Reactions of vinylidenecyclopropanes with diphenyl diselenide in the presence of AIBN and thermally-induced further transformations

Article abstract of DOI:10.1002/chem.201103461

In conclusion, we have developed a novel tandem reaction of VDCPs 1 with PhSeSePh to give the corresponding bicyclo[3.1.0]hexane derivatives 4 in good yields in the presence of AIBN, which could undergo a thermal-induced radical 1,4-hydrogen shift through

Full text of DOI:10.1002/chem.201103461

DOI: 10.1002/chem.201103461
Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide in the
Presence of AIBN and Thermally-Induced Further Transformations
Wei Yuan, Yin Wei, Min Shi,* and Yuxue Li*[a]
Vinylidenecyclopropanes (VDCPs) 1 bearing an allene
moiety connected with a highly strained cyclopropane have
been fascinating building blocks in organic synthesis and
have attracted much attention from organic chemists.[1] In
recent years, we and others have disclosed many useful
transformations of VDCPs in the presence of Lewis or
Brønsted acids as well as transition-metal catalysts, subse-
quently enriching the chemistry of VDCPs.[2–4] However, the
chemistry of VDCPs having newly introduced functional
groups such as alkene[4h] and hydroxyl group[4g] has been less
developed thus far. Herein, we wish to report a new chemi-
cal transformation of VDCPs 2 (having an additional alken-
yl group) with diphenyl diselenide in the presence of AIBN
and further transformations of these products. In our previ-
ous work, we have reported that VDCPs 1 could react with
diphenyl diselenide in the presence of AIBN to produce
conjugate diene derivatives 3 in good yields through a radi-
cal intermediate A along with a further transformation
(Scheme 1, reaction (1)).[5] Therefore, we envisaged that if
we used VDCPs 2 as substrates to react with diphenyl dise-
lenide in the presence of AIBN under the standard condi-
tions, an interesting intermolecular reaction might be able
to take place (Scheme 1, reaction (2)).
The initial examination was carried out using VDCP 2a
as the substrate to react with PhSeSePh (1.2 equiv) in the
presence of AIBN (5 mol%) in benzene at 808C and we
found that an interesting cyclized product 4a was formed in
82% yield within 3 h (Table 1, entry 1). Next, we attempted
Table 1. Conditions screening for the reaction of VDCP 2a with PhSe-
SePh in the presence of AIBN.
Entry[a]
Solvent
x
y
[h]
Yield
[%][b]
[equiv]
1
2
3
4
5
6
benzene
toluene
1,4-dioxane
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
1.2
1.2
1.2
1.2
1.2
1.5
1.8
1.2
3
3
3
3
1
1
1
1
82
84
80
84
90
86
90
90
7
8[c]
[a] The reactions were carried out using VDCPs 2a (0.2 mmol), PhSe-
SePh (x equiv) and AIBN (5 mol%) in solvent at 808C with x equiv and
y hours under argon. [b] Isolated product yields. [c] The reaction initiator
was BPO (dibenzoyl peroxide).
to optimize the reaction conditions and the results of these
experiments are summarized in Table 1. As can be seen in
Table 1, using toluene, 1,4-dioxane or acetonitrile (CH3CN)
as the solvent, 4a could be also obtained in good yields
(Table 1, entries 2–4). CH3CN was the solvent of choice, af-
fording the corresponding product 4a in 90% yield within
1 h (Table 1, entry 5). Increasing the employed amount of
PhSeSePh did not improve the yield of 4a (Table 1, entries 6
and 7). Dibenzoyl peroxide (BPO) was also found to be a
useful radical initiator in this reaction (Table 1, entry 8),
however, VDCP 2a did not react with PhSSPh under identi-
cal conditions.
Scheme 1. Reactions of VDCPs with diphenyl diselenide in the presence
of AIBN.
[a] W. Yuan, Dr. Y. Wei, Prof. M. Shi, Prof. Y. Li
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai
200032 (P.R. China)
Fax : (+86)21-64166128
E-mail: Mshi@mail.sioc.ac.cn
Under the optimized reaction conditions, the substrate
scope and limitations of the reaction were explored and the
results are summarized in Table 2. As shown in Table 2, as
for VDCPs 2b–2l, in which R1, R2, and R are aromatic
groups, could react smoothly with PhSeSePh to give the cor-
responding products 4b–4l in 67–94% yields whether they
Supporting information for this article (including spectroscopic charts
of the compounds shown in Tables 1–3, X-ray crystal data of 4i, 5l,
and 6a as well as the detailed descriptions of experimental proce-
dures) is available on the WWW under http://dx.doi.org/10.1002/
chem.201103461.
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Chem. Eur. J. 2012, 18, 1280 – 1285

COMMUNICATION
Table 2. Substrate scope of VDCPs 2 with PhSeSePh in the presence of AIBN.
formed phenyl selenium radical
in the presence of AIBN adds
to the allene moiety of VDCP
1a to give the corresponding
radical intermediate B, which
undergoes an intramolecular
Entry[a]
R1/R2/R
2
4
Yield
radical addition to give the rad-
ical intermediate C. Then, inter-
mediate C reacts with another
molecule of PhSeSePh to give
[%][b]
1
2
3
4
5
6
7
8
C6H5/C6H5/p-FC6H4
C6H5/C6H5/p-ClC6H4
C6H5/C6H5/p-BrC6H4
2b
2c
2d
2e
2 f
2g
2h
2i
4b
4c
4d
4e
4 f
4g
4h
4i
87
85
89
89
C6H5/C6H5/m-BrC6H4
C6H5/C6H5/p-CH3C6H4
C6H5/C6H5/p-CH3OC6H4
p-ClC6H4/C6H5/C6H5
p-ClC6H4/p-ClC6H4/C6H5
p-CH3C6H4/p-CH3C6H4/C6H5
p-CH3OC6H4/p-CH3OC6H4/C6H5
p-BrC6H4/p-BrC6H4/p-BrC6H4
C6H5/C6H5/CH3
the
corresponding
bicyclo-
94
AHCTUNGTERG[NNUN 3.1.0]hexane derivative 4a
67
along with the regeneration of
another phenyl selenium radical
to accomplish the radical reac-
tion cycle (Scheme 2). More-
over, the reaction of VDCP 2p
90[c]
91
9
2j
2k
2l
4j
4k
4l
86
85
10
11
12
81
2m
4m
36[d]
tethered with
a
4-pentenyl
group with PhSe radical pro-
ceeded smoothly to give the
corresponding product 4p in
high yield under the standard
conditions (Table 2, entry 15),
suggesting that the benzenese-
lenenyl radical would not add
to the tethered butenyl chain
since this addition could retard
the reaction rate significantly.
Since products 4 are bicyclo-
13
14
15
2n
2o
2p
–
4o
4p
91
91
[a] The reactions were carried out using VDCPs 2 (0.2 mmol), PhSeSePh (1.2 equiv) and AIBN (5 mol%) in
CH3CN at 808C within 1 h under argon. [b] Isolated product yields. [c] E- or Z-isomeric mixture (ratio=
1.2:1). [d] The yield was determined by H NMR spectroscopic data (1,3,5-trimethoxybenzene as internal stan-
AHCTUNGTRENNUNG
1
dard).
have electron-withdrawing or electron-donating substituents
on their aromatic rings (Table 2, entries 1–11). As for
VDCPs 2h, in which R1 and R2 were different aromatic
groups, the corresponding product 4h was obtained as an E/
Z isomeric mixture with a ratio of 1.2:1 (Table 2, entry 7).
In the case of VDCP 2m, in which R1 and R2 were aromatic
groups and R is a methyl group, the corresponding product
4m was formed in 36% yield (Table 2, entry 12). Using
alkyl-substituted VDCP 2n as substrate, no reaction oc-
curred (Table 2, entry 13); however, using alkyl-substituted
VDCP 2o as the substrate, the desired product 4o could be
also obtained in 91% yield as a mixture of diastereoisomers
(Table 2, entry 14). Furthermore, VDCP 2p tethered with a
methyl group with an olefin could also react with PhSeSePh
smoothly to give the corresponding product 4p in 91%
yield (Table 2, entry 15), suggesting a wide substrate scope.
The structure of 4i has been unambiguously determined by
X-ray diffraction (see the Supporting Information). At-
tempts to synthesize other alkyl-substituted substrates failed
to give the desired products (see the Supporting Information
for more details).
Scheme 2. A plausible reaction mechanism on the formation of 4a.
moiety, they can further undergo radical ring-opening/clos-
ing reactions at high temperature.[7] Therefore, by using 4a
as a reactant, we attempted to explore the further transfor-
mation of 4a. It was found that upon heating at 2008C with-
out any solvent, a new cyclohexene derivative 5a could be
obtained within 1 h in 97% yield stereoselectively in the Z
configuration (Table 3, entry 1) and no reaction occurred
upon heating at <1908C. The substrate scope has also been
On the basis of the previous literature,[5,6] a plausible
mechanism for the formation of 4 has been presented in
Scheme 2 by using 2a as the reaction model. First, the newly
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1281

M. Shi, Y. Li et al.
Table 3. Substrate scope of thermal-induced rearrangement of 4 upon heating at 2008C.
isotope labeling experiment to
examine the reaction outcome
by using dideuterated 2l
(Scheme 4, [D]-2l) as the reac-
tant and the reactions were car-
ried out under the standard
Yield conditions (Scheme 4; for the
Entry[a]
Ar1/Ar2/Ar3
4
5
[%][b]
details, see the Supporting In-
1
2
3
4
5
6
7
8
C6H5/C6H5/C6H5
C6H5/C6H5/p-FC6H4
C6H5/C6H5/p-ClC6H4
C6H5/C6H5/m-BrC6H4
C6H5/C6H5/p-CH3C6H4
C6H5/C6H5/p-CH3OC6H4
p-ClC6H4/C6H5/C6H5
p-ClC6H4/p-ClC6H4/C6H5
p-CH3C6H4/p-CH3C6H4/C6H5
p-BrC6H4/p-BrC6H4/p-BrC6H4
4a
4b
4c
4e
4 f
4g
4h
4i
5a
5b
5c
5e
5 f
5g
5hc
5i
97
97
97
89
93
85
92
92
87
97
formation). It was found that
product [D]-4l could be ob-
tained in 87% yield along with
D content>95%, which could
also undergo thermal-induced
rearrangement to give the cor-
responding product [D]-5l in
97% yield along a complete
1,4-D shift. Moreover, as for
the formation of 5l and [D]-5l
by employing 4l and [D]-4l as
9
10
4j
4l
5j
5l
11
12
4o
4p
5o
5p
97
97
reactants,
a
kinetic isotope
effect kH/kD ꢀ1.5 was observed
at 2008C under the standard
conditions (see the Supporting
Information), suggesting that
À
the C H bond cleavage is the
[a] Reactions were carried out without any solvents at 2008C within 1 h under argon. [b] Isolated product
yields. [c] Containing a pair of diastereomeric isomers, ratio: 1:1
rate-determining step and the
reaction proceeded through a
radical pathway.[9]
investigated and the results are summarized in Table 3. The
thermal-induced rearrangement of compounds 4a–4c and
4e–4l proceeded smoothly to give the corresponding prod-
ucts 5a–5c and 5e–5l in 85–97% yields, suggesting that the
electronic property of R1, R2, and R3 aromatic groups have
no influence on the reaction outcome (Table 3, entries 1–
10). Using alkyl-substituted 4o as the substrate, the corre-
sponding rearrangement product 5o could be also obtained
in 97% yield (Table 2, entry 11) and substrate 4p could be
also transformed to the desired product 5p in 97% yield
(Table 2, entry 12). As for product 4m, in which R is a
methyl group, a double bond migrated product 5m was ob-
tained in 97% yield under identical conditions (Scheme 3).
Scheme 4. Isotope labeling experiments.
The structure of 5l has been unambiguously determined by
X-ray diffraction to be in the Z configuration (see the Sup-
porting Information).
Density functional theory (DFT)[10] studies have also been
performed at UB3LYP[11]/6-31G* level with Gaussian 09
program to investigate the reaction pathway in the forma-
tion of 5 from 4.[12] To obtain more accurate energies, single
point calculations have been performed with the 6-311+
G** basis set. For each structure, harmonic vibration fre-
quency calculations have been carried out and thermal cor-
rections have been undertaken. All structures have been
shown as the transition states (with one imaginary frequen-
cy) or the stationary points (with no imaginary frequency).
The substrate 4 f (Ar1 =Ar2 =Ph, Ar3 =p-CH3C6H4) was
used in the calculation and the proposed reaction pathways
are shown in Scheme 5. In this reaction, the transition states
and intermediates are all characterized as biradicals. Their
Scheme 3. Thermal-induced rearrangement of 4m upon heating at 2008C.
It seems to us that the corresponding product 5 was pro-
duced through a new radical 1,4-H migration.[6b,8] To gain
more mechanistic insight into the reaction, we performed an
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Chem. Eur. J. 2012, 18, 1280 – 1285

Reactions of Vinylidenecyclopropanes
COMMUNICATION
primary structures can be con-
sidered as derivatives of tri-
methylene biradicals, which has
been well studied in the isomer-
ization of cyclopropane to pro-
pene.[13] The triplet states and
broken-symmetry (BS) singlet
states have been considered in
the calculation. The results
showed that the energies of the
triplet transition states are
much higher than those of sin-
glet ones (4 f-Ts1-T, 40.3 kcal
molÀ1,
4 f-Ts2-T,
53.9 kcal
molÀ1). Consequently the triplet
state pathway can be excluded.
This result is also consistent
with the previous experimental
observations that trimethylene
is a singlet biradical.[13a,b]
Scheme 5. The calculated reaction pathway in the formation of 5 f has been indicated. The selected Mulliken
spin densities are shown as italic and the relative free energies DG (298 K) are in kcalmolÀ1 calculated at the
UB3LYP/6-311+G**//UB3LYP/6-31G* level.
In the first step, the cyclopro-
pane unit in 4 f undergoes a ho-
À
molytic C C bond cleavage
through the singlet disrotation
ring-opening transition state 4 f-
Ts1-BS (20.9 kcalmolÀ1), lead-
ing to the slightly more stable
singlet biradical intermediate
4 f-Int-BS (18.1 kcalmolÀ1) (see
the Supporting Information;
Figure SI-6). The recombination
of 4 f-Int-BS is very fast be-
cause it just needs to overcome
an energy barrier of 2.8 kcal
Scheme 6. A plausible reaction mechanism for the formation of 5.
molÀ1. This result is consistent with the high level calculation
of cyclopropane ring-opening process.[13c,d] Due to the deloc-
alization of the radicals to the substituents, the opening bar-
rier is much lower for 4 f compared with that of cyclopro-
pane (about 65 kcalmolÀ1).[13d] The subsequent 1,4-hydrogen
transfer through 4 f-Ts2-BS (31.5 kcalmolÀ1) yields the cor-
responding product 5 f in the Z configuration (see the Sup-
porting Information; Figure SI-6). The overall barrier is
31.5 kcalmolÀ1, which is reasonable for a reaction occurring
at 2008C. The second step is the rate-determining step,
which is also consistent with the deuterium labeling experi-
ment. As shown in the rectangle in Scheme 5, the transition
states of the diphenylmethylene group abstracts the other
neighboring hydrogen atom (4 f-Ts2’-BS, 51.0 kcalmolÀ1; 4 f-
Ts2’-T, 50.3 kcalmolÀ1) can lead to another biradical inter-
mediate. However, this reaction pathway can be excluded
due to the high energy barrier. Therefore, the product (in
which the double bond has an E configuration) cannot be
formed.
at 2008C to give the corresponding biradical intermediate D
or intermediate E (Z configuration). The biradical inter-
mediate D is unstable because it suffers from the steric re-
pulsion between aromatic group and the CH2SePh group.
The biradical intermediate E can abstract the hydrogen
atom to give the corresponding biradical intermediate F in
the Z configuration. The recombination of biradical inter-
mediate F gives the cyclohexene derivative 5 when R’ is an
aromatic group (Scheme 6). On the other hand, when R’ is a
methyl group, the biradical intermediate F undergoes a radi-
cal 1,3-hydrogen shift and then a recombination to give the
corresponding product 5m (Scheme 6).
Aryl selenides can be easily oxidized to the corresponding
selenoxides, which can undergo a variety of interesting rear-
rangements through the elimination.[14,15] Therefore, further
transformation of 5a was performed in the presence of
H2O2 (30% aqueous solution) at low temperature. We
found that the cyclization product 6a was obtained in 57%
yield when the reaction was quenched by saturated NaHSO3
aqueous solution, but an allenic derivative 7a[16] was formed
in 58% yield when the reaction was quenched by saturated
FeSO4 aqueous solution (Scheme 7). The structure of 6a
was unambiguously determined by X-ray diffraction and it
On the basis of the above experiments and DFT calcula-
tions, the mechanism for the formation of 5 has been out-
lined in Scheme 6. Initially, bicycloACTHUNGTRENN[UNG 3.1.0]hexane derivative 4
À
undergoes a homolytic cleavages of C C bond upon heating
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M. Shi, Y. Li et al.
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was formed through the reaction of 7a with the in situ gen-
erated SO2 during the quenching process (see the Support-
ing Information).
In conclusion, we have developed a novel tandem reac-
tion of VDCPs 1 with PhSeSePh to give the corresponding
bicycloACHTUNGTRENNUNG[3.1.0]hexane derivatives 4 in good yields in the pres-
ence of AIBN, which could undergo a thermal-induced radi-
cal 1,4-hydrogen shift through a ring-opening pathway of al-
lylic cyclopropane to give the corresponding cyclohexene
derivatives 5 stereoselectively in the Z configuration and in
good yields at 2008C. Plausible reaction mechanisms have
been also proposed on the basis of deuterium labeling ex-
periments and DFT calculations. In addition, the cyclohex-
ene derivative 5a can be transformed into cyclic sulphone
6a and allene 7a in moderate yields in the presence of
H2O2. Further investigations on the mechanistic details of
the reaction as well as the further exploration of other
useful chemical transformations of vinylidenecyclopropanes
are in progress.
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Acknowledgements
We thank the Shanghai Municipal Committee of Science and Technology
(08dj1400100-2), National Basic Research Program of China ACHTUNTRGNEUNG(973)-
2009CB825300, and the National Natural Science Foundation of China
for financial support (21072206, 20472096, 20872162, 20672127, 20821002
and 20732008).
Keywords: 1,4-hydrogen shift
oxidation radical reactions
vinylidenecyclopropanes
·
diphenyl diselenide
ring-opening
·
·
·
·
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Received: November 4, 2011
Published online: January 2, 2012
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