.8 Hz, ArH), 6.84 (1H, d, J¼8.8 Hz, ArH), 7.06 (1H, d,
J¼8.8 Hz, ArH), 7.13–7.15 (1H, m, ArH), 7.18–7.21 (2H, m, ArH), 7.23–
7.26 (1H, m, ArH), 7.29–7.31 (2H, m, ArH); 13C NMR (75 MHz, CDCl3,
JC–F¼258.5 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
ꢁ107.7 to ꢁ107.5;
d
MS (ESI) m/z (%): 544 (100.00) [Mþþ23]; HRMS (MALDI) calcd for
C28H24NO4FS2Naþ (Mþþ23) requires 544.1023, found: 544.1006.
4.2.11. Compound 4
A white solid, mp 95–97 ꢀC; IR (CH2Cl2):
n
3422, 3292, 3027,
2932, 2856, 1954, 1666, 1495, 1444, 1230, 1171, 1034, 935, 764 cmꢁ1
1H NMR (300 MHz, CDCl3, TMS):
1.95 (3H, s, CH3), 2.56 (2H, dt,
;
TMS): d 21.5, 21.6, 22.7, 22.8, 55.1, 55.2, 113.2, 113.3, 116.3, 116.4,
d
122.7, 122.8, 123.0, 126.8, 127.0, 127.7, 127.9, 129.8, 129.9, 130.0,
130.1, 130.5, 130.8, 131.0, 131.1, 131.2, 131.3, 137.8, 137.9, 138.4, 139.1,
139.2,141.9,153.6 (d, JC–F¼256.6 Hz),153.7 (d, JC–F¼263.3 Hz),158.4,
J¼30.0, 8.8 Hz, CH2), 3.59 (2H, dt, J¼8.8, 8.8 Hz, CH2), 5.60 (1H, br s,
NH), 7.17–7.20 (2H, m, ArH), 7.23–7.39 (8H, m, ArH); 13C NMR
(75 MHz, CDCl3, TMS):
d
23.3, 30.6 (d, JC–F¼26.0 Hz), 37.0, 122.5 (d,
158.5; 19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ93.5 (0.5F, s), ꢁ93.1
JC–F¼12.0 Hz), 127.1, 127.6, 128.0, 128.6, 129.4, 129.5, 130.0, 130.1,
137.0, 138.2, 138.3, 155.4 (d, JC–F¼258.0 Hz), 169.9; MS (EI) m/z (%):
283 (6.10) [Mþ], 260 (10.48), 224 (100.00), 209 (21.98), 196 (32.52),
167 (16.37), 133 (15.84), 91 (10.54); 19F NMR (CDCl3, 282 MHz,
(0.5F, s); MS (EI) m/z (%): 322 (89.12) [Mþ], 307 (100.00), 261
(15.71), 221 (15.94), 165 (14.96), 133 (21.35), 91 (16.85), 77 (13.75);
HRMS (EI) calcd for C22H23OF (Mþ) requires 322.1733, found:
322.1736.
CFCl3):
d
ꢁ106.9 (t, JH–F¼11.8 Hz); HRMS (EI) calcd for C18H18NOF
(Mþ) requires 283.1372, found: 283.1371.
4.2.16. Compound 6e
A colorless oil; IR (CH2Cl2):
1630, 1593, 1441, 1372, 1173, 1016, 933, 924, 830, 732 cmꢁ1; 1H NMR
(300 MHz, CDCl3, TMS):
J¼4.0 Hz, CH3), 1.81 (3H, s, CH3), 4.51 (1H, d, J¼0.4 Hz, CH2), 4.95
(1H, d, J¼0.4 Hz, CH2), 7.06 (2H, d, J¼8.4 Hz, ArH), 7.21 (4H, d,
J¼8.4 Hz, ArH), 7.25–7.29 (2H, m, ArH); 13C NMR (75 MHz, CDCl3,
n 3082, 2980, 2914, 2856, 1981,
4.2.12. Compound 6a
A colorless oil; IR (CH2Cl2):
1444, 1372, 1173, 1089, 1075, 1012, 900, 767, 697 cmꢁ1
(300 MHz, CDCl3, TMS):
n
3082, 3028, 2856, 1982, 1632, 1599,
d
1.68 (3H, d, J¼4.0 Hz, CH3), 1.73 (3H, d,
;
1H NMR
d
1.68 (3H, d, J¼4.0 Hz, CH3), 1.71 (3H, d,
J¼4.0 Hz, CH3), 1.82 (3H, d, J¼0.8 Hz, CH3), 4.50–4.51 (1H, m, CH2),
4.91–4.92 (1H, m, CH2), 7.13–7.16 (2H, m, ArH), 7.18–7.24 (4H, m, ArH),
TMS):
d
21.5, 21.6, 22.7, 116.9, 121.4 (d, JC–F¼20.1 Hz), 128.2, 128.3,
7.29–7.31 (4H, m, ArH); 13C NMR (75 MHz, CDCl3, TMS):
d
21.0, 21.6,
128.5, 129.2, 130.4, 130.6, 131.1, 131.2, 131.3, 131.4, 133.0, 136.1, 136.9,
22.7, 116.4, 123.4 (d, JC–F¼19.3 Hz), 126.9, 127.0, 127.8, 127.9, 128.1,
128.2, 129.92, 129.97, 130.0, 130.1, 130.7, 138.1, 138.2, 138.3, 138.9,
139.0, 141.8, 154.7 (d, JC–F¼257.3 Hz); MS (EI) m/z (%): 292 (100.00)
[Mþ], 277 (99.72), 257 (25.19), 215 (58.49),183 (23.83),165 (24.47), 91
137.0, 139.0, 139.1, 141.4, 154.8 (d, JC–F¼260.2 Hz); 19F NMR (CDCl3,
282 MHz, CFCl3):
d
ꢁ90.1; MS (EI) m/z (%): 360 (81.61) [Mþ], 345
(100.00), 310 (19.60), 233 (65.83), 125 (38.12), 113 (16.99), 81
(67.39), 41 (41.79); HRMS (EI) calcd for C21H19Cl2F (Mþ) requires
360.0848, found: 360.0845.
(33.53), 77 (18.21); 19F NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ92.1; HRMS
(EI) calcd for C21H21F (Mþ) requires 292.1627, found: 292.1630.
4.2.17. Compound 6f
4.2.13. Compound 6b
A colorless oil; IR (CH2Cl2):
1491, 1443, 1372, 1172, 1016, 833, 699 cmꢁ1
CDCl3, TMS):
n
3081, 2982, 2915, 2862, 1981, 1630,
A colorless oil; IR (CH2Cl2):
1512, 1371, 1168, 1088, 1025, 932, 898, 760 cmꢁ1
(300 MHz, CDCl3, TMS):
n
3028, 3024, 2920, 2858, 1906, 1631,
;
1H NMR (300 MHz,
;
1H NMR
d
1.66 (2.5H, d, J¼4.4 Hz, CH3), 1.69 (0.5H, d, J¼4.4 Hz,
d
1.65 (3H, d, J¼3.6 Hz, CH3), 1.71 (3H, d,
CH3), 1.71 (2.5H, d, J¼5.2 Hz, CH3), 1.74 (0.5H, d, J¼5.2 Hz, CH3), 1.81
(2.5H, s, CH3), 1.82 (0.5H, s, CH3), 4.49 (0.85H, d, J¼1.2 Hz, CH2), 4.51
(0.15H, d, J¼0.8 Hz, CH2), 4.92–4.93 (0.85H, d, J¼1.2 Hz, CH2), 4.94
(0.15H, d, J¼0.8 Hz, CH2), 7.11–7.13 (2H, m, ArH), 7.18–7.32 (7H, m,
J¼3.6 Hz, CH3), 1.82 (3H, d, J¼0.8 Hz, CH3), 2.30 (3H, s, CH3), 2.32
(3H, s, CH3), 4.53 (1H, s, CH2), 4.92–4.93 (1H, m, CH2), 7.02 (4H, s,
ArH), 7.10 (2H, d, J¼8.4 Hz, ArH), 7.20 (2H, d, J¼8.4 Hz, ArH); 13C
NMR (75 MHz, CDCl3, TMS):
d
21.2, 21.6, 22.7, 22.8, 116.3, 123.1 (d,
ArH); 13C NMR (75 MHz, CDCl3, TMS):
d 20.9, 21.0, 21.6, 22.7, 32.0,
JC–F¼20.0 Hz), 128.4, 128.6, 129.8, 129.9, 130.8, 131.1, 135.4, 136.0,
116.6, 116.7, 122.2, 122.4, 126.5, 127.1, 127.9, 128.0, 128.04, 128.1,
128.3, 128.4, 129.3, 129.5, 129.8, 129.9, 129.98, 130.0, 130.5, 130.7,
131.2, 131.3, 132.8, 136.6, 138.4, 138.51, 138.54, 138.6, 141.6, 154.6 (d,
136.1, 136.4, 136.7, 137.7, 137.8, 142.0, 153.6 (d, JC–F¼257.0 Hz); 19F
NMR (CDCl3, 282 MHz, CFCl3):
d
ꢁ93.2 (t, JH–F¼3.1 Hz); MS (EI) m/z
(%): 320 (78.48) [Mþ], 305 (100.00), 285 (17.66), 213 (30.49), 197
(16.51), 123 (20.26), 91 (10.19), 77 (7.93); HRMS (EI) calcd for
C23H25F (Mþ) requires 320.1940, found: 320.1940.
JC–F¼259.8 Hz); 19F NMR (CDCl3, 282 MHz, CFCl3):
ꢁ91.4 (0.85F, s),
d
ꢁ90.8 (0.15F, s); MS (EI) m/z (%): 326 (91.19) [Mþ], 311 (100.00), 293
(48.58), 265 (51.07), 215 (89.61), 165 (35.43), 81 (40.53), 41 (66.39);

M. Jiang, M. Shi / Tetrahedron 65 (2009) 5222–5227
5227
HRMS (EI) calcd for C21H20ClF (Mþ) requires 326.1238, found:
326.1235.
and references therein; (b) Al-Dulayymi, J. R.; Baird, M. S. J. Chem. Soc., Perkin
Trans. 1994, 1547–1548; For some other papers related to vinyl-
idenecyclopropanes: (c) Maeda, H.; Hirai, T.; Sugimoto, A.; Mizuno, K. J. Org.
Chem. 2003, 68, 7700–7706; (d) Pasto, D. J.; Brophy, J. E. J. Org. Chem. 1991, 56,
4554–4556; For a recent review, see: (e) Maeda, H.; Mizuno, K. J. Synth. Org.
Chem. Jpn. 2004, 62, 1014–1025.
1
Acknowledgements
4. (a) Xu, G.-C.; Liu, L.-P.; Lu, J.-M.; Shi, M. J. Am. Chem. Soc. 2005, 127, 14552–
14553; (b) Shi, M.; Lu, J.-M.; Xu, G.-C. Tetrahedron Lett. 2005, 46, 4745–4748; (c)
Li, Q.-J.; Shi, M.; Timmons, C.; Li, G.-G. Org. Lett. 2006, 8, 625–628; (d) Shi, M.;
Lu, J. M. Synlett 2005, 2352–2356; (e) Lu, J. M.; Shi, M. Org. Lett. 2007, 9, 1805–
1808; (f) Lu, J.-M.; Shi, M. Org. Lett. 2006, 8, 5317–5320; (g) Shi, M.; Li, W.
Tetrahedron 2007, 63, 6654–6660; (h) Shi, M.; Yao, L.-F. Chem.dEur. J. 2008, 14,
8725–8731; (i) Lu, J.-M.; Zhu, Z.-B.; Shi, M. Chem.dEur. J. 2009, 15, 963–971; (j)
Zhu, Z.-B.; Shi, M. Chem.dEur. J. 2008, 14, 10219–10222; (k) Yao, L.-F.; Shi, M.
Chem.dEur. J. 2009, 15, 3875–3881.
Financial support from the Shanghai Municipal Committee of
Science and Technology (06XD14005 and 08dj1400100-2), National
Basic Research Program of China (973)-2009CB825300, and the
National Natural Science Foundation of China (20872162,
20672127, 20732008, 20821002 and 20702013) is greatly
acknowledged.
5. (a) Shao, L.-X.; Zhao, L.-J.; Shi, M. Eur. J. Org. Chem. 2004, 4894–4900; (b) Shao,
L.-X.; Huang, J.-W.; Shi, M. Tetrahedron 2004, 60, 11895–11901; (c) Shi, M.; Chen,
Y.; Xu, B.; Tang, J. Green Chem. 2003, 5, 85–88; (d) Shi, M.; Chen, Y. J. Fluorine
Chem. 2003, 122, 219–227; (e) Shi, M.; Jiang, M.; Liu, L.-P. Org. Biomol. Chem.
2007, 5, 438–440; (f) Poutsma, M. L.; Ibarbia, P. A. J. Am. Chem. Soc. 1971, 93,
440–450; (g) Smadja, W. Chem. Rev. 1983, 83, 263–320; (h) Hendrick, M. E.;
Hardie, J. A.; Jones, M., Jr. J. Org. Chem. 1971, 36, 3061–3062; (i) Sugita, H.;
Mizuno, K.; Saito, T.; Isagawa, K.; Otsuji, Y. Tetrahedron Lett. 1992, 33, 2539–
2542; (j) Mizuno, K.; Sugita, H.; Kamada, T.; Otsuji, Y. Chem. Lett. 1994, 449–452
and references cited therein; (k) Sydnes, L. K. Chem. Rev. 2003, 103, 1133–1150;
(l) Akasaka, T.; Misawa, Y.; Ando, W. Tetrahedron Lett. 1990, 31, 1173–1176; (m)
Mizuno, K.; Sugita, H.; Isagawa, K.; Goto, M.; Otsuji, Y. Tetrahedron Lett. 1993, 34,
5737–5738; (n) Mizuno, K.; Sugita, H.; Hirai, T.; Maeda, H. Chem. Lett. 2000,
1144–1145; (o) Mizuno, K.; Nire, K.; Sugita, H.; Maeda, H. Tetrahedron Lett. 2001,
42, 2689–2692.
Supplementary data
Spectroscopic data of the compounds shown in Tables 1–3 and
the detailed descriptions of experimental procedures. This material
is available free of charge via the Internet at the website. Supple-
mentary data associated with this article can be found in the online
version, at doi:10.1016/j.tet.2009.04.075.
References and notes
1. For the synthesis of MCPs, see: (a) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589–
635; (b) Houben Weyl: Carbocyclic Three-Membered Ring Compounds; de Meijere,
A., Ed.; Thieme: Stuttgart, 1996; Vol. E17a–c; For some reviews, see: (c) Naka-
mura, I.; Yamamoto, Y. Adv. Synth. Catal. 2002, 344, 111–129; (d) Brandi, A.;
Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Rev. 2003, 103, 1213–1270.
6. (a) Purrington, S. T.; Kagen, B. S.; Patrick, T. B. Chem. Rev. 1986, 86, 997–1018; (b)
Smart, B. E. Chem. Rev. 1996, 96, 1555–1556; (c) Dolbier, W. R. J. Fluorine Chem.
2005, 126, 157–163; (d) Jackel, C.; Koksch, B. Eur. J. Org. Chem. 2005, 4483–4503;
(e) O’Hagan, D. Chem. Soc. Rev. 2008, 37, 308–319; (f) Purser, S.; Moore, P. R.;
Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320–330; (g) Organo-
fluorine Chemistry; Uneyama, K., Ed.; Blackwell: Oxford, 2006.
2. For a recent review on the Lewis acid catalyzed ring-opening reactions of MCPs,
see: (a) Shao, L.-X.; Shi, M. Curr. Org. Chem. 2007, 11, 1135–1153; For some se-
lected papers on the Lewis acid catalyzed cycloaddition reactions, see: (b) Shi,
M.; Shao, L.-X.; Xu, B. Org. Lett. 2003, 5, 579–582; (c) Shao, L.-X.; Shi, M. Adv.
Synth. Catal. 2003, 345, 963–966; (d) Shi, M.; Xu, B.; Huang, J.-W. Org. Lett. 2004,
6, 1175–1178; (e) Shao, L.-X.; Xu, B.; Huang, J.-W.; Shi, M. Chem.dEur. J. 2006, 12,
510–517; (f) Huang, J.-W.; Shi, M. Synlett 2004, 2343–2346; (g) Shi, M.; Xu, B.
Tetrahedron Lett. 2003, 44, 3839–3842; For some selected papers from Kilburn’s
group, see: (h) Peron, G. L. N.; Norton, D.; Kitteringham, J.; Kilburn, J. D. Tet-
rahedron Lett. 2001, 42, 347–349; (i) Patient, L.; Berry, M. B.; Coles, S. J.;
Hursthouse, M. B.; Kilburn, J. D. Chem. Commun. 2003, 2552–2553; (j) Rajamaki,
S.; Kilburn, J. D. Chem. Commun. 2005, 1637–1639; For some selected papers
from Huang’s group, see: (k) Huang, X.; Zhou, H.-W. Org. Lett. 2002, 4, 4419–
4422; (l) Huang, X.; Zhou, H.-W.; Chen, W.-L. J. Org. Chem. 2004, 69, 839–842.
3. For the synthesis of diarylvinylidenecyclopropanes, please see: (a) Isagawa, K.;
Mizuno, K.; Sugita, H.; Otsuji, Y. J. Chem. Soc., Perkin Trans. 1 1991, 2283–2285
7. Nyffeler, P. T.; Duron, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C.-H. Angew.
Chem., Int. Ed. 2005, 44, 192–212.
8. (a) Baasner, B.; Hageman, H.; Tatlow, J. Organo-fluorine Compounds. In Houben-
Weyl Methods of Organic Chemistry; Georg Thieme: Stuttgart, New York, NY,
1999; Vol. E10a–c; additional and supplementary volume to the 4th edition.;
(b) Doherty, N. M.; Hoffmann, N. W. Chem. Rev. 1991, 91, 553–573.
9. (a) Lennart, E.; Ola, P. J. Chem. Soc., Perkin Trans. 2 1997, 893–898; (b) Jung, M. E.;
Toyota, A. J. Org. Chem. 2001, 8, 2624–2635; (c) Hill, B.; Liu, Y.; Taylor, S. D. Org.
Lett. 2004, 6, 4285–4288.
10. For the representative examples: (a) Zhou, H. W.; Huang, X.; Chen, W. L. Synlett
2003, 2080–2082; (b) Huang, X.; Fu, W. J. Synthesis 2006, 6, 1016–1020; (c)
Yang, Y. W.; Huang, X. J. Org. Chem. 2008, 73, 4702–4704.
11. Lu, J. M.; Shi, M. J. Org. Chem. 2008, 73, 2206–2210.