Ring-opening reactions of diarylvinylidenecyclopropanes by iodine and bromine

Article abstract of DOI:10.1016/j.tetlet.2005.08.130

Diarylvinylidenecyclopropanes undergo a novel ring-opening reaction upon treatment with iodine or bromine at 0-25°C in 1,2-dichloroethane to give the corresponding iodinated or brominated naphthalene derivatives in good to high yields within 3 h. The furt

Full text of DOI:10.1016/j.tetlet.2005.08.130

Tetrahedron
Letters
Tetrahedron Letters 46 (2005) 7609–7613
Ring-opening reactions of diarylvinylidenecyclopropanes
by iodine and bromine
Min Shi,a,* Ming Maa and Li-Xiong Shaob
aSchool of Chemistry and Pharmaceutics, East China University of Science and Technology, 130 Mei Long Road,
Shanghai 200237, China
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, China
Received 7 July 2005; revised 21 August 2005; accepted 24 August 2005
Available online 15 September 2005
Abstract—Diarylvinylidenecyclopropanes undergo a novel ring-opening reaction upon treatment with iodine or bromine at 0–25 ꢀC
in 1,2-dichloroethane to give the corresponding iodinated or brominated naphthalene derivatives in good to high yields within 3 h.
The further transformation of the corresponding iodinated or brominated naphthalene derivatives has been disclosed.
ꢁ 2005 Elsevier Ltd. All rights reserved.
Thermal and photochemical skeletal conversions of
vinylidenecyclopropanes 1 have attracted much atten-
tion from mechanistic, theoretical, spectroscopic, and
synthetic viewpoints in the past decades.1,2 Vinylidene-
cyclopropanes 1 also undergo a variety of unique addi-
tion reactions with electrophiles to give novel products
sometimes along with the formation of cyclopropane
ring-opened products.3
iodinated naphthalene derivative 2a was obtained in
51% yield along with trace of 3a in 1,2-dichloroethane
(DCE) at 0 ꢀC (Table 1, entry 1). However, with the mo-
lar ratio of 1a:I2 = 1:2, the iodinated naphthalene deriv-
ative 3a was obtained in 60% yield along with trace of 2a
under identical conditions (Table 1, entry 2). The yield
of 3a can be improved to 95% yield using large excess
amounts of iodine (molar ratio of 1a:I2 = 1:40) (Table
1, entry 4). In addition, when this reaction was carried
out at 0 ꢀC and 25 ꢀC (room temperature) with the mo-
lar ratio of 1a:I2 = 1:10, the corresponding iodinated
naphthalene derivative 3a can still be obtained in high
yields (93% and 95% isolated yields, respectively) (Table
1, entries 5 and 6). This reaction is fairly effective and
can complete within 3 h at 0 ꢀC or 25 ꢀC. The solvent
effects have been examined under identical conditions
(Table 1, entries 7–9). We found that DCE is the best
solvent in this reaction. In the bromination of 1a
under similar conditions, with the molar ratio of
1a:Br2 = 1:10 or 1:20, the corresponding brominated
naphthalene derivative 3a was obtained similarly in
75% and 78% yields at 25 ꢀC in DCE (Table 1, entries
10 and 11).
Previously, we reported that arylvinylidenecyclopro-
panes 1 undergo a novel rearrangement in the presence
of Lewis acids or Brønsted acids to give the correspond-
ing naphthalene derivatives in good to high yields under
mild conditions.4 In this letter, we wish to report the
addition reactions of diarylvinylidenecyclopropanes 1
with iodine or bromine under similar conditions to give
the corresponding cyclopropane ring-opened addition
products. We first carried out the reaction of diphenyl-
vinylidenecyclopropane 1a with iodine (I2) in a variety
of organic solvents and found that in the corresponding
iodinated naphthalene derivative either 2a or 3a was
formed in good yield depending on the employed
amounts of iodine. The results are summarized in Table
1. With the molar ratio of 1a:I2 = 1:1, the corresponding
Awide range of electronically and structurally diverse
diarylvinylidenecyclopropanes 1 can be employed in this
reaction under these optimized conditions. The results
are summarized in Table 2. As can be seen from Table
2, with respect to the electron-rich, electron-neutral,
and electron-poor diarylvinylidenecyclopropanes 1 (R1
Keywords: Diarylvinylidenecyclopropanes; Iodine; Bromine; Ring-
opening reaction; Naphthalene derivatives.
*
Corresponding author. Fax: +86 21 64166128; e-mail: mshi@pub.
sioc.ac.cn
0040-4039/$ - see front matter ꢁ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2005.08.130

7610
M. Shi et al. / Tetrahedron Letters 46 (2005) 7609–7613
Table 1. The ring-opening reaction of diphenylvinylidenecyclopropane 1a with iodine or bromine in a variety of solvents
C6H5
C6H5
C6H5
C6H5
+
X
X
C6H5
C6H5
+
.
X2
solvent, 3 h
CH2X
CH3
C6H5
1a
3a (X= I)
4a (X= Br)
2a (X= I)
Entry
Solvent
X2
Molar ratio
1a:X2
Temp./(ꢀC)
Yield/(%)a
2a
Yield/(%)a
3a or 4a
1
2
3
4
5
6
7
8
DCE
DCE
DCE
DCE
DCE
DCE
THF
Toluene
MeCN
DCE
DCE
I2
I2
I2
I2
I2
I2
I2
I2
1:1
1:2
1:5
0
0
0
0
0
25
0
0
0
25
25
51
Trace
Trace
60
83
95
93
95
62
56
61
0
0
0
0
0
0
0
0
0
1:40
1:10
1:10
1:10
1:10
1:10
1:20
1:10
9
10
11
I2
Br2
Br2
78
75
a Isolated yields.
Table 2. The ring-opening reaction of arylvinylidenecyclopropane 1 with excess iodine or bromine in DCE at 0 or 25 ꢀC
R1
R2
R1
R1
X
CH2X
X2
+
.
DCE, 3 h
R
R2
1
3 or 4
R = Me, MeO, F substituents in R1 group
Entrya
1 (R1/R2)
X2
Temp./ꢀC
Yield/(%)b
3 or 4
1
2
3
4
5
6
7
8
9
1b (C6H5/p-MeC6H4)
1c (C6H5/p-MeOC6H4)
1d (p-MeC6H4/C6H5)
1e (p-MeOC6H4/C6H5)
1f (p-FC6H4/C6H5)
I2
I2
I2
I2
I2
I2
Br2
Br2
Br2
0
0
0
0
0
25
25
25
25
3b, 68
3c, 64
3d, 85
3e, 84
3f, 20
3f, 73
4b, 44
4c, 61
4d, 46
1f (p-FC6H4/C6H5)
1b (C6H5/p-MeC6H4)
1c (C6H5/p-MeOC6H4)
1e (p-MeOC6H4/C6H5)
a All the reactions were carried out in a ratio of 1:I2 = 1:10.
b Isolated yields.
and R2 = aromatic group), these reactions with iodine
or bromine proceeded smoothly to give the correspond-
ing naphthalene derivatives 3 or 4 in moderate to good
yields within 3 h in most cases (Table 2, entries 1 to
9). For di(p-fluorophenyl)vinylidenecyclopropane 1f,
the corresponding rearranged product 3f was obtained
in 73% yield at 25 ꢀC (Table 2, entry 6). The structures
of 2a and 3 were determined by 1H and 13C NMR spec-
troscopic data, and HRMS or microanalyses. Their
spectroscopic and analytic data are shown in Supporting
Information. The crystal structure of 3b was further
determined by X-ray diffraction (Fig. 1).5
On the basis of our previous investigation on the Lewis
acids or Brønsted acids catalyzed rearrangement of di-
arylvinylidenecyclopropanes 1,4 a plausible mechanism
for the reaction of diarylvinylidenecyclopropanes 1 with
iodine is outlined in Scheme 1. The addition of iodine to
diphenylvinylidenecyclopropane 1a produces the inter-
mediate A, which undergoes the cyclopropane ring-
opening reaction to form the cationic intermediate B.6
The intramolecular Friedel–Crafts reaction affords the
intermediate C. The reprotonation and aromatization
of the intermediate D furnish the iodinated naphthalene
derivative 2a (Scheme 1). On the other hand, in the pres-

M. Shi et al. / Tetrahedron Letters 46 (2005) 7609–7613
7611
ence of large excess amount of I2, the addition of iodine
to the double bond of the intermediate C affords the
intermediate E which undergoes the ring-opening pro-
cess to form the cationic intermediate F,7 an allylic cat-
ionic intermediate. The aromatization of the cationic
intermediate F by elimination of HI furnishes the iodin-
ated naphthalene derivative 3a (Scheme 1).
The further transformation of 3a is shown in Scheme 2.
The coupling reaction of 3a with diphenyl diselenide
(PhSeSePh) in the presence of sodium borohydride
(NaBH4) and methanol (MeOH) with a molar ratio of
3a:PhSeSePh:NaBH4:CH3OH = 1:0.5:2:5 produced the
coupled product 5a in 89% yield in THF at room tem-
perature (Scheme 2).8 The further transformation of 5a
by Heck-type coupling reaction with excess amounts
of methyl acrylate (CH2@CHCO2CH3)9 in the presence
of Pd(II) catalyst and triethylamine (Et3N) is shown in
Scheme 3. The coupled product 6a was obtained in good
yield in DMF at 100 ꢀC (Scheme 3).
In this letter, we disclosed a novel ring-opening reaction
of diarylvinylidenecyclopropanes 1 upon treatment with
iodine or bromine to give the corresponding iodinated
or brominated naphthalene derivatives in good to high
yields within 3 h under mild conditions. In addition,
the further possible transformation of 3 has been
disclosed. Efforts are underway to elucidate the mecha-
nistic details and to extend the scope of this novel
reaction.
Figure 1. The ORTEP drawing of 3b.
C6H5
+
C6H5
C6H5
I
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
I2
I-
I-
+
I
B
A
-H+
I
H+
-H+
I
+
I
2a
+
intramolecular
Friedel-Crafts
reaction
H
C
D
I
I2
I
I-
C
I
I-
3a
+
+
H
I
E
F
Scheme 1. Aplausible reaction mechanism of arylvinylidenecyclopropanes 1 with iodine.

7612
M. Shi et al. / Tetrahedron Letters 46 (2005) 7609–7613
C6H5
C6H5
C6H5
C6H5
I
I
NaBH4, MeOH
+
Se Se
Se
THF, r.t.
CH2I
3a
5a, 89%yield
Scheme 2. The reaction of 3a with diphenyldiselenide in the presence of NaBH4 and MeOH.
2. For synthesis of vinylidenecyclopropanes, please see: (a)
Isagawa, K.; Mizuno, K.; Sugita, H.; Otsuji, Y. J. Chem.
Soc., Perkin Trans. 1 1991, 2283–2285, and references cited
therein; (b) Sasaki, T.; Eguchi, S.; Ohno, M.; Nakata, F. J.
Org. Chem. 1976, 41, 2408–2411; (c) Sasaki, T.; Eguchi, S.;
Ogawa, T. J. Org. Chem. 1974, 39, 1927–1930; (d) Sasaki,
T.; Eguchi, S.; Ogawa, T. Heterocycles 1975, 3, 193–196; (e)
Eguchi, S.; Arasaki, M. J. Chem. Soc., Perkin Trans. 1
1988, 1047–1050; (f) Sugita, H.; Mizuno, K.; Mori, T.;
Isagawa, K.; Otsuji, Y. Angew. Chem., Int. Ed. Engl. 1991,
30, 984–986; (g) Patrick, T. B. Tetrahedron Lett. 1974, 15,
1407–1408; (h) Al-Dulayymi, J. R.; Baird, M. S. J. Chem.
Soc., Perkin Trans. 1 1994, 1547–1548; (i) Patrick, T. B. J.
Org. Chem. 1977, 42, 3354–3356; (j) Hartzler, H. D. J. Am.
Chem. Soc. 1971, 93, 4527–4531.
3. The other papers related to vinylidenecyclopropanes. See:
for the reactions of vinylidenecyclopropanes with carbenes
and carbene complexes. (a) Crandall, J. K.; Paulson, D. R.;
Bunnell, C. A. Tetrahedron Lett. 1969, 4217–4220; (b) Hwu,
C.-C.; Wang, F.-C.; Yeh, M.-C. P. J. Organomet. Chem.
1994, 474, 123–128; (c) Billups, W. E.; Haley, M. M.; Boese,
R.; Blaser, D. Tetrahedron 1994, 50, 10693–10700; (d)
Maeda, H.; Hirai, T.; Sugimoto, A.; Mizuno, K. J. Org.
Chem. 2003, 68, 7700–7706; (e) Bloch, R.; Perchec, P. L.;
Conia, J.-M. Angew. Chem., Int. Ed. Engl. 1970, 9, 798–799;
(f) Pasto, D. J.; Yang, S. H. J. Org. Chem. 1986, 51, 1676–
1680; For the addition reactions to alkenylidenecyclopro-
panes. (g) Pasto, D. J.; Miles, M. F. J. Org. Chem. 1976, 41,
2608–2611; (h) Pasto, D. J.; Chen, A. F.-T.; Binsch, G. J.
Am. Chem. Soc. 1973, 95, 1553–1562; (i) Pasto, D. J.; Chen,
A. F.-T. J. Am. Chem. Soc. 1971, 93, 2562–2564; (j) Pasto,
D. J.; Borchardt, J. K.; Fehlner, T. P.; Baney, H. F.;
Schwartz, M. E. J. Am. Chem. Soc. 1976, 98, 526–529; (k)
Pasto, D. J.; Fehlner, T. P.; Schwartz, M. E.; Baney, H. F.
J. Am. Chem. Soc. 1976, 98, 530–534; (l) Pasto, D. J.; Miles,
M. F. J. Org. Chem. 1976, 41, 425–432; (m) Pasto, D. J.;
Chen, A. F.-T.; Cuirdaru, G.; Paquette, L. A. J. Org. Chem.
1973, 38, 1015–1026; (n) Gompper, R.; Lach, D. Tetra-
hedron Lett. 1973, 2683–2686; (o) Gompper, R.; Lach, D.
Tetrahedron Lett. 1973, 2687–2690; (p) Pasto, D. J.;
Wampfler, D. Tetrahedron Lett. 1974, 15, 1933–1936; (q)
Pasto, D. J.; Whitmer, J. L. J. Org. Chem. 1980, 45, 1987–
1990; (r) Pasto, D. J.; Brophy, J. E. J. Org. Chem. 1991, 56,
4556–4559; (s) Cairns, P. M.; Combie, L.; Pattenden, G.
Tetrahedron Lett. 1982, 23, 1405–1408; (t) Combie, L.;
Maddocks, P. J.; Pattenden, G. Tetrahedron Lett. 1978, 19,
3483–3486.
O
C
O
C6H5
C6H5
H2C
C
OMe
H
OMe
C6H5
5a
Se
Pd(OAc)2, Et3N, DMF, 100 oC
6a, 62%yield
Scheme 3. Heck-type coupling reaction of 5a with methyl acrylate.
Acknowledgments
We thank the State Key Project of Basic Research (Pro-
ject 973) (No. G2000048007), Shanghai Municipal Com-
mittee of Science and Technology, and the National
Natural Science Foundation of China for financial sup-
port (Nos. 20472096, 203900502, and 20272069).
Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.tetlet.
2005.08.130.
References and notes
1. (a) Poutsma, M. L.; Ibarbia, P. A. J. Am. Chem. Soc. 1971,
93, 440–450; (b) Smadja, W. Chem. Rev. 1983, 83, 263–320;
(c) Paulson, D. R.; Crandall, J. K.; Bunnell, C. A. J. Org.
Chem. 1970, 35, 3708–3714; (d) Hendrick, M. E.; Hardie, J.
A.; Jones, M., Jr., J. Org. Chem. 1971, 36, 3061–3062; (e)
Patrick, T. B.; Haynie, E. C.; Probst, W. J. J. Org. Chem.
1972, 37, 1553–1556; (f) Aue, D. H.; Meshishnek, M. H. J.
Am. Chem. Soc. 1977, 99, 223–231; (g) Sasaki, T.; Eguchi, S.;
Ogawa, T. J. Am. Chem. Soc. 1975, 97, 4413–4414; (h)
Sadler, I. H.; Stewart, J. A. G. J. Chem. Soc., Perkin Trans. 2
1973, 278–288; (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; (k) Akasaka, T.; Misawa, Y.;
Ando, W. Tetrahedron Lett. 1990, 31, 1173–1176; (l)
Mizuno, K.; Sugita, H.; Isagawa, K.; Goto, M.; Otsuji, Y.
Tetrahedron Lett. 1993, 34, 5737–5738; (m) Mizuno, K.;
Nire, K.; Sugita, H.; Otsuji, Y. Tetrahedron Lett. 1993, 34,
6563–6566; (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; (p) Mizuno, K.; Maeda, H.; Sugita, H.; Nishioka, S.;
Hirai, T.; Sugimoto, A. Org. Lett. 2001, 3, 581–584; (q)
Mizuno, K.; Sugita, H.; Hirai, T.; Maeda, H.; Otsuji, Y.;
Yasuda, M.; Hashiguchi, M.; Shima, K. Tetrahedron Lett.
2001, 42, 3363–3366; (r) Maeda, H.; Zhen, L.; Hirai, T.;
Mizuno, K. ITE Lett. Batteries, New Technol. Med. 2002, 3,
485–491; (s) Sydnes, L. K. Chem. Rev. 2003, 103, 1133–1150.
4. Xu, G.-C.; Ma, M.; Liu, L.-P.; Shi, M. Synlett 2005, 1869–
1872.
5. The crystal data of 3b have been deposited in CCDC with
deposition number 273884. Empirical Formula: C24H18I2;
Formula weight: 560.21; Crystal color, habit: colorless,
prismatic; Crystal dimensions: 0.516 · 0.475 · 0.438 mm;
Crystal system: monoclinic; Lattice type: primitive; Lattice
˚
˚
parameters: a = 11.6109(10) A, b = 9.9771(9) A, c =
˚
18.1552(16) A, a = 90ꢀ, b = 103.249(2)ꢀ, c = 90ꢀ, V =
2047.2(3) A ; Space group: P2(1)/n; Z = 4; Dcalc
3
˚
=

M. Shi et al. / Tetrahedron Letters 46 (2005) 7609–7613
7613
1.818 g/cm3; F000 = 1072; Diffractometer: Rigaku AFC7R;
Residuals: R; Rw: 0.0466, 0.1068.
6. (a) Fitjer, L. Angew. Chem., Int. Ed. Engl. 1975, 14, 360–361;
(b) Siehl, H.-U.; Aue, D. H. In Dicoordinated Carbocations;
Rappoport, Z., Stang, P. J., Eds.; John Wiley & Sons: New
York, 1997; pp 137–138; (c) Olah, G. A.; Reddy, V. P.;
Prakash, G. K. S. Chem. Rev. 1992, 92, 69–95.
Am. Chem. Soc. 2004, 126, 5309–5317; (c) Comasseto, J. V.;
Omori, A. T.; Porto, A. L. M.; Andrade, L. H. Tetrahedron
Lett. 2004, 45, 473–476; (d) Oddershede, J.; Henriksen, L.;
Larsen, S. Org. Biomol. Chem. 2003, 1, 1053–1060; (e)
Ranu, B. C.; Mandal, T.; Samanta, S. Org. Lett. 2003, 5,
1439–1441; (f) Shi, M.; Liu, L.-P.; Tang, J. Org. Lett. 2005,
7, 3085–3088.
7. (a) Heasley, G. E.; Smith, D. A.; Smith, J. N.; Heasley, V.
L.; Shellhamer, D. F. J. Org. Chem. 1980, 45, 5206–5209;
(b) Fahey, R. C.; Schneider, H. J. J. Am. Chem. Soc. 1968,
90, 4429–4434.
8. (a) Mioskowski, C. Tetrahedron Lett. 1994, 35, 5437–5440;
(b) Iwaoka, M.; Komatsu, H.; Katsuda, T.; Tomoda, S. J.
9. (a) Heck, R. F. Acc. Chem. Res. 1979, 12, 146–151; (b)
Dieck, H. A.; Heck, R. F. J. Am. Chem. Soc. 1974, 96,
1133–1136; (c) Heck, R. F.; Nolley, J. P., Jr. J. Org. Chem.
1972, 37, 2320–2322; (d) Plevyak, J. E.; Heck, R. F. J. Org.
Chem. 1978, 43, 2454–2456; (e) Chalk, A. J.; Magennis, S.
A. J. Org. Chem. 1976, 41, 273–278.