Reactions of vinylidenecyclopropanes with diphenyl diselenide in the presence of AIBN and further transformation to produce new naphthalene derivatives

Article abstract of DOI:10.1021/jo0522613

The reactions of vinylidencyclopropanes 1 with diphenyl diselenide 2 in the presence of AIBN produced the corresponding products 4 or 5 in moderate to good yields under mild conditions. The transformation of 4 to the corresponding methylenecyclopropanes 6

Full text of DOI:10.1021/jo0522613

Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide in
the Presence of AIBN and Further Transformation To Produce New
Naphthalene Derivatives
Min Shi*,†,‡ and Jian-Mei Lu†
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China, and East China UniVersity of Science and
Technology, 130 Meilong Road, Shanghai 200237 China
mshi@pub.sioc.ac.cn
ReceiVed October 31, 2005
The reactions of vinylidencyclopropanes 1 with diphenyl diselenide 2 in the presence of AIBN produced
the corresponding products 4 or 5 in moderate to good yields under mild conditions. The transformation
of 4 to the corresponding methylenecyclopropanes 6 was achieved by treatment with hydrogen peroxide
(H2O2) in toluene, and these were further transformed to the corresponding naphthalene derivatives 7 by
treatment with 30 mol % of TfOH in dichloromethane.
Introduction
and well-behaved transformations.4 We have recently reported
the reaction of vinylidenecyclopropanes 1 with diaryl diselenide
2 catalyzed by iodosobenzene diacetate 3 to give the corre-
sponding addition products 4 in moderate to good yields under
mild conditions via a cationic process (Scheme 1).5
Vinylidenecyclopropanes 1 are highly strained and reactive
allenes which undergo a number of facile cycloadditions
1
reactions
and other transformations2 of synthetic utility.
Furthermore, selenium-containing organic molecules are also
very useful compounds in synthetic organic chemistry.3 The
arylselenyl (ArSe-) and alkylselenyl (RSe-) functional groups
have tremendous synthetic utility by virtue of their versatile
During our ongoing investigation of this interesting addition
reaction, we found that vinylidenecyclopropanes 1 can also react
(2) (a) Mizuno, K.; Sugita, H.; Hirai, T.; Maeda, H. Chem. Lett. 2000,
1144. (b) Mizuno, K.; Maeda, H.; Sugita, H.; Nishioka, S.; Hirai, T.;
Sugimoto, A. Org. Lett. 2001, 3, 581. (c) Mizuno, K.; Sugita, H.; Kamada,
T.; Otsuji, Y. Chem. Lett. 1994, 449. (d) Maeda, H.; Hirai, T.; Sugimoto,
A.; Mizuno, K. J. Org. Chem. 2003, 68, 7700. (e) Pasto, D. J.; Miles, M.
F. J. Org. Chem. 1976, 41, 425. (f) Pasto, D. J.; Miles, M. F.; Chou, S.-K.
J. Org. Chem. 1977, 42, 3098. (g) Xu, G.-C.; Ma, M.; Liu, L.-P.; Shi, M.
Synlett 2005, 1869.
(3) Selected monographs: (a) Paulmier, C. Selenium Reagents and
Intermediates in Organic Synthesis; Pergamon: Oxford, 1986. (b) Orga-
noselenium Chemistry; Black, T. G., Ed.; Oxford: New York, 1999. (c)
Organoselenium Chemistry; Wirth, T., Ed.; Springer: Berlin, 2000.
(4) Yao, Q.-W.; Kinney, E. P.; Zheng, C. Org. Lett. 2004, 6, 2997.
(5) Shi, M.; Lu, J.-M. Synlett 2005, 2352.
* To whom correspondence should be addressed. Fax: 86-21-64166128.
† Shanghai Institute of Organic Chemistry.
‡ East China University of Science and Technology.
(1) (a) Mizuno, K.; Sugita, H.; Hirai, T.; Maeda, H.; Otsuji, Y.; Yasuda,
M.; Hashiguchi, M.; Shima, K. Tetrahedron Lett. 2001, 42, 3363. (b)
Mizuno, K.; Nire, K.; Sugita, H.; Otsuji, Y. Tetrahedron Lett. 1993, 34,
6563. (c) Sasaki, T.; Eguchi, S.; Ogawa, T. J. Am. Chem. Soc. 1975, 97,
4413. (d) Pasto, D. J.; Chen, A. F.-T.; Binsch, G. J. Am. Chem. Soc. 1973,
95, 1553. (e) Pasto, D. J.; Chen, A. F.-T. J. Am. Chem. Soc. 1971, 93,
2526. (f) Pasto, D. J.; Borchardt, J. K.; Fehlper, T. P.; Baney, H. F.;
Schwartz, M. E. J. Am. Chem. Soc. 1976, 98, 526. (g) Pasto, D. J.; Chen,
A. F.-T.; Clurdaru, G.; Paquette, L. A. J. Org. Chem. 1973, 38, 1015. (h)
Pasto, D. J.; Borchardt, J. K. J. Am. Chem. Soc. 1974, 96, 6937.
10.1021/jo0522613 CCC: $33.50 © 2006 American Chemical Society
Published on Web 02/02/2006
1920
J. Org. Chem. 2006, 71, 1920-1923

Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide
SCHEME 1. Reactions of Vinylidenecyclopropanes 1 with
Diaryl Diselenide 2 in the Presence of Iodosobenzene
Diacetate 3
SCHEME 2. Plausible Mechanism for the Formation of
4a-h
TABLE 1. Reaction of Vinylidenecyclopropanes 1 with Diphenyl
Diselenide 2 in the Presence of AIBN (5 mol %)
TABLE 2. Reactions of Vinylidenecyclopropanes 1i-k with
Diphenyl Diselenide 2 in the Presence of 5 mol % of AIBN
entrya
1 (R1/R2)
yieldb (%)
1
2
3
1i (C6H5/C6H5)
1j (C6H5/p-ClC6H4)
1k (C6H5/p-CH3C6H4)
5a, 66
5b, 43
5c, 57
a All reactions were carried out using 1 (0.2 mmol), 2 (0.24 mmol), and
AIBN (0.01 mmol) in benzene (1.0 mL) under reflux. b Isolated yields.
SCHEME 3. Plausible Mechanism for the Formation of 5a
a All reactions were carried out using 1 (0.2 mmol), 2 (0.24 mmol), and
AIBN (0.01 mmol) in benzene (1.0 mL) under reflux. b Isolated yields.c 5
mol % of BPO was used.
with diphenyl diselenide in the presence of AIBN to give the
same products 4 via a radical process in good yields. Addition-
ally, the conversion of 4 to the corresponding methylenecyclo-
propanes (MCPs) 6 has also been comprehensively examined.
Moreover, these novel MCPs can be easily converted to the
corresponding naphthalene derivatives 7 in good yields in the
presence of TfOH. Herein, the full details of these reactions
are described.
generated by cleavage of diphenyl diselenide with AIBN, adds
to the double bond of vinylidenecyclopropanes 1 from the
opposite side of the R2 group, presumably due to the steric
repulsion between the R2 and PhSe groups, to form the
corresponding radical intermediate B.6 Intermediate B reacts
with another diphenyl diselenide molecule in the same manner,
opposite from the R2 group, to afford product 4 with regenera-
tion of the phenylseleno radical A.
Furthermore, we found that diaryl-substituted vinylidenecy-
clopropanes 1i-k reacted with diphenyl diselenide in the
presence of AIBN to give the corresponding ring-opened
products 5a-c in moderate yields (Table 2, entries 1-3). The
proposed mechanism for the formation of 5a-c is shown in
Scheme 3. The cyclopropane radical intermediate C undergoes
ring-opening to give allylic radical intermediate D since
substitution by the two phenyl rings in the 3-position of the
Results and Discussion
Initial examination showed that when the radical initiator 2,2′-
azobis(2-methylpropionitrile) (AIBN) or benzoyl peroxide
(BPO) was added to the solution, the reaction of vinylidenecy-
clopropane 1a with diphenyl diselenide proceeded smoothly to
give the corresponding addition product 4a in 92% and 53%
yields, respectively, in refluxing benzene (Table 1, entries 1
and 2). The results are summarized in Table 1. For a variety of
symmetrical vinylidenecyclopropanes 1b-h, the corresponding
addition products 4b-h were obtained in moderate to good
yields (Table 1, entries 3-9). The structures of the products
were determined by NMR spectroscopic data, microanalysis,
and HRMS (Supporting Information). The stereochemistry of
product 4a has been determined by X-ray diffraction.5
A plausible mechanism for the formation of products 4 is
shown in Scheme 2. The phenylseleno radical A, which is
(6) Pasto, D. J.; Miels, F. M. J. Org. Chem. 1976, 41, 2068.
J. Org. Chem, Vol. 71, No. 5, 2006 1921

Shi and Lu
TABLE 3. Further Transformation of 4 by H2O2 (5.0 equiv) with
Pyridine (2.0 equiv) in Toluene
entry
4 (R1/R2)
yieldb (%)
E/Zc,d
7:1
50:1
>200:1
8:1
1
2
3
4
5
6
7
4a (C6H5/C6H5)
6a, 55
6b, 40
6c, 54
6d, 63
6e, 72
6f, 68
6g, 42
4b (p-MeC6H4/C6H5)
4c (p-FC6H4/C6H5)
4d (p-ClC6H4/C6H5)
4e (C6H5/p-ClC6H5)
4f (C6H5/p-MeC6H4)
4g (C6H5/p-MeOC6H4)
7:1
4:1
3:1
a All reactions were carried out with 4 (0.1 mmol), H2O2 (5 equiv), and
pyridine (2.0 equiv) in toluene (1.0 mL). b Isolated yields. c The stereo-
chemistry of 6c was determined by NOESY, and the other compounds were
tentatively assigned according to the general trend. d Determined by 1H
NMR spectroscopic data.
FIGURE 1. ORTEP drawing of E-6f.
SCHEME 4. Plausible Mechanism for the Transformation of
4
allylic radical intermediate D leads to a greater resonance
stabilization than observed in simple allylic radicals.7 Radical
intermediate D reacts with another diphenyl diselenide to
produce the corresponding ring-opened products 5a-c with
regeneration of the radical A. The two gem-aryl groups on the
cyclopropane ring of 1 are essential for the ring-opening reaction
to occur.
The further transformation of addition products 4 was
examined by treatment of them with hydrogen peroxide (H2O2)
in the presence of pyridine.8 We found that a series of novel
MCPs 6 were formed in moderate to good yields in toluene at
room temperature for 5 h and then at 70-80 °C for 12 h as
mixtures of E/Z isomers. The results are summarized in Table
3. Triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
and piperidine could also used as the base in these reactions,
but pyridine gave the best result. The product structures were
determined by NMR spectroscopic data, microanalyses, HRMS,
and X-ray diffraction. The X-ray crystal structure of E-6f is
shown in Figure 1.9 In addition, the E/Z ratios of 6 shown in
1
Table 3 were determined by H NMR spectroscopy, including
NOESY data (Supporting Information).
at the para position of the aryl ring, the corresponding MCP
E-6c was formed in a >200:1 ratio, presumably due to the
strongly electron-withdrawing nature of fluorine atom in addition
to the steric effects (Table 3, entry 3).
The formation of methylenecyclopropanes 6 can be rational-
ized through a2,3-sigmatropic rearrangment on the basis of
previous reports (Scheme 4).10 Selenide 4, which has two
conformations (4A and 4B), is oxidized by H2O2 to form the
corresponding intermediates 4E1 and 4E2, respectively. Because
of the steric repulsion between the R2 and PhSe groups in 4B,
4A should be the major conformer. Therefore, selenoxide 4E1
Interestingly, during our investigations of the further trans-
formation of the obtained products 6, we found that a series of
naphthalene derivatives 7 were formed in moderate to good
yields by the treatment of 6 with trifluoromethanesulfonic acid
(CF3SO3H/TfOH) (30 mol %) in dichloromethane at room
temperature for 1.5 h (Table 4, entries 1-7). A plausible reaction
mechanism is shown in Scheme 5. We believe that upon
treatment of 6a with TfOH, a cationic intermediate F is
formed.11 The allylic rearrangement of cationic intermediate F
produces the corresponding cationic intermediate G, which
undergoes ring-opening to generate the intermediate H.12 The
is the major product, which leads to intermediate 4F1 via a2,3
sigmatropic rearrangement. After treatment with aqueous satu-
rated Na2SO3 solution in pyridine, product E-6 was obtained
as the major product (Scheme 4). For 4c, having a fluorine atom
-
(7) Walborsky, H. M.; Chen, J.-C. J. Am. Chem. Soc. 1970, 92, 7573.
(8) (a) Halazy, S.; Krief, A. Tetrahedron Lett. 1981, 22, 2135. (b) Liu,
L.-P.; Shi, M. Chem. Commun. 2004, 2878.
(9) The crystal data of E-6f has been deposited at the CCDC, no.
270772: empirical formula, C30H26OSe; formula weight, 481.47; crystal
color, habit, colorless, prismatic; crystal system, monoclinic; lattice type,
primitive; lattice parameters, a ) 10.0830(10) Å, b ) 9.6407(10) Å, c )
25.028(3) Å, R ) 90°, â ) 101.187(2)°, γ ) 90°, V ) 2386.6(4) Å3; space
group, P2(1)/n; Z ) 4; Dcalc ) 1.340 g/cm3; F000 ) 992; diffractometer:
Rigaku AFC7R; residuals R, Rw, 0.0408, 0.0769.
(11) (a) Denmark, S. E.; Chen, C.-T. Tetrahedron lett. 1994, 35, 4327.
(b) Freund, T.; Scherf, U.; Mullen. K. Angew. Chem. 1994, 33, 2424. (c)
Chen, C.-T.; Chao, S.-D.; Yen, K.-C.; Chen, C.-H.; Chou, I.-C.; Hon, S.-
W. J. Am. Chem. Soc. 1997, 46, 11341.
(12) (a) Applequist, D. E.; Nickel, G. W. J. Org. Chem. 1979, 44, 321.
(b) Brown, H. C.; Rao, C. G.; Ravindranathan, M. J. Am. Chem. Soc. 1978,
100, 7946.
(10) For a recent review, see: Reich, H. J. Organoselenium Chemistry;
Liotta, D., Ed.; Wiley-Interscience: New York, 1987; pp 365-394.
1922 J. Org. Chem., Vol. 71, No. 5, 2006

Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide
TABLE 4. Treatment of 6 with TfOH (30 mol %)
presence of hydrogen peroxide (H2O2) in toluene. The corre-
sponding MCPs 6a-g were formed in moderate yields, and
these can be easily converted to the corresponding naphthalene
derivatives 7a-g by treatment with TfOH. Efforts are underway
to confirm the mechanistic details of these reactions and their
scope and limitations.
entry
6 (R1/R2)
6 (E/Z)
yieldb (%)
Experimental Section
1
2
3
4
5
6
7
6a (H/C6H5)
6b (Me/C6H5)
6c (F/C6H5)
7:1
50:1
>200:1
8:1
7a, 94
7b, 86
7c, 74
7d, 69
7e, 83
7f, 88
6g, 42
General Procedure for the Reaction of Vinylidenecyclopro-
panes 1 with Diphenyl Diselenide in the Presence of AIBN.
Under an argon atmosphere, vinylidenecyclopropanes 1 (0.2 mmol),
diphenyl diselenide (0.24 mmol), AIBN (0.01 mmol), and benzene
(1.0 mL) were added to a Schlenk tube. The mixture was stirred
under reflux for 10 h, and then the solvent was removed under
reduced pressure and the residue was purified by flash column
chromatography.
6d (Cl/C6H5)
6e (H/p-ClC6H4)
6f (H/p-MeC6H4)
6g (H/p-MeOC6H4)
7:1
4:1
3:1
a All reactions were carried out with 6 (0.1 mmol) and TfOH (30 mol
%) in CH2Cl2 (1.0 mL). b Isolated yields.
General Procedure for the Reaction of Products 4 with
Hydrogen Peroxide (H2O2) and Pyridine in Toluene. Compound
4 (0.1 mmol), 30% H2O2 (0.05 mL), pyridine (0.2 mmol), and
toluene (1.0 mL) were placed in a Schlenk tube. The mixture was
stirred at room temperature for 5 h, and then it was further stirred
at 70-80 °C for an additional 12 h. The mixture was diluted with
10 mL of saturated Na2SO3 solution and extracted with Et2O (3 ×
5.0 mL). The combined organic layers were dried over anhydrous
Na2SO4. The solvent was removed under reduced pressure, and the
residue was purified by flash column chromatography.
SCHEME 5. Plausible Mechanism for the Transformation of
5a
General Procedure for the Reaction of Compound 6 in the
Presence of TfOH. Under an argon atmosphere, compound 6 (0.1
mmol), 30 mol % of TfOH (0.03 mmol), and CH2Cl2 (1.0 mL)
were added into a Schlenk tube. The reaction mixture was stirred
at room temperature for 1.5 h, and then the solvent was removed
under reduced pressure and the residue was purified by flash column
chromatography.
intramolecular Friedel-Crafts reaction affords the intermediate
I from which the corresponding naphthalene derivative 7a is
ultimately produced via an aromatization process (Scheme 3).
Acknowledgment. We thank the State Key Project of Basic
Research (Project 973) (No. G2000048007), Shanghai Municipal
Committee of Science and Technology, and the National Natural
Science Foundation of China for financial support (Nos.
20472096, 203900502, and 20272069).
Conclusions
Supporting Information Available: 1H and 13C NMR spec-
troscopic data and analytic data for compounds 4-7 and X-ray
crystal data of E-6f. This material is available free of charge via
the Internet at http://pubs.acs.org.
We have disclosed an interesting radical addition reaction of
vinylidenecyclopropanes with diphenyl diselenide in the pres-
ence of AIBN to give the corresponding products 4a-h or 5a-c
in moderate to good yields under mild reaction conditions. The
further transformation of 4a-g has been also examined in the
JO0522613
J. Org. Chem, Vol. 71, No. 5, 2006 1923