BF3·OEt2-catalyzed intermolecular reactions of arylmethylenecyclopropanes with (E)-1,1,3-triarylprop-2-en-1-ols

Article abstract of DOI:10.1016/j.tet.2011.06.009

BF₃·OEt₂-catalyzed intermolecular reactions of arylmethylenecyclopropanes with (E)-1,1,3-triarylprop-2-en-1-ols produced the corresponding triene compounds, alcoholic derivatives or cyclobutane derivatives in moderate to excellent yi

Full text of DOI:10.1016/j.tet.2011.06.009

Tetrahedron 67 (2011) 5732e5739
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BF3$OEt2-catalyzed intermolecular reactions of arylmethylenecyclopropanes
with (E)-1,1,3-triarylprop-2-en-1-ols
*
Lei Wu, Min Shi
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 April 2011
Received in revised form 31 May 2011
Accepted 7 June 2011
Available online 14 June 2011
BF3$OEt2-catalyzed intermolecular reactions of arylmethylenecyclopropanes with (E)-1,1,3-triarylprop-2-
en-1-ols produced the corresponding triene compounds, alcoholic derivatives or cyclobutane derivatives
in moderate to excellent yields under mild conditions.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Lewis acid
Arylmethylenecyclopropanes
1,2-Aryl migration
Ring opening
Ring enlargement
Carbon cationic intermediate
1. Introduction
cyclopropane under mild conditions.7 On the basis of the above
results, herein, we wish to report a new intermolecular reaction of
Methylenecyclopropanes (MCPs) are highly strained but readily
accessible molecules that have been serving as useful building
blocks in organic synthesis for a long time.1 For example, in the
presence of transition metals or Lewis acids, MCPs can undergo
a variety of ring-opening/cycloaddition reactions because the relief
of ring strain provides a powerful thermodynamic driving force.2,3
Thus far, a number of interesting cycloadditions and ring enlarge-
ments/openings of MCPs have been explored. For example, Yama-
moto et al. reported cycloaddition reactions of MCPs with
aldehydes and imines, using a palladium catalyst, that afforded the
corresponding tetrahydrofuran and pyrrolidine skeletons in good
yields.4 In addition, we and others have developed a number of
heterocycle-forming reactions from MCPs and aldehydes or imines
as well as ring enlargements of MCPs in the presence of Lewis or
Brønsted acids.5,6 In our previous work, we have recently reported
Lewis acid-catalyzed cascade reactions of MCPs as well as vinyl-
idenecyclopropanes (VDCPs) with 1,1,3-triarylprop-2-yn-1-ols or
their methyl ethers or 1,6-diynes and 1,6-enynes to produce func-
tionalized methylenecyclobutene, cyclobutane, and cyclopropane
derivatives or 4-dihydro-1H-cyclopenta[b]naphthalene derivatives
and 1,2,3,8-tetrahydrocyclopenta[a]indene derivatives, respecti-
vely, in good to high yields depending on the substituents on the
MCPs 1 with (E)-1,1,3-triarylprop-2-en-1-ols 2 catalyzed by Lewis
acids to produce a variety of different products depending on the
electronic nature of the substrates in good to excellent total yields
under mild conditions.
2. Results and discussion
Initial examinations using diphenylmethylenecyclopropane (1a,
0.2 mmol) and (E)-1,1,3-triphenylprop-2-en-1-ol (2a, 0.2 mmol) as
the substrates in the presence of various Lewis acids (10 mol %)
were aimed at determining the best reaction conditions for this
interesting intermolecular reaction and the results of these exper-
iments are summarized in Table 1. We found that in the presence of
BF3$OEt2 (10 mol %), this intermolecular reaction could complete
with 5 min at room temperature in dichloromethane (DCM), giving
the triene compound 3aa in nearly quantitative yield as cis- and
trans-isomeric mixtures because of the position of the two phenyl
rings on the newly-formed double bond (Table 1, entry 1). Either no
reaction occurred or complex product mixtures were obtained
when other Lewis acids, such as Yb(OTf)3, Fe(OTf)2, In(OTf)3, and
Zr(OTf)4 were utilized as the catalysts (Table 1, entries 2e5). Even in
the presence of a Brønsted acid, such as trifluoromethanesulfonic
acid CF3SO3H (TfOH) (50 mol %), 3aa could also be produced in 97%
yield (Table 1, entry 6). Solvent effects have been examined with
BF3$OEt2 (10 mol %) at room temperature in 1,2-dichloroethane
* Corresponding author. E-mail address: mshi@mail.sioc.ac.cn (M. Shi).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.06.009

L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
5733
Table 1
significant effect on the reaction outcomes. As for MCPs 1b and 1c
bearing electron-withdrawing substituents, such as Cl atom and Br
atom on the aromatic rings, the corresponding triene products 3ba
and 3ca were produced in good yields along with the formation of
alcoholic compounds 4ba and 4ca in moderate yields (Table 2,
entries 5 and 6). As for MCP 1d bearing moderately electron-
donating substituents Me group on the aromatic rings, the corre-
sponding triene compound 3da was also obtained in nearly
quantitative yield (Table 2, entry 7). On the basis of 1H NMR NOESY
spectroscopic data, the major isomeric product in 3da was iden-
tified as cis-configuration with the two Ar3 rings at the same side
of the double bond (See the Supplementary data for more details).
But in the case of MCP 1e having strongly electron-donating
substituents MeO group on the aromatic rings, besides the triene
compound 3ea another type of alcoholic product 5ea and its di-
meric ether 6ea were also obtained in excellent total yield under
the standard conditions (Scheme 1).
Optimization of the reaction conditionsa
Ph
OH
Ph
Ph
Ph
Ph
Ph
cat (10 mol%)
solvent, rt, 5 min
Ph
Ph
+
Ph
Ph
2a
1a
3aa
1.0 equiv
1.0 equiv
Entry
Cat (10 mol %)
Solvent
Yieldb (%) (cis/trans)c
1
2
3
4
5
6
7
8
9
BF3$OEt2
Yb(OTf)3
In(OTf)3
Zr(OTf)4
Fe(OTf)2$2CH3CN
HOTf (50 mo l%)
BF3$OEt2
BF3$OEt2
BF3$OEt2
DCM
DCM
DCM
DCM
DCM
DCM
DCE
97 (1.0/0.5)
nr
Complex mixtures
Complex mixtures
nr
90 (1.0/0.5)
94 (1.0/0.5)
Complex mixtures
87 (1.0/0.5)
THF
Toluene
a
All reactions were conducted with MCP 1a (0.2 mmol, 1.0 equiv), (E)-1,1,3-tri-
phenylprop-2-en-1-o1 2a (0.2 mmol, 1.0 equiv), and the catalyst (10 mol %) in the
solvent (2.0 mL) at room temperature within 5 min otherwise specified.
b
Isolated yield.
c
Ratio of cis, trans-isomers determined by 1H NMR spectroscopic data.
(DCE), tetrahydrofuran (THF), and toluene. It was found that in THF,
complex product mixtures were formed and in DCE and toluene,
the desired product 3aa could also be obtained in good yields (Table
1, entries 7e9). Therefore, the optimized reaction conditions are
considered to carry out the reaction in DCE or DCM using MCPs 1
(1.0 equiv) and (E)-1,1,3-triarylprop-2-en-1-ols 2 (1.0 equiv) as the
substrates in the presence of BF3$OEt2 (10 mol %) at room
temperature.
Under these optimal reaction conditions, we next examined the
generality of this interesting triene compound-forming reaction
using a variety of starting materials MCPs 1 and (E)-1,1,3-
triarylprop-2-en-1-ols 2 as the substrates and the results are
shown in Table 2. As can be seen from Table 2, the corresponding
triene compounds 3 were obtained in good to excellent yields in
most cases. Using MCP 1a as the substrate, the electronic nature of
the aromatic rings in (E)-1,1,3-triarylprop-2-en-1-ols 2 has little
influence on the reaction outcomes (Table 2, entries 1e4). How-
ever, the substituents on the aromatic rings of MCPs have
Scheme 1. BF3$OEt2-catalyzed intermolecular reaction of 1e with 2a.
Furthermore, the structure of compound 5ea was un-
ambiguously determined by X-ray diffraction of its single-crystals.
The ORTEP drawing of 5ea is shown in Fig. 1 and its CIF data are
presented in the Supplementary data.8
Moreover, we also examined the reactions of other MCPs having
one methyl group and one aromatic ring with (E)-1,1,3-triarylprop-2-
en-1-ols under the standard conditions and the results of these ex-
periments are summarized in Table 3. As for MCP 1f in which Ar1 is
a phenyl group, methylenecyclobutane 7fa was formed in 78% yield
along with the formation of 8fa in 14% yield (Table 3, entry 1). Using
MCP 1g having an electron-withdrawing substituent Br atom on the
aromaticringassubstrateafforded themajorproduct 7gain62% yield
Table 2
BF3$OEt2-catalyzed intermolecular reactions of MCPs 1 with (E)-1,1,3-triarylprop-2-en-1-ols 2 under the optimal reaction conditionsa
Ar1
OH
Ar1
Ar1
OH
Ar3
Ar3
1.0 equiv
Ar3
Ar3
Ar3
.
Ar1
Ar1
BF3 OEt2 (10 mol%)
+
Ar2
+
Ar1
Ar2
DCM, rt, 5 min
Ar2
1
2
Ar3
1.0 equiv
3
4
Entry
Ar1
Ar2
Ar3
Yield of productb (%)
3 (cis/trans)c
4
1
2
3
4
5
6
7
1a
1a
1a
1a
1b
1c
1d
Ph
Ph
Ph
Ph
p-ClC6H4
p-BrC6H4
p-MeC6H4
2b
2c
2d
2e
2a
2a
2a
p-MeC6H4
p-ClC6H4
Ph
Ph
p-MeC6H4
p-BrC6H4
Ph
3ab, 90 (1 .0/0.5)
3ac, 85 (1.0/0.5)
3ad, 96 (1 .0/0.4)
3ae, 92 (1.0/0.6)
3ba, 63 (1.0/0.6)
3ca, 68 (1.0/0.5)
3da, 98 (1.0/0.5)
Ph
Ph
Ph
Ph
Ph
4ba, 32
4ca, 29
Ph
Ph
a
All reactions were conducted with MCP1 (0.2 mmol, 1.0 equiv), (E)-1,1,3-triarylprop-2-en-1-ol 2 (0.2 mmol, 1.0 equiv), and BF3$OEt2(10 mol %) in DCM (2.0 mL) at room
temperature within 5 min otherwise specified.
b
Isolated yield.
c
Ratios of cis, trans-isomers were determined by 1H NMR spectroscopic data.

5734
L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
Scheme 2. Transformation of 7he to 10 via Suzuki coupling reaction.
To investigate the reaction mechanism, a control experiment as
shown in Scheme 3 was conducted. With the addition of HOTf
(10 mol %), product 4ab could be transformed to the major isomer
cis-3ab in DCM in 59% yield, suggesting that triene compounds 3
might be derived from the corresponding alcohol products 4 with
the elimination of H2O during the reaction process.
OH
Ph
Fig. 1. ORTEP drawing of 5ea.
HOTf (10 mol%)
DCM, rt, 5 min
Ph
Ph
Ph
Ph
Ph
Ph
p-MeC6H4
Ph
p-MeC6H4
4ab
cis-3ab, 59% yield
Scheme 3. HOTf-Mediated transformation of 4ab to cis-3ab.
Table 3
BF3$OEt2-catalyzed intermolecular reactions of MCPs 1 with (E)-1,1,3-triarylprop-2-en-1-ols 2 under the optimal reaction conditionsa
Ar1
OH
OH
Ar1
BF3.OEt2 (10 mol%)
DCM, rt, 5 min
Ar2
Ar2
Ar1
+
Ar2
Ar2
Ph
Ar2
Ar2
+
Ph
1
2
Ph
1.0 equiv
1.0 equiv
7
8
Entry
1, Ar1
2, Ar2
Yield of the productb (%)
7
8 (cis/trans)c
1
2
3
4
1f, Ph
2a, Ph
2a, Ph
2a, Ph
2e, p-BrC6H4
7fa, 78
7ga, 62
7ha, 86
7he, 90
8fa, 14 (2.8:1.0)
8ga, 35 (4.6:1.0)
d
1g, p-BrC6H4
1h, p-MeC6H4
1h, p-MeC6H4
d
a
All reactions were conducted with MCPs 1 (0.2 mmol, 1.0 equiv), (E)-1,1,3-triarylprop-2-en-1-ols 2 (0.2 m mol, 1.0 equiv), and BF3$OEt2 (10 mol %) in DCM (2.0 mL) at room
temperature within 5 min otherwise specified.
b
Isolated yield.
c
Ratio of cis, trans-isomers was determined by 1H NMR spectroscopic data.
along with the minor product 8ga in 35% yield (Table 3, entry 2). But
under the standard reaction conditions, using MCP 1h bearing an
electron-rich aromatic ring as substrate mainly gave the corre-
sponding methylenecyclobutane 7ha in 86% yield (Table 3, entry 3).
Even in the reaction of MCP 1h with electron-deficient (E)-1,1,3-
triarylprop-2-en-1-ol 2e, the corresponding methylenecyclobutane
product 7he was exclusively obtained in 90% yield, further suggesting
that the electronic property of MCPs can significantly affect the re-
action outcome in this reaction (Table 3, entry 4). The structure of
methylenecyclobutane 7 and its Z-configuration of the double bond
were determined by the 2-D NMR spectroscopic data (HMQC, HMBC,
DEPT, and NOESY spectra) of compound 7he (see the Supplementary
data for the details).
In addition, compound 7he could also be transformed to the
corresponding biaryl compounds 10 via Suzuki coupling reaction
with various arylboronic acids 9 in good yields using 2-(dicyclo-
hexylphosphino)biphenyl (P) (10 mol %) as a ligand and Pd(OAc)2
(5 mol %) as a catalyst in the presence of KOtBu in toluene at 80 ꢀC
(Scheme 2).
On the basis of the above results, plausible reaction mecha-
nisms for the formation of the products 3, 4, 5, 6, 7, and 8 are
outlined in Schemes 4e6, respectively. All of the reactions are
initiated by the cationic intermediate A derived from 2 in the
presence of BF3$OEt2. As can be seen in Scheme 4, intermediate A
reacts with MCP 1 to afford intermediate B, which is stabilized by
two aromatic rings and one cyclopropane group,9 giving in-
termediate C via a ring enlargement process. The subsequent 1,2-
aryl migration of intermediate C furnishes a more stable cationic
intermediate D, which is followed by a ring opening process to
produce intermediate E. Elimination of
a proton from in-
termediate E gives triene product 3 and the reaction of in-
termediate E with H2O affords product 4. As can be seen from the
control experiment presented in Scheme 3, product 4 could be
transformed to the corresponding triene compound 3 by elimi-
nation of H2O. We assumed that the corresponding intermediate
E exists as a mixture of cis- and trans-isomers and the cis-isomer
may be liable to be attacked by H2O, giving cis-product 4
exclusively.

L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
5735
affords intermediate B0, which is then attacked by H2O along with
the cyclopropane ring opening process to furnish the correspond-
ing product 5ea. At the same time, intermediate B0 can also be
attacked by product 5ea to give the corresponding dimeric ether
product 6ea. In this case, the strongly electron-rich aromatic ring in
MCP 1e can significantly stabilize the sterically less hindered cat-
ionic intermediate B0, which can subsequently produce different
products 5ea and 6ea through the reaction with H2O and 5ea, re-
spectively rather than the ring enlargement as that mentioned in
Scheme 4.
As shown in Scheme 6, we can also see that the initial in-
termediate A reacts with MCP 1 to afford intermediate F, which
undergoes the similar cascade processes of ring enlargement, 1,2-
aryl migration and ring opening, and then reacts with H2O to give
the corresponding product 8. However, when the resonance-
stabilized intermediate A0 reacts with MCP 1, product 7 is formed
through a ring enlargement and a direct proton elimination path-
way from intermediate C0.
As can be seen from the above reaction mechanisms, the elec-
tronic property of the substrates on MCPs 1 mainly dominated the
reaction pathway to afford different kinds of products. The driving
force of each different reaction process is the generation of the
corresponding more stabilized cationic intermediates.
Scheme 4. A plausible mechanism for the formation 3 and 4.
p-MeOC6H4
p-MeOC6H4 1e
OH
Ph
BF3.OEt2
H2O
+
+
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
A
3. Conclusion
A'
2a
In conclusion, we have disclosed a BF3$OEt2-catalyzed in-
termolecular reaction of MCPs with (E)-1,1,3-triarylprop-2-en-1-ols
to afford a variety of different products effected by the electronic
property of the substituents on MCPs in excellent total yields under
mild conditions. The corresponding triene compounds, alcoholic
derivatives or cyclobutane derivatives were obtained in moderate
to good yields and the plausible reaction mechanisms for the for-
mation of the corresponding products have been proposed based
on the control experiment and previous literature. Efforts are un-
derway to further elucidate the reaction mechanism and to un-
derstand the scope and limitations of this interesting process.
p-MeOC6H4
+
Ph
p-MeOC6H4
Ph
Ph
O
2
Ph
)
B'
Ph
p-MeOC6H4
6ea
C6H4OMe-p
Ph
Ph
OH
Ph
p-MeOC6H4
5ea
C6H4OMe-p
Scheme 5. A plausible mechanism for the formation 5ae and 6ae.
4. Experimental section
4.1. General remarks
Melting points are uncorrected. 1H and 13C NMR were recorded
at 400 and 100 MHz, respectively. Mass spectra were recorded by EI
or MALDI and HRMS was measured by EI or MALDI method. Or-
ganic solvents used were dried by standard methods when nec-
essary. Commercially obtained reagents were used without further
purification. All reactions were monitored by TLC. Flash column
chromatography was carried out using 300e400 mesh silica gel
under increased pressure.
4.2. General procedure
Under an argon atmosphere, MCP 1 (0.20 mmol), (E)-1,1,3-
triarylprop-2-en-1-ol 2 (0.20 mmol, 1.0 equiv), and DCM (2.0 mL)
were added into a Schlenk tube. The reaction mixture was stirred at
room temperature (20 ꢀC), and then BF3$OEt2 (10 mol %) was added.
The reaction completed after 5 min monitored by TLC. The solvent
was removed under reduced pressure and the residue was purified
by a flash column chromatography to give the desired product 3e8.
Under an argon atmosphere, Compound 7he (0.20 mmol),
arylboronic acid 9 (0.40 mmol, 2.0 equiv) Pd(OAc)2 (5 mol %), 2-
(dicyclohexylphosphino)biphenyl (10 mol %), KOtBu (0.40 mmol,
2.0 equiv), and toluene (5.0 mL) were added into a Schlenk tube.
The reaction mixture was stirred at 80 ꢀC monitored by TLC. The
solvent was removed under reduced pressure and the residue was
Scheme 6. A plausible mechanism for the formation 7 and 8.
As for the formation of 5ea and 6ea in the reaction of MCP 1e
with 2a, a plausible mechanism is proposed in Scheme 5. Similarly,
the reaction is initiated by the formation of cationic intermediate A,
which tautomerizes to a less hindered cationic intermediate A0 via
an allylic rearrangement. The reaction of intermediate A0 with 1e

5736
L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
purified by a flash column chromatography to give the desired
product 10.
1H, CH), 6.70 (trans-, d, J¼11.6 Hz, 0.4H, CH), 6.81 (cis-, d, J¼11.2 Hz,
1H, CH), 6.97e7.37 (cis- and trans-, m, 32.2H, Ar). 13C NMR (CDCl3,
100 MHz, TMS)
d 21.0, 21.10, 21.13, 21.3, 31.1, 38.8, 122.4, 123.26,
4.2.1. Product 3aa (1.0:0.5 mixture of cis- and trans-isomers). A
123.34, 124.2, 124.3, 126.0, 126.1, 126.4, 126.6, 126.9, 127.2, 127.3,
127.5, 127.67, 127.73, 127.8, 127.9, 128.0, 128.1, 128.2, 128.3, 128.8,
129.3, 129.8, 130.0, 130.3, 130.5, 130.6, 130.7, 135.5, 136.8, 139.9,
137.0, 137.1, 137.2, 139.80, 139.85, 140.0, 142.10, 142.15, 142.3, 143.68,
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 3.19 (trans-, d,
J¼7.6 Hz, 1H, CH2), 3.61 (cis-, d, J¼7.6 Hz, 2H, CH2), 5.97 (trans-, t,
J¼7.6 Hz, 0.5H, CH), 6.07 (cis-, t, J¼7.6 Hz, 1H, CH), 6.28 (trans-, d,
J¼11.6 Hz, 0.5H, CH]), 6.56 (cis-, d, J¼11.6 Hz, 1H, CH]), 6.59
(trans-, d, J¼11.6 Hz, 0.5H, CH]), 6.85 (cis-, d, J¼11.6 Hz, 1H, CH]),
7.00e7.37 (cis- and trans-, m, 38.5H, Ar). 13C NMR (CDCl3, 100 MHz,
143.72,146.9. IR (CH2Cl2) n 3054, 3023, 2920, 2866, 1598,1511, 1493,
1443, 820, 759, 700 cmꢁ1. MS (%) m/z 502 (Mþ, 100), 335 (16), 308
(26), 229 (9), 215 (12), 205 (14), 195 (18), 167 (14), 115 (12), 105 (13),
91 (15). HRMS (EI) calcd for C39H34: 502.2661, found: 502.2665.
TMS) d 31.1, 38.9, 122.0, 124.2, 128.1, 125.5, 125.7, 126.1, 126.5, 126.6,
127.0, 127.1, 129.3, 127.5, 127.66, 127.75, 127.8, 128.1, 128.27, 128.32,
128.7, 129.3, 129.8, 130.0, 130.5, 130.6, 130.8, 136.3, 136.6, 139.68,
139.74, 139.8, 140.0, 140.6, 141.9, 142.2, 142.3, 142.5, 142.6, 142.8,
4.2.6. Product 3ae (1.0:0.6 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 3.20 (trans-, d,
142.9, 143.4,143.7,143.8,146.9. IR (CH2Cl2)
n
3055, 3026, 2928,1597,
J¼7.2 Hz, 1.2H, CH2), 3.60 (cis-, d, J¼7.2 Hz, 2H, CH2), 5.96 (trans-, t,
J¼7.2 Hz, 0.6H, CH), 6.04 (cis-, t, J¼7.2 Hz, 1H, CH), 6.21 (trans-, d,
J¼11.6 Hz, 0.6H, CH]), 6.46 (cis-, d, J¼11.6 Hz, 1H, CH]), 6.70
(trans-, d, J¼11.6 Hz, 0.6H, CH]), 6.77 (cis-, d, J¼11.6 Hz, 1H, CH]),
6.93e7.37 (cis- and trans-, m, 33.7H, Ar), 7.47e7.51 (cis- and trans-,
193, 1443, 1265, 1074, 1030, 763, 699, 638, 608 cmꢁ1. MS (%) m/z 474
(Mþ, 100), 307 (51), 281 (40), 215 (24), 191 (32), 167 (52), 115 (28),
91 (66), 77 (16), 57 (14). HRMS (EI) calcd for C37H30: 474.2348,
found: 474.2344.
m, 3.1H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 31.2, 38.9, 121.3,
4.2.2. Product 3ab (1.00:0.5 mixture of cis- and trans-isomers). A
121.6, 121.8, 124.8, 125.0, 125.99, 126.03, 126.1, 126.8, 127.0, 127.1,
127.3, 127.39, 127.44, 127.9, 128.0, 128.1, 128.2, 128., 128.4, 128.6,
128.9, 129.19, 129.26, 129.7, 130.0, 131.3, 131.5, 132.18, 132.222,
132.4, 138.1, 138.3, 139.6, 139.67, 139.70, 140.3, 140.8, 140.90, 140.94,
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 2.34 (cis- and trans-,
s, 4.5H, CH3), 3.18 (trans-, d, J¼7.6 Hz, 1H, CH2), 3.59 (cis-, d,
J¼7.2 Hz, 2H, CH2), 5.97 (trans-, t, J¼7.2 Hz, 0.5H, CH), 6.07 (cis-, t,
J¼7.2 Hz, 1H, CH), 6.25 (trans-, d, J¼11.2 Hz, 0.5H, CH), 6.54 (cis-, d,
J¼11.2 Hz, 1H, CH), 6.78 (trans-, d, J¼11.2 Hz, 0.5H, CH), 6.84 (cis-, d,
J¼11.2 Hz, 1H, CH), 6.86e7.39 (cis- and trans-, m, 36H, Ar). 13C NMR
141.6, 142.1, 142.2, 142.35, 142.45, 143.2, 144.9, 146.7. IR (CH2Cl2)
n
3055, 3025, 1488, 1443, 1398, 1072, 1010, 827, 758, 700 cmꢁ1. MS (%)
m/z 632 (Mþ2þ, 100), 630 (Mþ, 48), 465 (22), 438 (9), 384 (11), 358
(11), 325 (14), 307 (53), 281 (39), 229 (20), 215 (35), 203 (31), 191
(34), 167 (39), 115 (36), 91 (35). HRMS (EI) calcd for C37H28Br2:
630.0558, found: 630.0555.
(CDCl3, 100 MHz, TMS)
d 21.2, 21.3, 31.1, 36.1, 121.1, 124.20, 124.25,
124.3, 124.4, 125.0, 125.4, 125.5, 126.0, 126.1, 126.6, 126.8, 127.0,
127.2, 127.3, 127.6, 127.7, 127.8, 128.08, 128.11, 128.3, 128.6, 128.8,
129.0, 129.1, 129.3, 129.8, 130.0, 130.3, 130.6, 130.8, 130.9, 133.4,
133.9, 136.3, 136.4, 136.9, 137.1, 139.0, 139.8, 139.9, 140.5, 141.6,
4.2.7. Product 3ba (1.0:0.6 mixture of cis- and trans-isomers). A
142.3, 142.9, 143.2, 143.7, 146.0, 146.9, 150.2. IR (CH2Cl2)
n
3055,
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 3.16 (trans-, dd,
3024, 2924, 1597, 1493, 1443, 1265, 1031, 817, 764, 699 cmꢁ1. MS (%)
m/z 488 (Mþ, 100), 321 (36), 294 (22), 215 (15), 191 (18), 165 (16),
115 (18), 91 (20). HRMS (EI) calcd for C38H32: 488.2504, found:
488.2510.
J¼7.6, 0.8 Hz, 1.2H, CH2), 3.58 (cis-, d, J¼7.2 Hz, 2H, CH2), 5.95 (trans-
, t, J¼7.6 Hz, 0.6H, CH), 6.04 (cis-, t, J¼7.2 Hz, 1H, CH), 6.21 (trans-, d,
J¼11.6 Hz, 0.6H, CH), 6.54 (cis-, d, J¼11.6 Hz, 1H, CH), 6.72 (trans-, d,
J¼11.6 Hz, 0.6H, CH), 6.73 (trans-, d, J¼11.6 Hz, 0.6H, CH), 6.76 (cis-,
d, J¼11.6 Hz,1H, CH), 6.85 (cis-, d, J¼11.6 Hz,1H, CH), 6.89e6.93 (cis-
and trans-, m, 4.8H, Ar), 7.00e7.04 (cis- and trans-, m, 3.0H, Ar),
7.10e7.45 (cis- and trans-, m, 27.4H, Ar). 13C NMR (CDCl3, 100 MHz,
4.2.3. Product cis-3ab. A yellow liquid. 1H NMR (CDCl3, 400 MHz,
TMS)
d
2.30 (s, 3H, CH3), 3.59 (d, J¼6.8 Hz, 2H, CH2), 6.06 (t,
J¼6.8 Hz, 1H, CH), 6.52 (d, J¼11.6 Hz, 1H, CH), 6.83 (d, J¼11.6 Hz, 1H,
CH), 7.05 (d, J¼8.0 Hz, 2H, Ar), 7.16e7.20 (m, 11H, Ar), 7.23e7.27 (m,
6H, Ar), 7.34e7.38 (m, 5H, Ar).
TMS) d 31.1, 38.8, 122.6, 123.9, 124.0, 124.6, 124.9, 125.6, 126.0, 126.1,
126.7, 127.1, 127.2, 127.46, 127.55, 127.7, 128.14, 128.16, 128.18, 128.2,
128.35, 128.44, 128.7, 129.8, 130.6, 130.8, 131.1, 131.3, 132.3, 132.97,
133.06, 133.1, 133.4, 135.4, 136.6, 137.6, 137.7, 139.6, 139.7, 139.9,
140.0,140.4,140.6,140.7,141.7,142.2,142.2,142.4,142.7,143.3,144.1,
4.2.4. Product 3ac (1.00:0.5 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d
3.15 (trans-, d,
144.9. IR (CH2Cl2) n 3057, 3027, 2925, 1490, 1444, 1091, 1014, 826,
J¼7.2 Hz, 0.5H, CH2), 3.57 (cis-, d, J¼7.2 Hz, 2H, CH2), 5.93 (trans-, t,
J¼7.2 Hz, 0.5H, CH), 6.02 (cis-, t, J¼7.2 Hz, 1H, CH), 6.28 (trans-, d,
J¼11.2 Hz, 0.5H, CH), 6.51 (cis-, d, J¼11.2 Hz, 1H, CH), 6.68 (trans-, d,
J¼11.2 Hz, 0.5H, CH), 6.84 (cis-, d, J¼11.2 Hz, 1H, CH), 6.99e7.38 (cis-
766, 699 cmꢁ1. MS (%) m/z 542 (Mþ,10), 502 (43), 307 (28), 277 (25),
215 (35), 191 (40), 167 (47), 115 (42), 105 (52), 91 (100), 77 (54), 57
(43). HRMS (EI) calcd for C37H28Cl2: 542.1568, found: 542.1566.
and trans-, m, 36H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d
30.9, 38.7,
4.2.8. Product 4ba. A white solid, mp: 136e139 ꢀC. 1H NMR (CDCl3,
123.9, 124.6, 126.1, 126.8, 127.0, 127.3, 127.4, 127.50, 127.53, 127.8,
128.0, 128.08, 128.10, 128.13, 128.2, 128.4, 129.7, 130.0, 130.1, 130.5,
130.6, 132.8, 132.9, 139.0, 139.2, 139.6, 139.7, 139.8, 140.3, 141.8,
400 MHz, TMS) d 2.18 (s, 1H, OH), 2.36e2.40 (m, 2H, CH2),
2.71e2.75 (m, 2H, CH2), 6.49 (d, J¼11.6 Hz, 1H, CH]), 6.77 (d,
J¼11.6 Hz, 1H, CH]), 7.10e7.42 (m, 23H, Ar). 13C NMR (CDCl3,
142.2, 142.4, 142.6, 143.0, 143.2, 144.3. IR (CH2Cl2)
n
3078, 3055,
100 MHz, TMS) d 24.3, 41.0, 77.7, 123.6, 125.5, 126.0, 127.3, 127.38,
3026, 2958, 2926, 1489, 1443, 1093, 828, 766, 700 cmꢁ1. MS (%) m/z
508 (Mþ, 100), 341 (65), 328 (29), 314 (39), 303 (41), 279 (24), 215
(30), 191 (50), 167 (93), 115 (48), 91 (51). HRMS (EI) calcd for
C37H29Cl: 508.1958, found: 508.1594.
127.45, 127.6, 128.2, 128.3, 128.5, 130.6, 133.0, 139.6, 141.6, 141.8,
142.4, 143.8, 144.8. IR (CH2Cl2) n 3552, 3056, 3028, 1489, 1442, 1400,
1093, 1013, 907, 822, 766, 733, 700 cmꢁ1. MS (%) m/z 560 (Mþ, 12),
367 (27), 307 (15), 251 (16), 215 (31), 202 (32), 191 (38), 139 (99.5),
105 (52), 91 (100.0), 77 (38). HRMS (EI) calcd for C37H30Cl2O:
560.1674, found: 560.1661.
4.2.5. Product 3ad (1.0:0.4 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 2.25 (trans-, s, 1.2H,
CH3), 2.28 (trans-, s, 1.2H, CH3), 2.32 (cis-, s, 3H, CH3), 2.35 (cis-, s,
3H, CH3), 3.19 (trans-, d, J¼7.2 Hz, 0.8H, CH2), 3.60 (cis-, d, J¼7.2 Hz,
2H, CH2), 5.99 (trans-, t, J¼7.2 Hz, 0.4H, CH), 6.08 (cis-, t, J¼7.2 Hz,
1H, CH), 6.30 (trans-, d, J¼11.6 Hz, 0.4H, CH), 6.58 (cis-, d, J¼11.2 Hz,
4.2.9. Product 3ca (1.0:0.5 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 3.15 (trans-, d,
J¼7.6 Hz, 1.0H, CH2), 3.57 (cis-, d, J¼7.2 Hz, 2H, CH2), 5.96 (trans-, t,
J¼7.6 Hz, 0.5H, CH), 6.05 (cis-, t, J¼7.2 Hz, 1H, CH), 6.21 (trans-, d,

L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
5737
J¼11.6 Hz, 0.5H, CH), 6.54 (cis-, d, J¼11.6 Hz, 1H, CH), 6.72 (trans-, d,
J¼11.6 Hz, 0.5H, CH), 6.76 (cis-, d, J¼11.6 Hz, 1H, CH), 6.82e6.87 (cis-
and trans-, m, 5H, Ar), 6.96 (cis-, d, J¼8.8 Hz, 2H, Ar), 7.05 (cis-, d,
J¼8.8 Hz, 2H, Ar), 7.18e7.41 (cis- and trans-, m, 23.5H, Ar), 7.47 (cis-,
125.5, 126.1, 127.0, 127.2, 127.3, 127.4, 127.7, 128.08, 128.11, 128.2,
128.5, 128.7, 129.98, 130.03, 130.56, 130.63, 130.7, 130.9, 131.2,
132.2, 132.4, 135.4, 139.8, 140.9, 141.2, 142.0, 142.5, 143.5, 143.8,
158.6, 158.7, 162.8. IR (CH2Cl2) n 3056, 3029, 2932, 1603, 1510, 1445,
d, J¼8.8 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d
31.1, 38.8,
1253, 1168, 1031, 834, 769, 701 cmꢁ1. MS (%) m/z 534 (Mþ, 23), 367
(19), 354 (9), 277 (13), 253 (30), 242 (24), 227 (100), 135 (90), 105
(61), 91 (44), 77 (84). HRMS (EI) calcd for C39H34O2: 534.2559,
found: 534.2552.
120.5, 121.3, 121.6, 122.6, 123.90, 123.94, 124.6, 125.7, 126.0, 126.1,
126.7, 127.1, 127.2, 127.4, 127.5, 127.6, 127.7, 128.16, 128.20, 128.3,
128.7, 128.9, 129.9, 130.5, 130.6, 130.8, 131.0, 131.1, 131.2, 131.4, 131.6,
131.7, 135.3, 136.6, 138.1, 139.6, 139.8, 140.1, 140.7, 141.7, 142.4, 142.5,
4.2.14. Product 5ea. A white solid, mp: 155e158 ꢀC. 1H NMR (CDCl3,
142.7, 143.4, 144.1, 145.4. IR (CH2Cl2) n 3056, 3026, 2926, 1488, 1443,
1393, 1073, 1009, 821, 767, 699 cmꢁ1. MS (%) m/z 632 (Mþ2þ, 100),
630 (Mþ, 48), 465 (17), 384 (14), 358 (15), 325 (17), 307 (53), 280
(67), 215 (40), 202 (44), 191 (67), 167 (57), 115 (41), 91 (74), 77 (18).
HRMS (EI) calcd for C37H28Br2: 630.0558, found: 630.0550.
400 MHz, TMS)
d 2.36e2.44 (m, 1H, CH), 2.54e2.62 (m, 1H, CH),
3.29e3.35 (m, 1H, CH), 3.46e3.53 (m, 1H, CH), 3.67 (s, 3H, OCH3),
3.76 (s, 3H, CH3), 4.95 (d, J¼10.4 Hz, 1H, OH), 6.40 (d, J¼8.8 Hz, 2H,
Ar), 6.46 (d, J¼10.4 Hz, 1H, CH), 6.74 (d, J¼8.8 Hz, 2H, Ar), 6.82 (d,
J¼8.8 Hz, 2H, Ar), 6.96 (dd, J¼8.8, 1.2 Hz, 2H, Ar), 7.10e7.32 (m, 16H,
4.2.10. Product 4ca. A white solid, mp: 145e148 ꢀC. 1H NMR (CDCl3,
400 MHz, TMS) d 2.18 (s, 1H, OH), 2.35e2.39 (m, 2H, CH2), 2.71e2.75
Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 33.9, 47.6,55.0, 55.1, 62.3,
113.3, 113.8, 126.3, 127.0, 127.2, 127.78, 127.83, 128.0, 128.18, 128.24,
128.4, 129.5, 129.6, 130.0, 134.7, 134.8, 135.6, 139.4, 141.8, 142.9,
(m, 2H, CH2), 6.50 (d, J¼11.6 Hz, 1H, CH]), 6.78 (d, J¼11.6 Hz, 1H,
CH]), 7.09e7.39 (m, 23H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
143.2, 143.8, 157.7, 158.1. IR (CH2Cl2) n 3456, 3026, 2930, 1605, 1508,
1283, 1243, 1173, 1033, 832, 701 cmꢁ1. MS (%) m/z 552 (Mþ, 24), 367
(54), 341 (13), 321 (11), 269 (30), 227 (34), 191 (57), 165 (33), 121
(49), 91 (100), 57 (27). HRMS (EI) calcd for C39H36O3: 552.2264,
found: 552.2685.
d
24.3, 40.9, 77.8, 123.6, 125.5, 126.0, 127.3, 127.4, 127.5, 127.6, 127.7,
128.1, 128.2, 128.3, 128.4, 128.8, 130.5, 131.3, 131.4, 139.6, 141.6, 141.7,
142.3, 143.8, 145.2. IR (CH2Cl2) n 3557, 3055, 3027, 2926, 1487, 1442,
1396, 1074, 1009, 907, 817, 766, 733, 700 cmꢁ1. MS (%) m/z 650
(Mþ2þ, 16), 648 (Mþ, 8), 457 (34), 307 (19), 279 (20), 215 (38), 202
(37), 183 (63), 167 (43), 115 (43), 105 (67), 91 (100), 77 (43), 57 (35).
HRMS (EI) calcd for C37H30OBr2: 648.0663, found: 648.0651.
4.2.15. Product 6ea. A white solid, mp: 176e180 ꢀC. 1H NMR (CDCl3,
400 MHz, TMS)
d 2.16e2.23 (m, 1H, CH), 2.34e2.48 (m, 1H, CH),
2.68e2.78 (m, 1H, CH), 2.98e3.12 (m, 1H, CH), 3.67 (s, 3H, OCH3),
3.72 (s, 3H, CH3), 4.85 (dd, J¼10.4, 4.0 Hz, 1H, OH), 6.35 (dd, J¼10.0,
2.0 Hz, 1H, CH), 6.40 (dd, J¼8.8, 3.6 Hz, 2H, CH), 6.70 (dd, J¼8.8,
6.0 Hz, 2H, Ar), 6.76 (d, J¼8.4 Hz, 2H, Ar), 6.92 (t, J¼6.8 Hz, 2H, Ar),
6.99 (dd, J¼8.4, 1.2 Hz, 2H, Ar), 7.10e7.26 (m, 14H, Ar). 13C NMR
4.2.11. Product 3da (1.0:0.5 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 2.28 (cis-, s, 3H,
CH3), 2.30 (trans-, s, 1.5H, CH3), 2.34 (trans-, s, 1.5H, CH3), 2.36 (cis-,
s, 3H, CH3), 3.19 (trans-, d, J¼9.6 Hz, 1H, CH2), 3.60 (cis-, d, J¼9.2 Hz,
2H, CH2), 5.90 (trans-, t, J¼9.6 Hz, 0.5H, CH), 6.00 (cis-, t, J¼9.2 Hz,
1H, CH), 6.27 (trans-, d, J¼15.2 Hz, 0.5H, CH), 6.54 (cis-, d, J¼15.2 Hz,
1H, CH), 6.74 (trans-, d, J¼15.2 Hz, 0.5H, CH), 6.86 (cis-, d, J¼15.2 Hz,
1H, CH), 6.90e6.94 (cis- and trans-, m, 2.4H, Ar), 7.00e7.46 (cis- and
(CDCl3, 100 MHz, TMS) d 30.4, 47.7, 47.8, 55.0, 55.1, 69.5, 69.6, 113.2,
113.6, 126.1, 126.9, 127.2, 127.77, 127.84, 128.0, 128.1, 128.3, 129.6,
130.0, 134.9, 135.0, 135.6, 139.4, 141.2, 142.4, 143.2, 143.8, 157.6,
158.0. IR (CH2Cl2) n 3055, 3026, 2930, 1605, 1508, 1443, 1244, 1172,
trans-, m, 31.4H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 20.9, 21.1,
1034, 832, 767, 738, 701 cmꢁ1. MS (%) m/z 552 (MꢁC39H34O2þ, 2),
502 (4), 367 (4), 341 (4), 277 (21), 191 (16), 155 (18), 115 (21), 91
(59), 77 (39), 57 (63), 43 (100). HRMS (EI) calcd for C78H70O5:
1086.5223, found: 552.2665.
21.2, 22.6, 31.1, 38.9, 124.3, 125.3, 125.6, 126.1, 126.2, 127.0, 127.2,
127.28, 127.34, 127.4, 127.7, 128.0, 128.1, 128.2, 128.7, 128.9, 129.3,
129.6, 129.9, 130.5, 130.6, 136.4, 136.5, 136.6, 136.7, 136.9, 139.7,
139.8, 140.0, 140.1, 140.7, 140.8, 141.96, 142.00, 142.1, 142.4, 142.5,
142.6, 143.5, 143.7. IR (CH2Cl2) n 3053, 3024, 2955, 2923, 2855, 1509,
4.2.16. Product 7fa. A yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
1491, 1442, 1110, 1074, 765, 698, 502 cmꢁ1. MS (%) m/z 502 (Mþ, 85),
335 (47), 307 (37), 279 (26), 265 (18), 229 (25), 215 (41), 202 (45),
195 (71), 178 (42), 167 (55), 129 (38), 115 (50), 105 (79), 91 (100), 77
(50). HRMS (EI) calcd for C39H34: 502.2661, found: 502.2660.
d
1.69 (s, 3H, CH3), 1.89e1.96 (m, 1H, CH), 2.18e2.24 (m, 1H, CH),
2.51e2.59 (m, 1H, CH), 2.74e2.81 (m, 1H, CH), 6.80 (d, J¼12.0 Hz,1H,
Ar), 6.99 (d, J¼11.2 Hz, 1H, Ar), 7.05e7.42 (m, 19H, Ar). 13C NMR
(CDCl3, 100 MHz, TMS)
d 23.6, 29.4, 39.0, 43.0, 120.5, 121.5, 124.1,
4.2.12. Product cis-3da. A white solid, mp: 135e136 ꢀC. 1H NMR
124.2, 125.7, 126.3, 127.17, 127.25, 127.4, 127.6, 127.9, 128.1, 128.6,
130.8, 136.1, 137.2, 139.9, 142.8, 144.4, 149.2. IR (CH2Cl2) n 3057, 3026,
(CDCl3, 400 MHz, TMS) d 2.28 (s, 3H, CH3), 2.37 (s, 3H, CH3), 3.59 (d,
2962, 1493, 1443, 1029, 761, 699, 530 cmꢁ1. MS (%) m/z 412 (Mþ, 35),
291 (6), 248 (10), 191 (25), 178 (16), 165 (19), 115 (6), 91 (100), 71
(26), 57 (41). HRMS (EI) calcd for C32H28: 412.2191, found: 412.2195.
J¼9.2 Hz, 2H, CH2), 5.99 (t, J¼9.2 Hz, 1H, CH), 6.52 (d, J¼15.2 Hz, 1H,
CH), 6.85 (d, J¼15.2 Hz,1H, CH), 7.00e7.06 (m, 4H, Ar), 7.11e7.40 (m,
19H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 21.0, 21.3, 31.1, 124.3,
125.6, 126.17, 126.25, 127.0, 127.2, 127.3, 127.4, 127.7, 128.07, 128.14,
128.2, 128.7, 129.0, 129.9, 130.6, 136.66, 136.72, 137.0, 139.76, 139.80,
140.8, 141.97, 142.05, 142.6, 143.5.
4.2.17. Product 8fa (1.0:0.4 mixture of cis- and trans-isomers). A
white solid, mp: 121e126 ꢀC. 1H NMR (CDCl3, 400 MHz, TMS)
d 1.46
(trans-, s,1.2H, CH3),1.59 (cis-, s, 3H, CH3),1.94e2.03 (cis- and trans-,
m, 2.8H, CH2), 2.23e2.30 (trans-, m, 0.4H, CH2), 2.34e2.41 (trans-,
m, 0.4H, CH2), 2.50e2.57 (cis-, m, 1H, CH2), 2.73e2.81 (cis-, m, 1H,
CH2), 6.16 (trans-, d, J¼11.2 Hz, 0.4H, CH), 6.44 (cis-, d, J¼11.2 Hz, 1H,
CH), 6.66 (trans-, d, J¼11.2 Hz, 0.4H, CH), 6.82 (cis-, d, J¼11.2 Hz, 1H,
CH), 7.09e7.22 (cis- and trans-, m, 0.9H, Ar), 7.29e7.42 (cis- and
trans-, m, 25.1H, Ar), 7.46e7.48 (cis- and trans-, m, 2H, Ar). 13C NMR
4.2.13. Product 3ea (1.0:0.3 mixture of cis- and trans-isomers). A
yellow liquid. 1H NMR (CDCl3, 400 MHz, TMS)
d 3.19 (trans-, d,
J¼6.8 Hz, 0.6H, CH2), 3.60 (cis-, d, J¼6.8 Hz, 2H, CH2), 3.75 (cis-, s,
3H, OCH3), 3.78 (trans-, s, 0.9H, OCH3), 3.808 (cis-, s, 3H, OCH3),
3.814 (trans-, s, 0.9H, OCH3), 5.82 (trans-, t, J¼6.8 Hz, 0.3H, CH),
5.92 (cis-, t, J¼6.8 Hz, 1H, CH), 6.26 (trans-, d, J¼11.2 Hz, 0.3H, CH),
6.53 (cis-, d, J¼11.2 Hz, 1H, CH), 6.73e6.98 (cis- and trans-, m, 8.7H,
Ar), 7.08 (cis-, d, J¼8.8 Hz, 2H, Ar), 7.14e7.29 (cis- and trans-, m,
16.8H, Ar), 7.33e7.40 (cis- and trans-, m, 4.7H, Ar). 13C NMR (CDCl3,
(CDCl3,100 MHz, TMS) d (cis- and trans-) 24.7, 30.8, 43.5, 74.9,123.9,
124.7, 124.8, 125.1, 126.0, 127.69, 127.05, 127.3, 127.6, 128.1, 128.30,
128.32, 128.8, 130.6, 139.8, 141.9, 142.3, 142.5, 143.2, 147.2. IR
(CH2Cl2)
n
2956, 2925, 2853, 1445, 974, 763, 699 cmꢁ1. MS (%) m/z
100 MHz, TMS)
d (cis- and trans-) 31.1, 38.9, 55.17, 55.20, 55.4,
430 (Mþ, 17), 412 (5), 307 (18), 215 (15), 202 (15), 191 (13), 121 (22),
113.2,113.36,113.43,113.6,114.0,124.3,124.6, 125.22,125.26,125.3,

5738
L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
105 (27), 91 (49), 77 (18), 57 (20). HRMS (EI) calcd for C32H30O:
430.2297, found: 430.2289.
IR (CH2Cl2) n 2962, 2924, 2852, 1487, 1262, 1093, 1020, 802,
704 cmꢁ1. MS (MALDI) m/z 578.3 (Mþ). HRMS (MALDI) calcd for
C45H38: 578.2960, found: 578.2968.
4.2.18. Product 7ga. A yellow liquid. 1H NMR (CDCl3, 400 MHz,
TMS)
d
1.66 (s, 3H, CH3), 1.88e1.95 (m, 1H, CH), 2.13e2.19 (m, 1H,
4.2.23. Product 10b. A yellow solid, mp: 152e156 ꢀC. 1H NMR
CH), 2.50e2.56 (m, 1H, CH), 2.75e2.79 (m, 1H, CH), 6.78 (d,
J¼11.2 Hz, 1H, Ar), 6.91 (d, J¼8.4 Hz, 2H, Ar), 6.97 (d, J¼11.2 Hz, 1H,
(CDCl3, 400 MHz, TMS) d 1.73 (s, 3H, CH3), 1.94e2.01 (m, 1H, CH),
2.22e2.28 (m, 1H, CH), 2.30 (s, 3H, CH3), 2.58e2.64 (m, 1H, CH),
2.80e2.86 (m, 1H, CH), 6.84 (d, J¼11.2 Hz, 1H, Ar), 6.98 (d, J¼8.4 Hz,
2H, Ar), 7.05e7.16 (m, 6H, Ar), 7.37e7.41 (m, 6H, Ar), 7.44e7.53 (m,
7H, Ar), 7.62 (d, J¼8.4 Hz, 2H, Ar), 7.64 (d, J¼8.4 Hz, 2H, Ar). 13C NMR
Ar), 7.02e7.41 (m, 16H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 23.5,
29.3, 38.7, 42.7, 119.6, 121.7, 124.1, 124.2, 126.5, 127.3, 127.4, 127.6,
127.9, 128.1, 129.0, 130.7, 131.0, 136.1, 136.6, 139.8, 142.8, 143.0, 143.7,
148.3. IR (CH2Cl2)
n
3057, 2961, 2927, 1487, 1443, 1080, 1008, 760,
(CDCl3, 100 MHz, TMS) d 20.9, 23.8, 29.7, 39.0, 42.7, 121.2, 124.1,
700, 520 cmꢁ1. MS (%) m/z 492 (Mþ2þ, 100), 490 (Mþ, 100), 319
(10), 294 (27), 243 (18), 229 (17), 215 (29), 191 (48), 167 (32), 142
(22), 115 (40), 91 (44). HRMS (EI) calcd for C32H27Br: 490.1296,
found: 490.1299.
124.8,126.3,126.7,126.8,127.1,128.1,128.2,128.7,128.9,129.0,131.4,
133.4, 133.5, 135.2, 136.0, 138.0, 138.8, 138.9, 139.0, 139.1, 141.4,
142.1, 144.8, 146.3. IR (CH2Cl2) n 2957, 2925, 2854, 1484, 1263, 1094,
1059, 1019, 819, 744 cmꢁ1. MS (MALDI) m/z 646.2 (Mþ). HRMS
(MALDI) calcd for C45H36Cl2: 646.2182, found: 646.2187.
4.2.19. Product 8ga (1.0:0.3 mixture of cis- and trans-isomers). A
white solid, mp: 119e123 ꢀC. 1H NMR (CDCl3, 400 MHz, TMS)
d
1.41
4.2.24. Product 10c. A yellow solid, mp: 149e151 ꢀC. 1H NMR
(trans-, s, 0.9H, CH3),1.53 (cis-, s, 3H, CH3),1.94e1.98 (cis- and trans-,
m, 2.6H, CH2), 2.18e2.26 (trans-, m, 0.3H, CH2), 2.32e2.40 (trans-,
m, 0.3H, CH2), 2.46e2.54 (cis-, m, 1H, CH2), 2.72e2.80 (cis-, m, 1H,
CH2), 6.14 (trans-, d, J¼11.2 Hz, 0.3H, CH), 6.44 (cis-, d, J¼11.2 Hz, 1H,
CH), 6.66 (trans-, d, J¼11.2 Hz, 0.3H, CH), 6.79 (cis-, d, J¼11.2 Hz, 1H,
CH), 7.09e7.44 (cis- and trans-, m, 24.7H, Ar). 13C NMR (CDCl3,
(CDCl3, 400 MHz, TMS) d 1.25e1.30 (m, 6H, 2CH3), 1.72 (s, 3H, CH3),
1.93e1.99 (m, 1H, CH), 2.21e2.30 (m, 1H, CH), 2.30 (s, 3H, CH3),
2.56e2.75 (m, 5H, CH and 2CH2), 2.80e2.86 (m, 1H, CH), 6.86 (d,
J¼11.2 Hz, 1H, Ar), 6.98 (d, J¼8.4 Hz, 2H, Ar), 7.04e7.14 (m, 6H, Ar),
7.26 (d, J¼8.4 Hz, 2H, Ar), 7.31 (d, J¼8.4 Hz, 2H, Ar), 7.36e7.40 (m,
4H, Ar), 7.45e7.47 (m, 1H, Ar), 7.51e7.53 (m, 4H, Ar), 7.63 (d,
J¼8.4 Hz, 2H, Ar), 7.66 (d, J¼8.4 Hz, 2H, Ar). 13C NMR (CDCl3,
100 MHz, TMS)
d (cis- and trans-) 24.6, 30.6, 30.9, 33.8, 42.2, 43.3,
74.5, 74.6, 120.6, 123.8, 125.2, 125.9, 126.7, 126.8, 127.1, 127.38,
127.45, 127.5, 128.0, 128.1, 128.3, 128.4, 128.8, 130.6, 131.1, 131.3,
100 MHz, TMS) d 15.6, 20.9, 23.7, 28.5, 29.4, 39.0, 42.7, 121.5, 124.1,
124.3, 126.3, 126.6, 126.7, 126.8, 126.9, 127.1, 128.1, 128.2, 128.3,
128.4, 128.6, 131.3, 135.2, 136.1, 137.4, 138.0, 138.1, 138.5, 140.0, 141.6,
139.7, 141.8, 142.0, 142.4, 143.4, 146.2. IR (CH2Cl2)
n 3054, 2956,
2925, 1489, 1442, 1078, 1008, 827, 765, 699, 530 cmꢁ1. MS (%) m/z
510 (Mþ2þ, 7), 508 (Mþ, 6), 307 (10), 215 (12), 202 (13), 191 (13),
165 (10), 115 (18), 91 (44), 57 (40). HRMS (EI) calcd for C32H29BrO:
508.1402, found: 508.1400.
142.0, 143.4, 143.5, 144.7, 146.4. IR (CH2Cl2) n 3026, 2961, 2924,
2856, 1461, 1261, 1091, 1019, 822, 749, 730 cmꢁ1. MS (MALDI) m/z
634.4 (Mþ). HRMS (MALDI) calcd for C49H46: 634.3587, found:
634.3594.
4.2.20. Product 7ha. A yellow liquid. 1H NMR (CDCl3, 400 MHz,
Acknowledgements
TMS)
d 1.70 (s, 3H, CH3), 1.90e1.97 (m, 1H, CH), 2.19e2.25 (m, 1H,
CH), 2.28 (s, 3H, CH3), 2.54e2.60 (m,1H, CH), 2.76e2.81 (m,1H, CH),
Financial support from the Shanghai Municipal Committee of
Science and Technology (08dj1400100-2), National Basic Research
Program of China (973)-2009CB825300, and the National Natural
Science Foundation of China (21072206, 20472096, 20872162,
20672127, 20821002, and 20732008) are greatly acknowledged.
6.78 (d, J¼11.2 Hz, 1H, Ar), 6.96e7.42 (m, 19H, Ar). 13C NMR (CDCl3,
100 MHz, TMS)
d 20.8, 23.7, 29.5, 39.0, 42.6, 121.4, 124.1, 124.3,
126.2, 127.1, 127.2, 127.4, 127.6, 128.1, 128.6, 130.8, 135.1, 136.1, 137.3,
139.9,142.7,142.9,144.7,146.3. IR (CH2Cl2) n 3054, 6024, 2925,1493,
1443, 1376, 1018, 815, 760, 699 cmꢁ1. MS (%) m/z 426 (Mþ, 25), 233
(11), 215 (12), 191 (24), 165 (18), 115 (28), 105 (31), 91 (39), 71 (55),
57 (95). HRMS (EI) calcd for C33H30: 426.2348, found: 426.2353.
Supplementary data
4.2.21. Product 7he. A yellow liquid. 1H NMR (CDCl3, 400 MHz,
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.tet.2011.06.009.
TMS)
d 1.72 (s, 3H, CH3), 1.91e1.98 (m, 1H, CH), 2.20e2.26 (m, 1H,
CH), 2.30 (s, 3H, CH3), 2.50e2.58 (m,1H, CH), 2.74e2.82 (m,1H, CH),
6.68 (d, J¼11.2 Hz, 1H, Ar), 6.95e6.98 (m, 3H, Ar), 7.05 (d, J¼8.0 Hz,
2H, Ar), 7.10e7.19 (m, 7H, Ar), 7.40 (d, J¼8.0 Hz, 2H, Ar), 7.41e7.43
(m,1H, Ar), 7.55 (d, J¼8.0 Hz, 2H, Ar). 13C NMR (CDCl3, 75 MHz, TMS)
References and notes
1. For recent reviews, see: (a) Nakamura, I.; Yamamoto, Y. Adv. Synth. Catal. 2002,
344, 111e129; (b) Brandi, A.; Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Rev. 2003,
103, 1213e1270; (c) Nakamura, E.; Yamago, S. Acc. Chem. Res. 2002, 35, 867e877;
(d) Shao, L.-X.; Shi, M. Curr. Org. Chem. 2007, 11, 1135e1137; (e) Lautens, M.;
Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49e92; (f) de Meijere, A.; Kozhushkov, S.
I.; Khlebnikov, A. F. Top. Curr. Chem. 2000, 207, 89e147; (g) Binger, P.; Wedemann,
P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113e119; (h) de
Meijere, A.; Kozhushkov, S. I. A. Eur. J. Org. Chem. 2000, 3809e3822; (i) Rubin, M.;
Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117e3179; (j) Yamago, S.; Na-
kamura, E. Org. React. 2002, 61, 1e217; (k) de Meijere, A.; Kozhushkov, S. I.; Spath,
T.; von Seebach, M.; Lohr, S.; Nuske, H.; Pohomann, T.; Es-Sayed, M.; Brase, S.
Pure Appl. Chem. 2000, 72, 1745e1756; (l) For the synthesis of MCPs, see: Brandi,
A.; Goti, A. Chem. Rev. 1998, 98, 589e636.
2. Selected recent articles about transition metal-catalyzed reactions of MCPs: (a)
Camacho, D. H.; Nakamura, I.; Saito, S.; Yamamoto, Y. J. Org. Chem. 2001, 66,
270e275; (b) Lautens, M.; Meyer, C.; Lorenz, A. J. Am. Chem. Soc. 1996, 118,
10676e10677; (c) Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 9597e9605; (d)
Saito, S.; Masuda, M.; Komagawa, S. J. Am. Chem. Soc. 2004, 126, 10540e10541;
(e) Shi, M.; Wang, B.-Y.; Huang, J.-W. J. Org. Chem. 2005, 70, 5606e5610; (f)
Nakamura, I.; Itagaki, H.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6458e6459; (g)
Tsukada, N.; Hibuya, A.; Nakamura, I.; Yamamoto, Y. J. Am. Chem. Soc. 1997, 119,
8123e8124; (h) Suginome, M.; Matsuda, T.; Ito, Y. J. Am. Chem. Soc. 2000, 122,
d
20.9, 23.8, 29.0, 8.8, 42.6, 120.6, 124.1, 125.1, 126.4, 127.1, 127.6,
128.2, 128.6, 129.1, 131.3, 131.5, 132.4, 135.2, 135.8, 138.3, 138.8,
140.0, 141.3, 144.8, 146.1. IR (CH2Cl2) n 2962, 2925, 1507, 1340, 1094,
1018, 806, 744 cmꢁ1. MS (MALDI) m/z 584.1 (Mþ). HRMS (MALDI)
calcd for C33H28Br2: 582.0545, found: 582.0552.
4.2.22. Product 10a. A yellow solid, mp: 144e146 ꢀC. 1H NMR
(CDCl3, 400 MHz, TMS)
d 1.72 (s, 3H, CH3), 1.94e2.00 (m, 1H, CH),
2.22e2.28 (m, 1H, CH), 2.30 (s, 3H, CH3), 2.57e2.64 (m, 1H, CH),
2.81e2.87 (m, 1H, CH), 6.87 (d, J¼11.6 Hz, 1H, Ar), 6.99 (d, J¼8.0 Hz,
2H, Ar), 7.06 (d, J¼8.0 Hz, 2H, Ar), 7.09e7.15 (m, 3H, Ar), 7.31e7.54
(m,14H, Ar), 7.60 (d, J¼8.0 Hz, 2H, Ar), 7.68 (d, J¼8.0 Hz, 2H, Ar), 7.70
(d, J¼8.0 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 20.9, 23.8,
29.5, 39.0, 42.7,121.4,124.1,124.5,126.3,126.8,126.88,126.92,127.0,
127.1, 127.27, 127.32, 127.4, 128.16, 128.21, 128.7, 128.76, 128.84,
131.3, 135.2, 136.1, 137.6, 138.8, 140.0, 140.1, 140.6, 141.9, 144.7, 146.3.

L. Wu, M. Shi / Tetrahedron 67 (2011) 5732e5739
5739
11015e11016; (i) Scott, M. E.; Bethuel, Y.; Lautens, M. J. Am. Chem. Soc. 2007, 129,
1482e1483.
2606e2609; (j) Yao, L.-F.; Wei, Y.; Shi, M. J. Org. Chem. 2009, 74, 9466e9469; (k)
Jiang, M.; Shi, M. J. Org. Chem. 2009, 74, 2516e2520; (l) Qi, M.-H.; Shao, L.-X.; Shi, M.
Dalton Trans. 2010, 39, 8829e8834; (m) Wu, L.; Shi, M. Chem. Eur. J. 2010, 16,
5163e5172.
6. (a) Ma, S.-M.; Zhang, J.-L. J. Am. Chem. Soc. 2003, 125, 12386e12387; (b)
Lautens, M.; Han, W. J. Am. Chem. Soc. 2002, 124, 6312e6316; (c) Lautens, M.;
Han, W.; Liu, J. H.-C. J. Am. Chem. Soc. 2003, 125, 4028e4029; (d) Scott, M. E.;
Han, W.; Lautens, M. Org. Lett. 2004, 6, 3309e3312; (e) Scott, M. E.; Lautens, M.
Org. Lett. 2005, 7, 3045e3047; (f) Furstner, A.; Aissa, C. J. Am. Chem. Soc. 2006,
128, 6306e6307.
7. (a) Yao, L.-F.; Shi, M. Org. Lett. 2007, 9, 5187e5190; (b) Shi, M.; Yao, L.-F. Chem.
Eur. J. 2008, 14, 8725e8731; (c) Yao, L.-F.; Shi, M. Chem. Eur. J. 2009, 15,
3875e3881.
8. The crystal data of 5ea have been deposited in the CCDC with number 737131.
Empirical formula: C39H36O3; formula weight: 552.68; crystal color, habit: col-
orless, prismatic; crystal system: monoclinic; lattice type: primitive; lattice
3. Selected recent articles about Lewis acid-mediated reactions of MCPs: (a) Shi,
M.; Xu, B. Org. Lett. 2002, 4, 2145e2148; (b) Xu, B.; Shi, M. Org. Lett. 2003, 5,
1415e1418; (c) Huang, X.; Zhou, H.-W. Org. Lett. 2002, 4, 4419e4422; (d) Huang,
J.-W.; Shi, M. Tetrahedron Lett. 2003, 44, 9343e9347 and references cited therein;
(e) Huang, X.; Miao, M.-Z. J. Org. Chem. 2008, 73, 6884e6887; (f) Yu, L.; Huang, X.
Synlett 2007, 1371e1374.
4. (a) Camacho, D. H.; Nakamura, I.; Saito, S.; Yamamoto, Y. Angew. Chem., Int. Ed.
1999, 38, 3365e3367; (b) Nakamura, I.; Oh, B. H.; Saito, S.; Yamamoto, Y. Angew.
Chem., Int. Ed. 2001, 40, 1298e1300; (c) Oh, B. H.; Nakamura, I.; Saito, S.; Ya-
mamoto, Y. Tetrahedron Lett. 2001, 42, 6203e6205; (d) Oh, B. H.; Nakamura, I.;
Saito, S.; Yamamoto, Y. Heterocycles 2003, 61, 247e257; (e) Brase, S.; de Meijere,
A. Angew. Chem., Int. Ed. Engl. 1995, 34, 2545e2547; (f) Nakamura, I.; Nemoto, T.;
Yamamoto, Y.; de Meijere, A. Angew. Chem., Int. Ed. 2006, 45, 5176e5179.
5. (a) Shi, M.; Xu, B.; Huang, J.-W. Org. Lett. 2004, 6,1175e1178; (b) Shi, M.; Shao, L.-X.;
Xu, B. Org. Lett. 2003, 5, 579e582; (c) Shao, L.-X.; Xu, B.; Huang, J.-W.; Shi, M. Chem.
Eur. J. 2006, 12, 510e517; (d) Huang, J.-W.; Shi, M. Synlett 2004, 2343e2346; (e)
Patient, L.; Berry, M. B.; Kilburn, J. D. Tetrahedron Lett. 2003, 44, 1015e1017; (f) Shi,
M.; Liu, L. P.; Tang, J. J. Am. Chem. Soc. 2006, 128, 7430e7431; (g) Shao, L.-X.; Li, J.;
Wang, B.-Y.; Shi, M. Eur. J. Org. Chem. 2010, 6448e6453; (h)Jiang, M.; Wei, Y.; Shi, M.
Eur. J. Org. Chem. 2010, 3307e3311; (i) Jiang, M.; Shi, M. Org. Lett. 2010, 12,
ꢀ
ꢀ
ꢀ
a
parameters: a¼18.198 (2) A, b¼10.4605 (13) A, c¼17.281 (2) A,
¼90ꢀ,
¼107.086
b
3
ꢀ
(3)ꢀ,
g
¼90 , V¼3144.5 (7) A ; space group: P2(1)/c; Z¼4; Dcalc¼1.167 g/cm3;
ꢀ
F000¼1176; diffractometer: Rigaku AFC7R; residuals: R; Rw: 0.0576, 0.1331.
9. For a review of cyclopropylmethyl cations, see: Richey, H. G., Jr. In Carbonium
Ions; Olah, G. A., Schleyer, P. v. R., Eds.; Wiley-Interscience: New York, NY, 1972;
Vol. III, Chapter 25.