Lewis-acid-catalyzed reactions of bis(4-alkoxyphenyl)methanol with (diarylmethylene)- and (dialkylmethylene)cyclopropanes

Article abstract of DOI:10.1002/ejoc.200900546

Bis(4-methoxyphenyl)methanol (2a) can be transformed by BF ₃·OEt₂-catalyzed reactions of (arylmethylene) cyclopropanes 1 to the corresponding polysubstituted cyclopentenes 3 as the major products along with methylenecyclobutanes and

Full text of DOI:10.1002/ejoc.200900546

FULL PAPER
DOI: 10.1002/ejoc.200900546
Lewis-Acid-Catalyzed Reactions of Bis(4-alkoxyphenyl)methanol with
(Diarylmethylene)- and (Dialkylmethylene)cyclopropanes
Liang-Feng Yao[a] and Min Shi*[a,b]
Keywords: Lewis acids / Synthetic methods / Cycloalkenes / Strained molecules
Bis(4-methoxyphenyl)methanol (2a) can be transformed by
BF3·OEt2-catalyzed reactions of (arylmethylene)cyclopro-
panes 1 to the corresponding polysubstituted cyclopentenes
3 as the major products along with methylenecyclobutanes
and dienes as minor products. The reaction conditions are
mild, yields are moderate to good. In the reactions of ali-
phatic methylenecyclopropanes with bis(4-methoxyphenyl)-
methanol (2a), cyclopentenes 3o–q were produced in good
yields under the standard conditions. Interesting results were
obtained from the reactions of 1-[cyclopropylidene(4-meth-
oxyphenyl)methyl]-4-methoxybenzene (1e) with bis(4-alk-
oxyphenyl)methanols 2: polysubstituted cyclopentene deriv-
atives 5 were obtained in good yields under mild reaction
conditions. Plausible reaction mechanisms based on the deu-
terium-labeling and control experiments are proposed.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
interesting Lewis-acid-catalyzed reaction of MCPs 1 with
bis(4-alkoxyphenyl)methanols 2 to produce cyclopentenes 3
as the major products along with methylenecyclobutanes
and diene derivatives 4a–c as the minor products. We could
also prepare novel polysubstituted cyclopentenes 5 in mod-
erate to good yields under mild conditions.
Introduction
Methylenecyclopropanes (MCPs) are highly strained but
readily accessible molecules, which can serve as useful
building blocks in organic synthesis.[1] Their most interest-
ing aspect is that MCPs can undergo a variety of ring-open-
ing and cycloaddition reactions to give interesting products
in the presence of transition metals or Lewis acids. Indeed,
the relief of ring strain can provide a powerful thermo-
dynamic driving force.[2,3] Thus far, a number of interesting
cycloadditions and ring enlargements of MCPs have been
explored. For example, Yamamoto et al. reported cycload-
dition reactions of MCPs with aldehydes and imines using
a palladium catalyst, affording the corresponding tetra-
hydrofuran (THF) and pyrrolidine skeletons in good
yields.[4] In addition, we as well as other groups have devel-
oped a number of heterocycle-forming reactions starting
from MCPs and aldehydes or imines as well as ring enlarge-
ments of MCPs in the presence of Lewis or Brønsted ac-
ids.[5,6] Recently, we have been investigating the Lewis-acid-
mediated ring-opening reactions of MCPs 1 with a number
of electrophiles such as phenylsulfenyl chloride and phen-
ylselenyl chloride as well as 3-methoxy-1,3,3-triarylprop-1-
yne or 1,1,3-triarylprop-2-yn-1-ol under mild conditions.[7]
A variety of novel products could be obtained in good
yields by a simple one-step reaction. Herein, we report an
Results and Discussion
We performed initial examinations with (diphenylmethyl-
ene)cyclopropane 1a (0.2 mmol) and bis(4-methoxyphenyl)-
methanol 2a (0.24 mmol) as substrates in the presence of
various Lewis acids (10 mol-%) in 1,2-dichloroethane
(DCE) to determine the best catalyst for this intermolecular
reaction. The results of these experiments are summarized
in Table 1. Except in THF or using Yb(OTf)3 as the Lewis
acid, the reactions proceeded smoothly with various Lewis
acids in a variety of solvents at room temperature (20 °C),
giving cyclopentene 3a and methylenecyclobutane 4aa
along with ring-opened diene products 4ab and 4ac as (E/
Z) mixtures in 63–84% total yields, respectively (Table 1,
Entries 1–7 and 10–12). Using BF3·OEt2 as the catalyst af-
forded 3a in the highest yield, perhaps due to its mild cata-
lytic ability in the above reaction compared with that of
M(OTf)n (n = 3 or 4, Table 1, Entry 1). Further increasing
or decreasing the amount of BF3·OEt2 provided no im-
provement in the total yield (Table 1, Entries 8 and 9). In
view of the total yield of this reaction, we used 10 mol-%
of BF3·OEt2 as our optimal catalyst loading. We obtained
the best result by using BF3·OEt2 (10 mol-%) as the catalyst
in DCE at room temperature (20 °C), which afforded 3a in
52% yield and a 72% total yield including 4aa–ac (Table 1,
Entry 1).
[a] Laboratory for Advanced Materials & Institute of Fine Chemi-
cals, East China University of Science and Technology,
130 Mei Long Lu, Shanghai 200237, P. R. China
[b] State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, P. R. China
E-mail: Mshi@mail.sioc.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200900546.
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Table 1. Optimization of the reaction conditions.
[a] All reactions were carried out with 1a (0.2 mmol), 2a (0.24 mmol) and Lewis acid (10 mol-%) in various solvents (2.0 mL) at room
temperature. [b] Isolated yields. [c] Total yields of 4aa–ac in which the (E) configuration of 4ab has been determined by NOE spectroscopy
(see the Supporting Information). [d] The ratios of 4aa/4ab/4ac were determined by 1H NMR spectroscopy. [e] The reaction mixtures
were stirred for 24 h. [f] 20 mol-% of BF3·OEt2 was used. [g] 5 mol-% of BF3·OEt2 was used.
Next, we attempted to improve the yield of 3a by ad- mixture of 4aa–ac in 13% total yield, respectively (Table 2,
justing the ratios of 1a and 2a. The results of these experi- Entry 1). Increasing the amount of 1a to 2.0 equiv. or
ments are shown in Table 2. We found that using 1.0 equiv. 2.5 equiv. to react with 2a (1.0 equiv.) afforded 3a in 67 and
of 1a and 1.5 equiv. of 2a produced 3a in 45% yield and a 73% yields along with a mixture of 4aa–ac in 28% and 14%
Table 2. Further optimization of the reaction conditions.
1
[a] Isolated yields. [b] Total yield of 4aa–ac. [c] The ratios of 4aa/4ab/4ac were determined by H NMR spectroscopy.
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Lewis-Acid-Catalyzed Reactions of Bis(4-Alkoxyphenyl)methanol
total yields, respectively (Table 2, Entries 2 and 3). Further formed (Scheme 1). Thus, these studies outlined the fact
increases of the amount of 1a provided no improvement in that the reaction is determined by the substituted pattern
the yield (Table 2, Entry 4).
of 1 and the electronic nature and the steric effect of 2.
With these optimized reaction conditions in hand, we
next turned our interest to the screening of the substrates.
The results of these experiments are summarized in Table 3.
We obtained the corresponding cyclopentene derivatives 3
in 25–78% yields along with the minor products 4 in 8–
32% total yields. These studies highlighted the fact that
substituents on the aromatic rings of 1 did not significantly
affect the reaction outcomes (Table 3, Entries 1–7). Various
strongly electron-donating alkoxy groups on the aromatic
rings of 2 had little influence on the yields of 3 (Table 3,
Scheme 1. Reaction of monosubstituted MCPs with 2a.
1
We determined product structures by H and 13C NMR
Entries 9–13). MCP 1iϪhaving an ortho-chloro atom on the spectroscopy and HRMS or microanalyses. We determined
aromatic ringϪproduced the corresponding cyclopentene 3i the crystal structure of 3a by X-ray diffraction (Figure 1),
in only 25% yield, presumably due to steric hindrance. We and its CIF data were deposited in a data base.[9] Moreover,
note that the strongly electron-donating group on the aro- we determined the (E) configuration of 4ab by NOE studies
matic ring of 2 is essential in the reaction because when (Figure 2, see the details in the Supporting Information).[8]
using diphenylmethanol or bis(4-chlorophenyl)methanol as
Furthermore, we observed an interesting phenomenon
1
the reactant, no reaction occurred under identical condi- on the basis of H NMR spectroscopic data; when it was
tions. Moreover, it is noteworthy that, using triphenylmeth- stored at –18 °C for two weeks, the diene product 4ab could
anol as the substrate to react with 1, no reaction occurred be completely transformed into another diene 4aB by allylic
under identical conditions perhaps due to a steric effect. isomerization (Scheme 2). We unambiguously determined
Furthermore, using monosubstituted MCPs to react with the structure of 4aB by X-ray diffraction, and the ORTEP
2a under identical conditions, complex product mixtures drawing is depicted in Figure 3.[9]
Table 3. Reactions of MCPs 1 with 2, catalyzed by BF3·OEt2, under the optimized conditions.
1
[a] Isolated yields. [b] For unsymmetrical substrates, diastereomers in a 1:1 ratio were obtained on the basis of H NMR spectroscopy.
1
[c] The total yields of 4a–c. [d] The ratios of 4a/4b/4c were determined by H NMR spectroscopy. [e] For unsymmetrical substrates, the
E/Z or Z/E ratio was 1:1.
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In order to have a better understanding of the reaction
mechanism, we next carried out a deuterium-labeling ex-
periment with 2a-d as the substrate under the optimized
conditions and found that the corresponding 3a-d was
formed in 66% yield with Ͼ99% D incorporation, suggest-
ing that only aryl migration takes place in this reaction
(Scheme 3).
Scheme 3. Deuterium-labeling experiment of the reaction.
On the basis of deuterium-labeling experiment, we out-
lined a plausible reaction mechanism as shown in Scheme 4.
In the presence of BF3·OEt2, 2a produces cationic interme-
diate A, which reacts with MCP 1 to afford cationic inter-
mediate B. Intermediate B undergoes a ring expansion to
give cationic intermediate C, which can proceed through
two different reaction pathways. The deprotonation of C
gives the minor product 4a (path a). A 1,2-aryl shift pro-
duces intermediate D.[10] Intermediate D undergoes a 1,2-
alkyl shift to intermediate E, which undergoes deproton-
ation to produce the major products 3a–n (paths b and c).
As for the products 4b and 4c, cationic intermediate C un-
dergoes a 1,2-aryl shift to furnish cationic intermediate D,
which undergoes a ring-opening process to afford cationic
intermediate F. The deprotonation of intermediate F pro-
duces the products 4b and 4c.
Figure 1. ORTEP drawing of 3a.
Figure 2. NOE studies on 4ab.
Scheme 2. Transformation of 4ab to 4aB.
Scheme 4. A plausible reaction mechanism for the formation of 3
and 4.
Figure 3. ORTEP drawing of 4aB.
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Lewis-Acid-Catalyzed Reactions of Bis(4-Alkoxyphenyl)methanol
Table 4. The reactions of aliphatic MCPs 1j–m with 2a in the presence of BF3·OEt2.
[a] Isolated yields.
Furthermore, we found that in the case of aliphatic MCP Table 5. Optimization of the reaction conditions.
1j, product 3o formed in 52% yield rather than the desired
cyclopentene derivative of 3a–n, presumably because the de-
protonation in this particular case proceeded through
path d (Table 4, Entry 1 and Scheme 4). Moreover, we also
examined aliphatic MCPs 1k–m in this reaction, and the
results of these experiments are summarized in Table 4. The
reactions proceeded smoothly to deliver the corresponding
cyclopentene derivatives 3p–r in good yields varying from
61–67% under the standard conditions, suggesting that the
substituents on the aromatic rings have little influence on
the reaction outcome.
Interestingly, we found that using 1.0 equiv. of MCP 1e,
having a strongly electron-donating methoxy group on the
benzene ring, to react with 1.2 equiv. of 2a afforded a new
product 5a in 55% yield under the standard conditions
(Table 5, Entry 1). We also unambiguously determined the
structure of 5a by X-ray diffraction, and the ORTEP draw-
ing is depicted in Figure 4.[9] Next, we attempted to improve
the yield of 5a by adjusting the ratios of 1e and 2a similarly.
The results are shown in Table 5. When we used 1.0 equiv.
of 1e and 2.0 equiv. of 2a, 5a formed in 59% yield. Increas-
ing the amount of 2a to 2.5 equiv. and 3.0 equiv. improved
the isolated yields of 5a to 63% and 68%, respectively
(Table 5, Entries 3 and 4). Further increasing the amount
of 2a (4.0 equiv.) furnished no improvement in the yield.
Thus, the optimized reaction conditions constitute a re-
action in DCE at room temperature (20 °C) with 1.0 equiv.
of 1e and 3.0 equiv. of 2a in the presence of BF3·OEt2
(10 mol-%) for 3 h. Under these optimized conditions, we
next examined the generality of this reaction using a variety
of starting materials 2, and the results are outlined in
Table 6. The corresponding cyclopentene derivatives 5
formed in 50–57% yields (Table 6, Entries 1–4). Substitu-
ents on the aromatic rings of 2 have little influence on the
reaction outcome. Moreover, we also determined the struc-
ture of 5b by X-ray diffraction, and the ORTEP drawing is
[a] Isolated yields.
Figure 4. ORTEP drawing of 5a.
In order to clarify the reaction route for the formation
depicted in Figure 5.[9] More interestingly, on the basis of of 5, we performed two control experiments (Scheme 5). We
crystal data, the similar products 5a and 5b have different found that the reaction of 4eb and 4ec [(E/Z) mixtures,
space groups (P21/c and P-1, respectively).
0.1 mmol] with 2a (0.2 mmol) under standard conditions
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Table 6. Reactions of 1e with 2b–f under the optimized reaction conditions.
[a] Isolated yields.
Figure 5. ORTEP drawing of 5b.
Scheme 5. A control experiment and plausible reaction mechanism
for the formation of 5.
delivered the desired product 5a in 55% yield (Scheme 5).
Moreover, the reaction of 3e (0.1 mmol) with 2a (0.2 mmol)
under the standard conditions afforded a complex product
mixture rather than the desired product 5a (Scheme 5). On
the basis of these above results, a plausible reaction mecha-
nism to account for the formation of 5 is shown in
deuterium-labeling and control experiments have been pro-
posed. Further studies regarding the mechanistic details
and scope of this process are in progress.
Experimental Section
Scheme 4. The addition of cationic intermediate
A
(Scheme 5) to 4eb and 4ec produces intermediate G, which
undergoes an intramolecular electrophilic addition to give
Typical Procedure for the Reaction of MCPs 1 with Bis(4-alk-
oxyphenyl)methanol 2: MCP 1a (0.25 mmol, 52 mg) and bis(4-
the cationic intermediate H. The deprotonation of interme- methoxyphenyl)methanol 2a (0.1 mmol, 24 mg) were dissolved in
DCE (2.0 mL), and BF3·OEt2 (10 mol-%) was added. The mixture
was stirred for 3.0 h at room temperature (25 °C). The solvent was
removed in vacuo, and the residue was purified by flash column
chromatography on silica gel with petroleum ether/EtOAc (40:1) as
an eluent to afford a white solid 3a (32 mg, 73%) and the mixture
of 4aa–4ac (6 mg, 14%). Since these reaction products, having elec-
tron-rich substituents on the aromatic rings, are quite labile during
purification and recrystallization (the solid product will become an
oily product along with some decomposed byproducts during
recrystallization), we could not send all of them for elemental
diate H affords the corresponding cyclopentene 5a.
In conclusion, we have found an interesting procedure
wherein diaryl or aliphatic MCPs can react with bis(alkoxy-
phenyl)methanols to provide cyclopentenes as the major
products along with cyclobutanes and diene derivatives as
the minor products under mild conditions. In the presence
of BF3·OEt2, MCP 1e, with a strongly electron-donating
methoxy group, reacts with bis(alkoxyphenyl)methanol to
produce novel polysubstituted cyclopentene derivatives in
good yields. Plausible reaction mechanisms based on the analyses.
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Lewis-Acid-Catalyzed Reactions of Bis(4-Alkoxyphenyl)methanol
MCP 1e (0.2 mmol, 53 mg) and bis(4-methoxyphenyl)methanol
(2a) (0.6 mmol, 146 mg) were dissolved in DCE (2.0 mL), and
BF3·OEt2 (10 mol-%) was added at room temperature. The mixture
was stirred for 3 h. The solvent was removed in vacuo, and the
residue was purified by flash column chromatography on silica gel
with petroleum ether/EtOAc (10:1) as an eluent to give a white
solid 5a (98 mg, 68%).
2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ = 43.8, 55.0,
55.2, 60.0, 60.8, 113.4, 113.8, 121.7, 127.3, 127.5, 127.70, 127.73,
129.4, 129.8, 130.1, 130.4, 131.3, 131.6, 143.5, 145.5, 149.8, 157.9,
158.9 ppm. IR (CH Cl ): ν = 3052, 3000, 2932, 2907, 2836, 2288,
˜
2
2
2043, 1893, 1607, 1582, 1573, 1510, 1491, 1464, 1442, 1420, 1398,
1303, 1258, 1177, 1142, 1112, 1093, 1035, 1013, 1003, 972, 892,
864, 814, 787, 767, 737, 705, 673, 622, 607, 561, 535 cm–1. MS (%):
m/z = 500 (100) [M]+, 121 (40), 165 (15), 237 (15), 239 (21), 252
(37), 265 (61), 379 (22), 501 (34), 502 (67). HRMS (EI): calcd. for
C31H26O2Cl2 500.1310; found 500.1295.
3a: A white solid (32 mg, 73%), m.p. 151–153 °C. 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.70 (dd, J = 3.0, 16.2 Hz, 1 H,
CH2), 3.61 (s, 3 H, OCH3), 3.74 (s, 3 H, OCH3), 3.77 (d, J =
16.2 Hz, 1 H, CH2), 4.79 (s, 1 H, CH), 6.19 (s, 1 H, =CH), 6.51 (d,
J = 8.1 Hz, 2 H, Ar), 6.79 (d, J = 8.1 Hz, 2 H, Ar), 6.86 (d, J =
8.7 Hz, 2 H, Ar), 6.94–7.04 (m, 5 H, Ar), 7.13–7.22 (m, 5 H, Ar),
7.37 (d, J = 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz,
TMS): δ = 43.8, 54.9, 55.1, 59.9, 61.6, 113.1, 113.7, 122.1, 125.3,
125.5, 127.2, 127.3, 127.5, 128.1, 128.2, 128.8, 130.0, 131.2, 145.3,
3e: A colorless oil (28 mg, 57%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.65 (dd, J = 2.4, 16.2 Hz, 1 H, CH2), 3.64 (s, 3 H,
OCH3), 3.66 (s, 3 H, OCH3), 3.68 (s, 3 H, OCH3), 3.72 (s, 3 H,
OCH3), 3.78 (d, J = 16.2 Hz, 1 H, CH2), 4.70 (s, 1 H, CH), 6.19
(s, 1 H, =CH), 6.53 (d, J = 8.4 Hz, 2 H, Ar), 6.56 (d, J = 8.4 Hz,
2 H, Ar), 6.72 (d, J = 8.4 Hz, 2 H, Ar), 6.79 (d, J = 8.4 Hz, 2 H,
Ar), 6.85–6.89 (m, 4 H, Ar), 7.11 (d, J = 8.4 Hz, 2 H, Ar), 7.37 (d,
J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ
= 44.2, 54.9, 55.0, 55.1, 55.2, 60.2, 60.3, 112.5, 112.8, 113.2, 113.4,
113.5, 113.7, 122.2, 127.3, 128.3, 128.4, 128.9, 129.8, 130.0, 131.5,
137.8, 144.3, 145.7, 157.0, 157.3, 157.7, 158.7 ppm. IR (CH2Cl2):
145.6, 151.9, 157.7, 158.8 ppm. IR (CH Cl ): ν = 3054, 3000, 2932,
˜
2
2
2906, 2835, 2045, 1946, 1875, 1607, 1581, 1511, 1493, 1463, 1443,
1302, 1256, 1178, 1111, 1035, 830, 807, 789, 773, 756, 744, 700,
600, 531 cm–1. MS (%): m/z = 432 (100) [M]+, 91 (7), 121 (12), 165
(9), 239 (9), 265 (24), 311 (27), 324 (8), 341 (8), 433 (35). C31H28O2
(432.2089): calcd. C 86.08, H 6.52; found C 86.23, H 6.74. HRMS
(EI): calcd. for C31H28O2 432.2089; found 432.2104.
ν = 3035, 2999, 2932, 2906, 2835, 2058, 1607, 1581, 1510, 1463,
˜
1441, 1301, 1249, 1178, 1111, 1036, 909, 822, 787, 754, 732, 611,
598, 579, 543 cm–1. MS (%): m/z = 492 (100) [M]+, 121 (73), 371
(70), 227 (60), 253 (56), 252 (46), 493 (37), 385 (31). HRMS (EI):
calcd. for C33H32O4 492.2300; found 492.2301.
3b: A colorless oil (28 mg, 61%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.16 (s, 3 H, CH3), 2.26 (s, 3 H, CH3), 2.67 (dd, J =
3.3, 16.2 Hz, 1 H, CH2), 3.61 (s, 3 H, OCH3), 3.71 (d, J = 16.2 Hz,
1 H, CH2), 3.73 (s, 3 H, OCH3), 4.75 (s, 1 H, CH), 6.18 (s, 1 H,
=CH), 6.51 (d, J = 8.7 Hz, 2 H, Ar), 6.76–6.88 (m, 8 H, Ar), 6.98
(d, J = 8.1 Hz, 2 H, Ar), 7.09 (d, J = 8.1 Hz, 2 H, Ar), 7.35 (d, J
= 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ =
20.8, 20.9, 44.0, 54.9, 55.1, 59.9, 60.9, 113.1, 113.7, 122.2, 127.3,
127.8, 127.9, 128.2, 128.3, 128.6, 130.0, 131.4, 134.5, 134.9, 142.4,
3f: A colorless oil (40 mg, 68%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.63 (dd, J = 3.6, 16.5 Hz, 1 H, CH2), 3.66 (s, 3 H,
OCH3), 3.68 (d, J = 16.5 Hz, 1 H, CH2), 3.76 (s, 3 H, OCH3), 4.66
(s, 1 H, CH), 6.16 (s, 1 H, =CH), 6.54 (d, J = 8.4 Hz, 2 H, Ar),
6.77–6.85 (m, 6 H, Ar), 7.02 (d, J = 8.4 Hz, 2 H, Ar), 7.15 (d, J =
8.4 Hz, 2 H, Ar), 7.30 (d, J = 8.4 Hz, 2 H, Ar), 7.33 (d, J = 8.4 Hz,
2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ = 43.8, 55.0,
55.2, 59.9, 61.0, 113.5, 113.8, 119.6, 119.8, 121.7, 127.3, 127.7,
129.8, 129.9, 130.38, 130.43, 130.5, 130.7, 143.9, 145.6, 150.3,
145.7, 149.2, 157.6, 158.7 ppm. IR (CH Cl ): ν = 3050, 2998, 2922,
˜
2
2
2835, 2045, 1891, 1607, 1582, 1573, 1512, 1463, 1442, 1302, 1246,
1177, 1111, 1036, 1003, 892, 864, 836, 808, 786, 750, 737, 702, 611,
575, 534 cm–1. MS (%): m/z = 460 (100) [M]+, 105 (12), 121 (26),
239 (12), 265 (15), 339 (48), 355 (15), 461 (37). HRMS (EI): calcd.
for C33H32O2 460.2402; found 460.2396.
158.0, 159.0 ppm. IR (CH Cl ): ν = 2929, 2835, 2359, 2342, 1683,
˜
2
2
1652, 1606, 1558, 1509, 1488, 1472, 1457, 1437, 1418, 1394, 1302,
1256, 1177, 1111, 1075, 1035, 1009, 835, 808, 786, 763, 529 cm–1.
MS (%): m/z = 588 (51) [M]+, 121 (52), 239 (22), 265 (55), 388 (26),
390 (25), 589 (20), 590 (100). HRMS (EI): calcd. for C31H26O2Br2
588.0297; found 588.0300.
3c: A colorless oil (29 mg, 62%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.64 (dd, J = 3.3, 16.5 Hz, 1 H, CH2), 3.63 (s, 3 H,
OCH3), 3.70 (d, J = 16.5 Hz, 1 H, CH2), 3.74 (s, 3 H, OCH3), 4.68
(s, 1 H, CH), 6.17 (s, 1 H, =CH), 6.53 (d, J = 8.4 Hz, 2 H, Ar),
6.69 (d, J = 8.7 Hz, 1 H, Ar), 6.72 (d, J = 8.7 Hz, 1 H, Ar), 6.79
(d, J = 8.7 Hz, 2 H, Ar), 6.82–6.93 (m, 6 H, Ar), 7.12 (dd, J = 5.4,
8.7 Hz, 2 H, Ar), 7.35 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR
(CDCl3, 75 MHz, TMS): δ = 44.1, 54.9, 55.1, 60.3, 60.6, 113.3,
113.8, 114.0 (d, JC,F = 20.6 Hz), 114.3 (d, JC,F = 20.6 Hz), 121.8,
3g: A colorless oil (30 mg, 64%); (syn or anti isomer) 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.66 (dd, J = 3.3, 16.5 Hz, 1 H,
CH2), 3.61 (s, 3 H, OCH3), 3.71 (d, J = 16.5 Hz, 1 H, CH2), 3.74
(s, 3 H, OCH3), 4.70 (s, 1 H, CH), 6.17 (s, 1 H, =CH), 6.51 (d, J
= 8.7 Hz, 2 H, Ar), 6.77–7.02 (m, 8 H, Ar), 7.12–7.22 (m, 4 H, Ar),
1
7.35 (d, J = 8.7 Hz, 2 H, Ar) ppm. (anti or syn isomer) H NMR
127.3, 127.8, 129.4 (d, JC,F = 7.4 Hz), 129.8, 130.2 (d, JC,F
8.0 Hz), 130.7, 140.9, 141.0, 145.5, 147.3, 157.9, 158.9, 160.7 (d, J
= 242.7 Hz), 160.9 (d, J = 243.9 Hz) ppm. IR (CH Cl ): ν = 3058,
=
(CDCl3, 300 MHz, TMS): δ = 2.70 (dd, J = 3.3, 16.5 Hz, 1 H,
CH2), 3.63 (s, 3 H, OCH3), 3.74 (s, 3 H, OCH3), 3.76 (d, J =
16.5 Hz, 1 H, CH2), 4.76 (s, 1 H, CH), 6.18 (s, 1 H, =CH), 6.54 (d,
J = 8.7 Hz, 2 H, Ar), 6.77–7.02 (m, 8 H, Ar), 7.12–7.22 (m, 4 H,
Ar), 7.35 (d, J = 8.7 Hz, 2 H, Ar) ppm. (syn or anti isomer) 13C
NMR (CDCl3, 75 MHz, TMS): δ = 43.6, 54.9, 55.0, 59.8, 61.1,
113.2, 113.75, 121.9, 125.6, 127.3, 127.4, 127.6, 128.0, 128.7, 129.5,
130.2, 130.7, 131.0, 144.1, 145.5, 150.4, 157.8, 158.8 ppm. (anti or
syn isomer) 13C NMR (CDCl3, 75 MHz, TMS): δ = 44.0, 55.0,
55.1, 60.0, 61.3, 113.3, 113.8, 121.9, 125.7, 127.3, 127.6, 127.9,
128.7, 129.5, 129.9, 130.7, 130.8, 131.3, 144.7, 145.5, 151.3, 157.8,
˜
2
2
3000, 2933, 2907, 2836, 2043, 1962, 1885, 1757, 1607, 1583, 1573,
1514, 1463, 1442, 1418, 1406, 1305, 1261, 1163, 1140, 1108, 1035,
1015, 893, 865, 834, 787, 756, 737, 718, 701, 624, 610, 589, 573,
535, 508 cm–1. MS (%): m/z = 468 (100) [M]+, 109 (15), 121 (36),
133 (11), 239 (16), 265 (27), 347 (24), 360 (12). HRMS (EI): calcd.
for C31H26O2F2 468.1901; found 468.1900.
3d: A colorless oil (28 mg, 55%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.63 (dd, J = 3.3, 16.5 Hz, 1 H, CH2), 3.64 (s, 3 H,
OCH3), 3.69 (d, J = 16.5 Hz, 1 H, CH2), 3.75 (s, 3 H, OCH3), 4.67
(s, 1 H, CH), 6.16 (s, 1 H, =CH), 6.54 (d, J = 8.4 Hz, 2 H, Ar),
6.77–6.89 (m, 6 H, Ar), 7.00 (d, J = 8.4 Hz, 2 H, Ar), 7.08 (d, J =
158.9 ppm. IR (CH Cl ): ν = 3054, 2932, 2906, 2835, 1607, 1574,
˜
2
2
1510, 1492, 1463, 1443, 1398, 1303, 1256, 1177, 1111, 1093, 1035,
1013, 832, 813, 787, 754, 737, 700, 605, 560, 534 cm–1. MS (%):
8.7 Hz, 2 H, Ar), 7.14 (d, J = 8.7 Hz, 2 H, Ar), 7.34 (d, J = 8.7 Hz, m/z = 466 (100) [M]+, 121 (46), 165 (20), 237 (13), 252 (26), 265
Eur. J. Org. Chem. 2009, 4971–4982
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4977

L.-F. Yao, M. Shi
FULL PAPER
(45), 310 (16), 344 (12), 345 (28), 467 (36), 468 (41). HRMS (EI):
calcd. for C31H27O2Cl 466.1700; found 466.1707.
3.80 (d, J = 16.2 Hz, 1 H, CH2), 3.81 (t, J = 6.6 Hz, 2 H, OCH2),
3.93 (t, J = 6.6 Hz, 2 H, OCH2), 4.82 (s, 1 H, CH), 6.22 (s, 1 H,
=CH), 6.54 (d, J = 8.4 Hz, 2 H, Ar), 6.81 (d, J = 8.4 Hz, 2 H, Ar),
6.88 (d, J = 8.4 Hz, 2 H, Ar), 6.98–7.08 (m, 5 H, Ar), 7.16–7.26
(m, 5 H, Ar), 7.40 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ = 14.0, 22.6, 25.7, 29.2, 31.5, 31.6, 43.8, 59.9,
61.6, 67.6, 67.8, 113.8, 114.2, 121.9, 125.3, 125.5, 127.2, 127.3,
127.5, 127.9, 128.1, 128.9, 129.9, 131.0, 145.4, 145.7, 151.9, 157.2,
3h: A colorless oil (35 mg, 78%); (syn or anti isomer) 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.66 (dd, J = 3.3, 16.5 Hz, 1 H,
CH2), 3.61 (s, 3 H, OCH3), 3.71 (d, J = 16.5 Hz, 1 H, CH2), 3.74
(s, 3 H, OCH3), 4.70 (s, 1 H, CH), 6.17 (s, 1 H, =CH), 6.51 (d, J
= 8.7 Hz, 2 H, Ar), 6.77–7.02 (m, 8 H, Ar), 7.12–7.22 (m, 4 H, Ar),
1
7.35 (d, J = 8.7 Hz, 2 H, Ar) ppm. (anti or syn isomer) H NMR
158.4 ppm. IR (CH Cl ): ν = 3055, 2957, 2855, 1939, 1881, 1607,
˜
2
2
(CDCl3, 300 MHz, TMS): δ = 2.70 (dd, J = 3.3, 16.5 Hz, 1 H,
CH2), 3.63 (s, 3 H, OCH3), 3.75 (s, 3 H, OCH3), 3.76 (d, J =
16.5 Hz, 1 H, CH2), 4.76 (s, 1 H, CH), 6.18 (s, 1 H, =CH), 6.54 (d,
J = 8.7 Hz, 2 H, Ar), 6.77–7.02 (m, 8 H, Ar), 7.12–7.22 (m, 4 H,
Ar), 7.35 (d, J = 8.7 Hz, 2 H, Ar) ppm. (syn or anti isomer) 13C
NMR (CDCl3, 75 MHz, TMS): δ = 43.8, 54.9, 55.1, 60.0, 61.0,
113.1, 113.3, 113.9 (d, J = 22.6 Hz), 122.0, 125.5, 125.7, 127.3,
127.6, 128.0, 128.7, 129.5 (d, J = 7.6 Hz), 129.9, 130.9, 131.0, 141.2,
145.0, 145.5, 145.6, 147.58, 151.5, 157.7, 158.79, 160.6 (d, J =
243.1 Hz) ppm. (anti or syn isomer) 13C NMR (CDCl3, 75 MHz,
TMS): δ = 44.1, 54.9, 55.1, 60.3, 61.1, 113.3, 113.7, 114.2 (d, J =
20.9 Hz), 122.0, 125.5, 125.7, 127.3, 127.6, 128.0, 128.7, 129.9,
130.2 (d, J = 7.4 Hz), 130.9, 131.0, 141.2, 145.0, 145.6, 147.6, 151.5,
1580, 1509, 1493, 1469, 1444, 1390, 1302, 1243, 1176, 1112, 1033,
937, 907, 888, 864, 831, 780, 756, 744, 699, 670, 649, 620, 556, 531
cm–1. MS (%): m/z = 572 (100) [M]+, 43 (60), 91 (11), 167 (10), 381
(13), 573 (48), 574 (11). HRMS (EI): calcd. for C41H48O2 572.3654;
found 572.3666.
3l: A colorless oil (27 mg, 55%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.69 (dd, J = 3.0, 16.5 Hz, 1 H, CH2), 3.75 (d, J =
16.5 Hz, 1 H, CH2), 4.31 (d, J = 4.8 Hz, 2 H, OCH2), 4.46 (d, J =
4.8 Hz, 2 H, OCH2), 4.77 (s, 1 H, CH), 5.18 (dd, J = 1.5, 10.5 Hz,
1 H, =CH2), 5.24 (dd, J = 1.5, 10.5 Hz, 1 H, =CH2), 5.27 (dd, J =
1.5, 17.1 Hz, 1 H, =CH2), 5.34 (dd, J = 1.5, 17.1 Hz, 1 H, =CH2),
5.87–6.05 (m, 2 H, =CH), 6.18 (s, 1 H, =CH), 6.51 (d, J = 8.4 Hz,
2 H, Ar), 6.79 (d, J = 8.4 Hz, 2 H, Ar), 6.84 (d, J = 8.4 Hz, 2 H,
Ar), 6.91–7.03 (m, 5 H, Ar), 7.10–7.22 (m, 5 H, Ar), 7.34 (d, J =
8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ =
43.7, 59.9, 61.6, 68.4, 68.6, 113.9, 114.5, 117.3, 117.6, 122.2, 125.3,
125.5, 127.2, 127.3, 127.5, 128.1, 128.3, 128.8, 129.9, 131.3, 133.2,
157.8, 158.83, 160.8 (d, J = 242.9 Hz) ppm. IR (CH Cl ): ν = 3055,
˜
2
2
3000, 2933, 2907, 2836, 2043, 1884, 1607, 1582, 1510, 1463, 1443,
1418, 1303, 1258, 1177, 1141, 1110, 1035, 1015, 909, 891, 864, 835,
787, 771, 752, 736, 700, 648, 628, 610, 578, 537 cm–1. MS (%): m/z
= 450 (100) [M]+, 121 (43), 265 (37), 451 (34), 329 (33), 252 (25),
165 (25), 239 (23). HRMS (EI): calcd. for C31H27O2F 450.1994;
found 450.1995.
133.3, 145.3, 145.5, 151.8, 156.7, 157.8 ppm. IR (CH Cl ): ν =
˜
2
2
3055, 2957, 2855, 1939, 1881, 1607, 1580, 1509, 1493, 1469, 1444,
1390, 1302, 1243, 1176, 1112, 1033, 937, 907, 888, 864, 831, 780,
756, 744, 699, 670, 649, 620, 556, 531 cm–1. MS (%): m/z = 484
(100) [M]+, 41 (98), 91 (31), 115 (21), 147 (11), 165 (21), 167 (42),
191 (36), 309 (14), 485 (39). HRMS (EI): calcd. for C35H32O2
484.2402; found 484.2407.
3i: A colorless oil (13 mg, 25%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.99 (dd, J = 3.0, 16.8 Hz, 1 H, CH2), 3.65 (d, J =
16.8 Hz, 1 H, CH2), 3.67 (s, 3 H, OCH3), 3.75 (s, 3 H, OCH3), 4.61
(s, 1 H, CH), 6.21 (s, 1 H, =CH), 6.53 (d, J = 8.7 Hz, 2 H, Ar),
6.67–6.70 (m, 4 H, Ar), 6.74 (d, J = 8.7 Hz, 2 H, Ar), 6.92 (d, J =
8.7 Hz, 2 H, Ar), 7.17–7.54 (m, 6 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ = 40.0, 55.1, 55.2, 61.1, 61.3, 113.4, 113.8, 123.2,
126.0, 127.2, 127.7, 127.8, 128.6, 128.9, 129.6, 130.7, 131.9, 134.7,
3m: A colorless oil (22 mg, 45%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.70 (dd, J = 3.0, 16.2 Hz, 1 H, CH2), 3.37 (s, 3 H,
OCH3), 3.45 (s, 3 H, OCH3), 3.77 (d, J = 16.2 Hz, 1 H, CH2), 4.78
(s, 1 H, CH), 5.00 (s, 2 H, OCH2), 5.14 (s, 2 H, OCH2), 6.22 (s, 1
H, =CH), 6.63 (d, J = 8.4 Hz, 2 H, Ar), 6.85 (d, J = 8.4 Hz, 2 H,
Ar), 6.92–7.01 (m, 7 H, Ar), 7.1–7.20 (m, 5 H, Ar), 7.38 (d, J =
8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ =
43.8, 55.9, 56.0, 59.9, 61.6, 94.3, 94.4, 115.5, 116.0, 122.7, 125.3,
125.5, 127.2, 127.3, 127.5, 128.1, 128.8, 129.3, 130.0, 132.4, 145.2,
142.8, 143.7, 146.0, 158.1, 158.9 ppm. IR (CH Cl ): ν = 3052, 3000,
˜
2
2
2954, 2932, 2835, 1887, 1607, 1583, 1573, 1510, 1492, 1465, 1441,
1399, 1303, 1256, 1177, 1111, 1093, 1035, 1013, 863, 837, 815, 786,
753, 738, 681, 626, 607, 539 cm–1. MS (%): m/z = 500 (100) [M]+,
121 (62), 125 (13), 165 (26), 227 (20), 239 (24), 252 (31), 265 (86),
501 (36), 502 (69), 503 (23). HRMS (EI): calcd. for C31H26O2Cl2
500.1310; found 500.1303.
145.4, 151.8, 155.5, 156.4 ppm. IR (CH Cl ): ν = 3054, 2997, 2928,
˜
2
2
3j: A colorless oil (28 mg, 60%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 1.27 (t, J = 6.9 Hz, 3 H, CH3), 1.36 (t, J = 6.9 Hz, 3 H,
CH3), 2.69 (dd, J = 2.7, 16.9 Hz, 1 H, CH2), 3.76 (d, J = 16.9 Hz,
1 H, CH2), 3.82 (q, J = 6.9 Hz, 2 H, OCH2), 3.96 (q, J = 6.9 Hz,
2 H, OCH2), 4.77 (s, 1 H, CH), 6.17 (s, 1 H, =CH), 6.49 (d, J =
8.4 Hz, 2 H, Ar), 6.76 (d, J = 8.4 Hz, 2 H, Ar), 6.84 (d, J = 8.4 Hz,
2 H, Ar), 6.93–7.03 (m, 5 H, Ar), 7.11–7.22 (m, 5 H, Ar), 7.35 (d,
J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS): δ
= 14.7, 14.8, 43.8, 59.9, 61.6, 63.0, 63.3, 113.7, 114.2, 122.0, 125.3,
125.5, 127.2, 127.3, 127.5, 128.1, 128.9, 130.0, 131.1, 145.4, 145.6,
2848, 2824, 2786, 1994, 1947, 1888, 1727, 1606, 1578, 1510, 1443,
1406, 1312, 1240, 1200, 1150, 1111, 1077, 1000, 921, 888, 864, 808,
789, 772, 757, 744, 699, 669, 656, 631, 619, 594, 555, 531 cm–1. MS
(%): m/z = 492 (100) [M]+, 167 (86), 169 (63), 91 (53), 115 (42), 101
(40), 191 (40), 69 (38). HRMS (EI): calcd. for C33H32O4 492.2301;
found 492.2309.
3n: A colorless oil (27 mg, 57%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 2.42 (t, J = 2.4 Hz, 1 H, CH), 2.47 (t, J = 2.4 Hz, 1 H,
CH), 2.70 (dd, J = 3.0, 16.2 Hz, 1 H, CH2), 3.75 (d, J = 16.2 Hz,
1 H, CH2), 4.47 (d, J = 2.4 Hz, 2 H, OCH2), 4.62 (d, J = 2.4 Hz,
2 H, OCH2), 4.78 (s, 1 H, CH), 6.21 (s, 1 H, =CH), 6.56 (d, J =
8.4 Hz, 2 H, Ar), 6.86 (d, J = 8.4 Hz, 4 H, Ar), 6.91–7.03 (m, 5 H,
Ar), 7.11–7.22 (m, 5 H, Ar), 7.37 (d, J = 8.4 Hz, 2 H, Ar) ppm.
13C NMR (CDCl3, 75 MHz, TMS): δ = 43.7, 55.6, 59.8, 61.6, 75.2,
75.6, 78.5, 78.6, 114.1, 114.6, 122.7, 125.3, 125.5, 127.2, 127.3,
127.5, 128.0, 128.8, 128.9, 129.9, 132.0, 145.1, 145.2, 151.7, 155.8,
151.9, 157.1, 158.2 ppm. IR (CH Cl ): ν = 3054, 2979, 2927, 2903,
˜
2
2
2848, 1943, 1882, 1607, 1580, 1509, 1493, 1477, 1443, 1392, 1302,
1244, 1177, 1116, 1090, 1047, 1002, 923, 863, 828, 803, 778, 756,
744, 699, 669, 648, 619, 548, 531 cm–1. MS (%): m/z = 460 (100)
[M]+, 107 (15), 165 (15), 293 (20), 325 (25), 461 (35). HRMS (EI):
calcd. for C33H32O2 460.2402; found 460.2410.
3k: A colorless oil (34 mg, 60%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 0.92–0.94 (m, 6 H, CH3), 1.33–1.54 (m, 12 H, CH2),
156.7 ppm. IR (CH Cl ): ν = 3290, 3053, 2924, 2850, 2121, 1878,
˜
2
2
1605, 1509, 1493, 1444, 1375, 1304, 1266, 1219, 1178, 1114, 1030,
1.67–1.80 (m, 4 H, CH2), 2.74 (dd, J = 3.0, 16.2 Hz, 1 H, CH2), 925, 864, 832, 783, 757, 744, 700, 644, 553, 530 cm–1. MS (%): m/z
4978
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4971–4982

Lewis-Acid-Catalyzed Reactions of Bis(4-Alkoxyphenyl)methanol
= 480 (76) [M]+, 191 (100), 167 (95), 91 (89), 115 (89), 165 (89), 178
(75), 460 (36), 459 (34), 291 (34), 121 (30), 171 (29), 417 (28).
(53), 192 (43). HRMS (EI): calcd. for C35H28O2 480.2089; found HRMS (EI): calcd. for C30H31O2Cl: 458.2013; found 458.2014.
480.2093.
1
4aa and 4ac: A colorless oil (6 mg, 14%); 4aa: H NMR (CDCl3,
3o: A colorless oil (22 mg, 52%). 1H NMR (CDCl3, 300 MHz,
300 MHz, TMS): δ = 2.72–2.83 (m, 4 H, CH2), 3.67 (s, 3 H, OCH3),
TMS): δ = 1.46–1.82 (m, 8 H, CH2), 2.06 (t, J = 7.2 Hz, 2 H, CH2),
3.76 (s, 3 H, OCH3), 6.50 (d, J = 8.7 Hz, 2 H, Ar), 6.67 (d, J =
2.27–2.34 (m, 1 H, CH), 2.82 (t, J = 7.2 Hz, 2 H, CH2), 3.72 (s, 3
8.7 Hz, 2 H, Ar), 7.12–7.26 (m, 8 H, Ar), 7.32–7.35 (m, 4 H, Ar)
ppm. 4ac: 1H NMR (CDCl3, 300 MHz, TMS): δ = 3.55 (d, J =
H, OCH3), 3.86 (s, 3 H, OCH3), 6.64 (d, J = 8.7 Hz, 2 H, Ar), 6.89
(d, J = 8.7 Hz, 2 H, Ar), 6.98 (d, J = 8.7 Hz, 2 H, Ar), 7.01 (d, J
6.9 Hz, 2 H, CH2), 3.80 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 6.04
(t, J = 6.9 Hz, 1 H, =CH), 6.49–7.35 (m, 19 H, Ar) ppm. IR
= 8.7 Hz, 2 H, Ar), 7.14–7.30 (m, 5 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ = 30.9, 33.0, 33.3, 35.0, 43.6, 52.7, 55.0, 55.1,
(CH Cl ): ν = 3043, 2996, 2955, 2836, 2359, 2342, 1788, 1686, 1664,
˜
2
2
113.0, 113.6, 125.8, 126.7, 128.2, 128.8, 130.1, 130.7, 131.1, 135.3,
145.5, 147.7, 157.8, 158.2 ppm. IR (CH Cl ): ν = 3058, 3027, 2999,
1602, 1572, 1506, 1463, 1442, 1409, 1289, 1248, 1178, 1166, 1109,
1032, 1014, 830, 795, 766, 616, 576, 540 cm–1. MS (%): m/z = 432
(100) [M]+, 121 (29), 239 (20), 265 (34), 311 (38), 433 (36). HRMS
(EI): calcd. for C31H28O2 432.2091; found 432.2089.
˜
2
2
2926, 2850, 2063, 1884, 1605, 1570, 1513, 1441, 1338, 1284, 1248,
1178, 1106, 1053, 1035, 895, 830, 802, 788, 757, 700, 626, 586, 570,
540 cm–1. MS (%): m/z = 424 (71) [M]+, 91 (16), 121 (27), 171
(48), 292 (21), 305 (100), 306 (25), 425 (25). HRMS (EI): calcd. for
C30H32O2 424.2402; found 424.2403.
4ca, 4cb and 4cc: A colorless oil (9 mg, 19%); 4ca: 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.66–2.70 (m, 2 H, CH2), 2.76–2.82
(m, 2 H, CH2), 3.69 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 6.53 (d,
J = 8.7 Hz, 2 H, Ar), 6.64 (d, J = 8.7 Hz, 2 H, Ar), 6.73 (d, J =
8.7 Hz, 2 H, Ar), 6.90 (d, J = 8.7 Hz, 2 H, Ar), 6.93 (d, J = 8.7 Hz,
2 H, Ar), 7.12 (d, J = 8.7 Hz, 2 H, Ar), 7.23 (d, J = 8.7 Hz, 4 H,
3p: A white solid (32 mg, 65%), m.p. 188–190 °C. 1H NMR
(CDCl3, 400 MHz, TMS): δ = 1.52–1.57 (m, 2 H, CH2), 1.64–1.71
(m, 4 H, CH2), 1.81–1.85 (m, 2 H, CH2), 2.07 (t, J = 7.2 Hz, 2 H,
CH2), 2.31–2.39 (m, 1 H, CH), 2.83 (t, J = 7.2 Hz, 2 H, CH2), 3.71
(s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 6.64–6.66 (m, 2 H, Ar), 6.89–
6.91 (m, 2 H, Ar), 6.98–7.03 (m, 4 H, Ar), 7.24–7.33 (m, 3 H, Ar),
7.39–7.43 (m, 2 H, Ar), 7.49–7.55 (m, 2 H, Ar), 7.56–7.58 (m, 2 H,
Ar) ppm. 13C NMR (CDCl3, 100 MHz, TMS): δ = 30.9, 33.1, 33.3,
35.0, 43.2, 52.8, 55.06, 55.12, 113.1, 113.7, 126.93, 126.97, 127.01,
127.2, 128.7, 128.8, 130.1, 130.8, 131.1, 135.4, 138.8, 141.1, 145.5,
1
Ar) ppm. 4cb: H NMR (CDCl3, 300 MHz, TMS): δ = 3.19 (d, J
= 7.2 Hz, 2 H, CH2), 3.72 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3),
6.10 (t, J = 7.2 Hz, 1 H, =CH), 6.33 (s, 1 H, =CH), 6.53–7.23 (m,
1
16 H, Ar) ppm. 4cc: H NMR (CDCl3, 300 MHz, TMS): δ = 3.52
(d, J = 6.9 Hz, 2 H, CH2), 3.79 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3),
5.95 (t, J = 6.9 Hz, 1 H, =CH), 6.53–7.23 (m, 17 H, Ar) ppm. IR
(CH Cl ): ν = 3041, 2999, 2955, 2836, 2359, 2342, 1782, 1683, 1662,
˜
2
2
146.8, 157.8, 158.3 ppm. IR (CH Cl ): ν = 3026, 2924, 2848, 1882,
˜
2
2
1602, 1572, 1506, 1463, 1442, 1409, 1289, 1248, 1178, 1161, 1106,
1032, 1014, 830, 795, 766, 616, 576, 540 cm–1. MS (%): m/z = 468
(97) [M]+, 109 (20), 121 (34), 265 (16), 361 (21), 373 (100), 374
(28), 469 (35). HRMS (EI): calcd. for C31H26O2F2: 468.1893; found
468.1901.
1605, 1571, 1510, 1485, 1461, 1439, 1409, 1287, 1240, 1173, 1106,
1054, 1028, 908, 827, 788, 765, 736, 698, 586, 562, 545, 511 cm–1.
MS (%): m/z = 500 (55) [M]+, 305 (100), 171 (47), 292 (31), 306
(24), 501 (23), 121 (22), 180 (10). C36H36O2 (500.2715): calcd. C
86.36, H 7.25; found C 86.68, H 7.23. HRMS (EI): calcd. for
C30H36O2 500.2715; found 500.2717.
4da, 4db and 4dc: A colorless oil (5 mg, 10%); 4da: 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.65–2.69 (m, 2 H, CH2), 2.77–2.81
(m, 2 H, CH2), 3.69 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 6.54 (d,
J = 8.7 Hz, 2 H, Ar), 6.65 (d, J = 8.7 Hz, 2 H, Ar), 6.73 (d, J =
8.7 Hz, 2 H, 2 H, Ar), 7.12 (d, J = 8.7 Hz, 2 H, Ar), 7.21 (s, 8 H,
3q: A white solid (30 mg, 67%), m.p. 163–165 °C. 1H NMR
(CDCl3, 400 MHz, TMS): δ = 1.47–1.55 (m, 2 H, CH2), 1.63–1.69
(m, 5 H, CH2), 2.07 (t, J = 7.2 Hz, 2 H, CH2), 2.21 (s, 3 H, CH3),
2.27 (s, 3 H, CH3), 2.43–2.50 (m, 1 H, CH), 2.82 (t, J = 7.2 Hz, 2
H, CH2), 3.72 (s, 3 H, OCH3), 3.84 (s, 3 H, OCH3), 6.64–6.66 (m,
2 H, Ar), 6.89–6.93 (m, 3 H, Ar), 6.96–7.02 (m, 5 H, Ar), 7.14 (d,
J = 8.0 Hz, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz, TMS): δ
= 19.3, 20.8, 30.1, 33.1, 33.3, 35.2, 38.7, 52.9, 55.06, 55.10, 113.0,
113.7, 125.2, 126.7, 128.8, 130.1, 130.8, 131.0, 131.1, 134.9, 135.1,
1
Ar) ppm. 4db: H NMR (CDCl3, 300 MHz, TMS): δ = 3.19 (d, J
= 7.5 Hz, 2 H, CH2), 3.77 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3),
6.15 (t, J = 7.5 Hz, 1 H, =CH), 6.32 (s, 1 H, =CH) 6.54–7.21 (m,
1
16 H, Ar) ppm. 4dc: H NMR (CDCl3, 300 MHz, TMS): δ = 3.52
(d, J = 6.3 Hz, 2 H, CH2), 3.73 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3),
6.00 (t, J = 6.3 Hz, 1 H, =CH) 6.54–7.21 (m, 17 H, Ar) ppm. IR
135.4, 142.5, 145.6, 157.8, 158.3 ppm. IR (CH Cl ): ν = 3032, 2999,
˜
2
2
(CH Cl ): ν = 3032, 3000, 2955, 2933, 2835, 2360, 2342, 1683, 1604,
˜
2
2
2926, 2849, 1605, 1570, 1442, 1283, 1246, 1178, 1105, 1053, 1035,
909, 829, 788, 733, 591, 568, 539 cm–1. MS (%): m/z = 452 (65)
[M]+, 305 (100), 132 (46), 171 (46), 119 (31), 292 (27), 121 (27), 453
(25). C32H36O2 (452.2715): calcd. C 84.91, H 8.02; found C 85.37,
1575, 1508, 1463, 1441, 1419, 1398, 1287, 1248, 1176, 1091, 1033,
1013, 830, 756, 738, 519 cm–1. MS (%): m/z = 500 (100) [M]+, 121
(62), 135 (17), 165 (21), 239 (36), 252 (21), 253 (22), 265 (54), 389
(49), 501 (38), 502 (73) 503 (25). HRMS (EI): calcd. for
C31H26O2Cl2 500.1309; found 500.1310.
H
7.83. HRMS (EI): calcd. for C32H36O2 452.2715; found
452.2714.
1
3r: A colorless oil (28 mg, 61%). 1H NMR (CDCl3, 400 MHz, 4ea and 4ec: A colorless oil (16 mg, 32%); 4ea: H NMR (CDCl3,
TMS): δ = 1.11–1.26 (m, 3 H, CH2), 1.55–1.67 (m, 3 H, CH2),
1.74–1.77 (m, 2 H, CH2), 2.04–2.08 (m, 2 H, CH2), 2.66–2.74 (m,
300 MHz, TMS): δ = 2.65–2.69 (m, 2 H, CH2), 2.74–2.79 (m, 2 H,
CH2), 3.68 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 3.78 (s, 6 H, 2
1 H, CH), 2.81 (t, J = 7.2 Hz, 1 H, CH2), 3.70 (s, 3 H, OCH3), OCH3), 6.52 (d, J = 8.7 Hz, 2 H, Ar), 6.65–6.78 (m, 8 H, Ar), 7.12
3.81 (s, 3 H, OCH3), 6.62–6.64 (m, 2 H, Ar), 6.85–6.90 (m, 2 H,
Ar), 6.93–6.96 (m, 4 H, Ar), 7.06–7.10 (m, 2 H, Ar), 7.21–7.24 (m,
2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz, TMS): δ = 23.3, 33.1,
33.40, 33.43, 33.9, 40.4, 42.9, 53.9, 55.0, 55.1, 113.0, 113.7, 128.2,
128.3, 128.8, 129.8, 130.0, 130.5, 131.1, 131.3, 135.6, 145.2, 146.0,
(d, J = 8.7 Hz, 2 H, Ar), 7.22 (d, J = 8.7 Hz, 2 H, Ar), 7.25 (d, J
= 8.7 Hz, 2 H, Ar) ppm. 4ec: H NMR (CDCl3, 300 MHz, TMS):
δ = 3.54 (d, J = 6.6 Hz, 2 H, CH2), 3.78 (s, 3 H, OCH3), 3.79 (s, 3
H, OCH3), 3.82 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 5.89 (t, J =
1
6.6 Hz, 1 H, =CH), 652–7.25 (m, 17 H, Ar) ppm. IR (CH Cl ): ν
˜
2
2
157.9, 158.3 ppm. IR (CH Cl ): ν = 3032, 2997, 2927, 2849, 1882,
= 3033, 2997, 2953, 2928, 2835, 2359, 2342, 1605, 1575, 1507, 1463,
1441, 1289, 1248, 1178, 1112, 1036, 829, 802 cm–1. MS (%): m/z =
492 (83) [M]+, 121 (27), 227 (11), 253 (12), 371 (14), 384 (11), 385
˜
2
2
1605, 1511, 1493, 1463, 1442, 1283, 1247, 1178, 1091, 1035, 1013,
908, 828, 732, 572, 530 cm–1. MS (%): m/z = 458 (100) [M]+, 415
Eur. J. Org. Chem. 2009, 4971–4982
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4979

L.-F. Yao, M. Shi
(100), 386 (29), 493 (30). HRMS (EI): calcd. for C33H32O4: ppm. 13C NMR (CDCl3, 100 MHz, TMS): δ = 34.9, 55.19, 55.21,
FULL PAPER
492.2300; found 492.2301.
113.7, 113.9, 124.6, 125.2, 127.27, 127.32, 127.4, 127.7, 128.2,
129.0, 130.7, 131.8, 134.6, 139.5, 139.9, 142.8, 143.3, 157.9, 158.8
4fa, 4fb and 4fc: A colorless oil (18 mg, 31%); 4fa: 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.64–2.68 (m, 2 H, CH2), 2.77–2.81
(m, 2 H, CH2), 3.70 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 6.54 (d,
J = 8.7 Hz, 2 H, Ar), 6.64 (d, J = 8.7 Hz, 2 H, Ar), 6.72 (d, J =
8.7 Hz, 2 H, Ar), 7.11 (d, J = 8.7 Hz, 2 H, Ar), 7.15 (d, J = 8.7 Hz,
4 H, Ar), 7.35 (d, J = 8.7 Hz, 4 H, Ar) ppm. 4fb: 1H NMR (CDCl3,
300 MHz, TMS): δ = 3.18 (d, J = 6.6 Hz, 2 H, CH2), 3.73 (s, 3 H,
OCH3), 3.78 (s, 3 H, OCH3), 6.15 (t, J = 6.6 Hz, 1 H, =CH), 6.32
(s, 1 H, =CH), 6.54–7.35 (m, 16 H, Ar) ppm. 4fc: 1H NMR (CDCl3,
300 MHz, TMS): δ = 3.51 (d, J = 6.9 Hz, 2 H, CH2), 3.82 (s, 3 H,
OCH3), 3.83 (s, 3 H, OCH3), 6.01 (t, J = 6.9 Hz, 1 H, =CH), 6.54–
ppm. IR (CH Cl ): ν = 3028, 2932, 2834, 1608, 1510, 1442, 1284,
˜
2
2
1247, 1178, 1111, 1074, 1036, 898, 829, 804, 766, 746, 701, 600
cm–1. MS (%): m/z = 432 (100) [M]+, 121 (48), 433 (37), 311 (35),
265 (24), 165 (19), 310 (18), 91 (17). HRMS (EI): calcd. for
C31H28O2 432.2091; found 432.2089.
5a: A white solid (98 mg, 68%), m.p. 244–246 °C. 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.39 (dd, J = 10.2, 16.2 Hz, 1 H,
CH2), 2.56 (dd, J = 7.8, 16.2 Hz, 1 H, CH2), 3.21 (d, J = 10.5 Hz,
1 H, CH), 3.63 (s, 3 H, OCH3), 3.67 (s, 3 H, OCH3), 3.72 (s, 9 H,
3 OCH3), 3.87 (s, 3 H, OCH3), 4.23–4.32 (m, 1 H, CH), 6.41 (d, J
= 8.7 Hz, 2 H, Ar), 6.44 (d, J = 8.7 Hz, 2 H, Ar), 6.52 (d, J =
8.7 Hz, 2 H, Ar), 6.57 (d, J = 8.7 Hz, 2 H, Ar), 6.65 (d, J = 8.7 Hz,
2 H, Ar), 6.68 (d, J = 8.7 Hz, 2 H, Ar), 6.84 (d, J = 8.7 Hz, 2 H,
Ar), 6.91 (d, J = 8.7 Hz, 2 H, Ar), 6.97 (d, J = 8.7 Hz, 2 H, Ar),
7.00 (d, J = 8.7 Hz, 2 H, Ar), 7.12 (d, J = 8.7 Hz, 2 H, Ar), 7.17
(d, J = 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz, TMS):
δ = 41.6, 52.1, 53.0, 54.8, 55.0, 55.1, 55.2, 68.1, 112.0, 112.5, 112.7,
112.8, 113.1, 113.6, 128.7, 129.5, 129.6, 129.8, 130.1, 130.7, 131.1,
131.3, 132.1, 135.9, 136.6, 136.8, 138.3, 143.9, 157.1, 157.2, 157.4,
7.35 (m, 17 H, Ar) ppm. IR (CH Cl ): ν = 2953, 2927, 2835, 2360,
˜
2
2
1653, 1604, 1570, 1558, 1507, 1487, 1458, 1439, 1289, 1248, 1177,
1076, 1034, 1008, 829, 796 cm–1. MS (%): m/z = 588 (48) [M]+, 121
(47), 265 (22), 433 (81), 434 (25), 435 (77), 436 (22), 589 (18), 590
(100), 591 (34), 592 (54), 593 (17). HRMS (EI): calcd. for
C31H26O2Br2 588.0302; found 588.0300.
1
4ha, 4hb and 4hc: A colorless oil (10 mg, 22%). H NMR (CDCl3,
300 MHz, TMS): δ = 2.68–2.73 (m, 2 H, CH2), 2.76–2.81 (m, 2 H,
CH2), 3.68 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 6.52 (d, J = 8.7 Hz,
2 H, Ar), 6.66 (d, J = 8.7 Hz, 2 H, Ar), 6.72 (d, J = 8.7 Hz, 2 H,
Ar), 6.90 (t, J = 8.7 Hz, 2 H, Ar), 7.13 (d, J = 8.7 Hz, 2 H, Ar),
157.6, 158.0, 158.2 ppm. IR (CH Cl ): ν = 3033, 3000, 2933, 2905,
˜
2
2
2834, 2532, 2054, 1890, 1606, 1581, 1514, 1461, 1441, 1419, 1336,
1290, 1254, 1177, 1115, 1035, 831, 788, 773, 738, 704, 684, 653,
642, 632, 617, 599, 584, 566, 543, 517 cm–1. MS (%): m/z = 718 (2)
[M]+, 227 (100), 478 (37), 357 (29), 121 (26), 240 (18), 228 (18), 491
(16), 238 (15). C48H46O6 (718.89): calcd. C 80.20, H 6.45; found C
80.25, H 6.61. HRMS (EI): calcd. for C48H46O6 718.3294; found
718.3306.
7.24–7.28 (m, 5 H, Ar) ppm. IR (CH Cl ): ν = 3055, 2999, 2954,
˜
2
2
2836, 2538, 2358, 2048, 1888, 1683, 1662, 1602, 1574, 1506, 1463,
1443, 1289, 1248, 1177, 1161, 1033, 831, 812, 797, 765, 702, 576,
557, 539 cm–1. MS (%): m/z = 450 (100) [M]+, 121 (34), 343 (18),
355 (34), 373 (63), 374 (19), 451 (37). HRMS (EI): calcd. for
C31H27O2F: 450.1991; found 450.1995.
4ka and 4kb: A colorless oil (5 mg, 8%); 4ka: 1H NMR (CDCl3,
300 MHz, TMS): δ = 0.83–0.90 (m, 6 H, CH3), 1.27–1.45 (m, 12
H, CH2), 1.66–1.77 (m, 4 H, CH2), 2.72–2.80 (m, 4 H, 2 CH2), 3.79
(t, J = 6.6 Hz, 2 H, OCH2), 3.90 (t, J = 6.6 Hz, 2 H, OCH2), 6.49
(d, J = 8.7 Hz, 2 H, Ar), 6.65 (d, J = 8.7 Hz, 2 H, Ar), 6.71 (d, J
= 8.7 Hz, 2 H, Ar), 7.10–7.23 (m, 8 H, Ar), 7.33 (d, J = 8.7 Hz, 4
H, Ar) ppm. 4kb: 1H NMR (CDCl3, 300 MHz, TMS): δ = 3.22 (d,
J = 7.5 Hz, 2 H, CH2), 6.19 (t, J = 7.5 Hz, 1 H, =CH), 6.35 (s, 1
5b: A white solid (77 mg, 50%), m.p. 197–199 °C. 1H NMR
(CDCl3, 300 MHz, TMS): δ = 1.26–1.36 (m, 12 H, 4 CH3), 2.38
(dd, J = 10.5, 15.9 Hz, 1 H, CH2), 2.56 (dd, J = 7.5, 15.9 Hz, 1 H,
CH2), 3.19 (d, J = 10.5 Hz, 1 H, CH), 3.70 (s, 3 H, OCH3), 3.78–
3.98 (m, 11 H, CH2 and OCH3), 4.22–4.32 (m, 1 H, CH), 6.40 (d,
J = 9.3 Hz, 2 H, Ar), 6.44 (d, J = 9.3 Hz, 2 H, Ar), 6.50–6.73 (m,
8 H, Ar), 6.81–7.00 (m, 8 H, Ar), 7.12 (d, J = 8.7 Hz, 2 H, Ar),
7.18 (d, J = 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz,
TMS): δ = 14.76, 14.84, 41.6, 52.2, 53.1, 55.1, 55.2, 62.9, 63.1, 63.2,
68.1, 112.0, 112.5, 113.2, 113.4, 113.7, 113.9, 114.1, 128.7, 129.5,
129.9, 130.0, 130.7, 131.1, 131.3, 132.1, 135.8, 136.6, 136.8, 138.2,
143.9, 156.6, 156.8, 157.0, 157.1, 157.5, 158.0 ppm. IR (CH2Cl2):
H, =CH), 6.49–7.33 (m, 18 H, Ar) ppm. IR (CH Cl ): ν = 3057,
˜
2
2
2930, 2858, 2357, 2054, 1653, 1604, 1575, 1506, 1469, 1446, 1285,
1245, 1177, 1031, 830, 760, 701 cm–1. MS (%): m/z = 572 (100)
[M]+, 43 (73), 107 (18), 495 (70), 496 (28), 573 (46), 574 (11).
HRMS (EI): calcd. for C41H48O2 572.3652; found 572.3654.
ν = 3035, 2979, 2932, 2904, 2835, 1606, 1581, 1509, 1478, 1463,
˜
1
1442, 1392, 1298, 1251, 1178, 1116, 1045, 923, 828, 808, 739, 611,
549, 518 cm–1. MS (%): m/z = 774 (18) [M]+, 506 (100), 255 (75),
519 (47), 227 (35), 268 (20), 371 (18). C52H54O6 (775.00): calcd. C
80.59, H 7.02; found C 80.57, H 7.28. HRMS (EI): calcd. for
C52H54O6 774.3929; found 774.3920.
4ab: A white solid (1 mg, 1%), m.p. 90–92 °C. H NMR (CDCl3,
300 MHz, TMS): δ = 3.22 (d, J = 7.8 Hz, 2 H, CH2), 3.71 (s, 3 H,
OCH3), 3.78 (s, 3 H, OCH3), 6.18 (t, J = 7.8 Hz, 1 H, =CH), 6.35
(s, 1 H, =CH), 6.64 (d, J = 8.4 Hz, 2 H, Ar), 6.81 (d, J = 8.4 Hz,
2 H, Ar), 6.89 (d, J = 8.4 Hz, 2 H, Ar), 7.03 (d, J = 8.4 Hz, 2 H,
Ar), 7.12–7.37 (m, 10 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz,
TMS): δ = 40.6, 55.06, 55.12, 113.2, 113.8, 125.8, 126.7, 126.96,
127.01, 127.3, 128.0, 128.1, 129.6, 129.8, 130.09, 130.14, 133.6,
5c: A colorless oil (102 mg, 50%). 1H NMR (CDCl3, 300 MHz,
TMS): δ = 0.86–0.90 (m, 12 H, CH3), 1.27–1.38 (m, 24 H, CH2),
1.57–1.75 (m, 8 H, CH2), 2.38 (dd, J = 7.8, 15.9 Hz, 1 H, CH2),
2.57 (dd, J = 7.5, 15.9 Hz, 1 H, CH2), 3.20 (d, J = 10.8 Hz, 1 H,
CH), 3.71 (s, 3 H, OCH3), 3.74–3.98 (m, 11 H, CH2 and CH3),
4.20–4.32 (m, 1 H, CH), 6.40 (d, J = 9.3 Hz, 2 H, Ar), 6.43 (d, J
= 9.3 Hz, 2 H, Ar), 6.50–6.72 (m, 8 H, Ar), 6.77–7.00 (m, 8 H, Ar),
7.12 (d, J = 9.3 Hz, 2 H, Ar), 7.19 (d, J = 9.3 Hz, 2 H, Ar) ppm.
13C NMR (CDCl3, 75 MHz, TMS): δ = 14.0, 22.6, 25.65, 25.70,
139.6, 139.8, 142.6, 142.9, 157.8, 158.4 ppm. IR (CH Cl ): ν =
˜
2
2
3028, 2926, 2853, 2834, 1608, 1510, 1461, 1442, 1287, 1247, 1178,
1074, 1035, 900, 830, 805, 766, 745, 701, 600 cm–1. MS (%): m/z =
432 (100) [M]+, 121 (48), 433 (37), 311 (35), 265 (24), 165 (19), 310
(18), 91 (17). HRMS (EI): calcd. for C31H28O2: 432.2091; found
432.2089.
4aB: A white solid (25 mg, 98%), m.p. 94–96 °C. 1H NMR (CDCl3, 29.2, 29.3, 31.5, 41.6, 52.1, 53.1, 55.1, 55.2, 67.5, 67.7, 68.1, 112.0,
300 MHz, TMS): δ = 3.73 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 112.5, 113.3, 113.4, 113.7, 113.8, 113.9, 114.1, 128.7, 129.4, 129.5,
4.06 (s, 2 H, CH2), 6.72 (d, J = 11.4 Hz, 1 H, =CH), 6.74 (d, J = 129.8, 129.9, 130.7, 131.1, 131.4, 132.0, 132.1, 135.8, 136.7, 136.8,
8.7 Hz, 2 H, Ar), 6.81 (d, J = 8.7 Hz, 2 H, Ar), 7.09 (d, J = 11.4 Hz, 138.2, 143.8, 156.8, 157.0, 157.1, 157.2, 157.7, 158.0 ppm. IR
1 H, =CH), 7.17 (d, J = 8.7 Hz, 2 H, Ar), 7.23–7.44 (m, 12 H, Ar)
(CH Cl ): ν = 3035, 2931, 2859, 1606, 1581, 1509, 1468, 1390, 1285,
˜
2 2
4980
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4971–4982

Lewis-Acid-Catalyzed Reactions of Bis(4-Alkoxyphenyl)methanol
1244, 1178, 1114, 1036, 938, 830, 787, 728, 614, 552 cm–1. ESI-MS
(%): m/z = 1021 [M + Na]+. HRMS (ESI): calcd. for C68H86O6
1021.6324; found 1021.6317.
[1]
[2]
For recent reviews, see: a) I. Nakamura, Y. Yamamoto, Adv.
Synth. Catal. 2002, 344, 111–129; b) A. Brandi, S. Cicchi, F. M.
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the synthesis of MCPs, see: A. Brandi, A. Goti, Chem. Rev.
1998, 98, 589–636.
Selected recent articles about transition-metal-catalyzed reac-
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Yamamoto, J. Org. Chem. 2001, 66, 270–275; b) M. Lautens,
C. Meyer, A. Lorenz, J. Am. Chem. Soc. 1996, 118, 10676–
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W. Huang, J. Org. Chem. 2005, 70, 5606–5610; f) I. Nakamura,
H. Itagaki, Y. Yamamoto, J. Org. Chem. 1998, 63, 6458–6459;
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Chem. Soc. 1997, 119, 8123–8124; h) M. Suginome, T. Mat-
suda, Y. Ito, J. Am. Chem. Soc. 2000, 122, 11015–11016; i)
M. E. Scott, Y. Bethuel, M. Lautens, J. Am. Chem. Soc. 2007,
129, 1482–1483.
Selected recent articles about Lewis-acid-mediated reactions of
MCPs: a) M. Shi, B. Xu, Org. Lett. 2002, 4, 2145–2148; b) B.
Xu, M. Shi, Org. Lett. 2003, 5, 1415–1418; c) X. Huang, H.-
W. Zhou, Org. Lett. 2002, 4, 4419–4422; d) J.-W. Huang, M.
Shi, Tetrahedron Lett. 2003, 44, 9343–9347; e) .-F. Yao, M. Shi,
Org. Lett. 2007, 9, 5187–5190 and references cited herein.
a) D. H. Camacho, I. Nakamura, S. Saito, Y. Yamamoto, An-
gew. Chem. Int. Ed. 1999, 38, 3365–3367; b) I. Nakamura,
B. H. Oh, S. Saito, Y. Yamamoto, Angew. Chem. Int. Ed. 2001,
40, 1298–1300; c) B. H. Oh, I. Nakamura, S. Saito, Y. Yamam-
oto, Tetrahedron Lett. 2001, 42, 6203–6205; d) B. H. Oh, I.
Nakamura, S. Saito, Y. Yamamoto, Heterocycles 2003, 61, 247–
257; e) S. Braese, A. de Meijere, Angew. Chem. Int. Ed. Engl.
1995, 34, 2545–2547; f) I. Nakamura, T. Nemoto, Y. Yamam-
oto, A. de Meijere, Angew. Chem. Int. Ed. 2006, 45, 5176–5179.
a) M. Shi, B. Xu, J.-W. Huang, Org. Lett. 2004, 6, 1175–1178;
b) M. Shi, L.-X. Shao, B. Xu, Org. Lett. 2003, 5, 579–582; c)
L.-X. Shao, B. Xu, J.-W. Huang, M. Shi, Chem. Eur. J. 2006,
12, 510–517; d) J.-W. Huang, M. Shi, Synlett 2004, 2343–2346;
e) L. Patient, M. B. Berry, J. D. Kilburn, Tetrahedron Lett.
2003, 44, 1015–1017.
a) S.-M. Ma, J.-L. Zhang, J. Am. Chem. Soc. 2003, 125, 12386–
12387; b) M. Lautens, W. Han, J. Am. Chem. Soc. 2002, 124,
6312–6316; c) M. Lautens, W. Han, J. H.-C. Liu, J. Am. Chem.
Soc. 2003, 125, 4028–4029; d) M. E. Scott, W. Han, M. Laut-
ens, Org. Lett. 2004, 6, 3309–3312; e) M. E. Scott, M. Lautens,
Org. Lett. 2005, 7, 3045–3047. Ring enlargement of MCPs; f)
M. Shi, L. P. Liu, J. Tang, J. Am. Chem. Soc. 2006, 128, 7430–
7431; g) A. Furstner, C. Aissa, J. Am. Chem. Soc. 2006, 128,
6306–6307.
5d: A white solid (90 mg, 53%), m.p. 182–184 °C. 1H NMR
(CDCl3, 300 MHz, TMS): δ = 2.39 (dd, J = 10.8, 16.2 Hz, 1 H,
CH2), 2.56 (dd, J = 7.2, 16.2 Hz, 1 H, CH2), 3.20 (d, J = 10.5 Hz,
1 H, CH), 3.70 (s, 3 H, OCH3), 3.85 (s, 3 H, OCH3), 4.22–4.51 (m,
9 H, CH2 and CH), 5.17–5.38 (m, 8 H, =CH2), 5.88–6.06 (m, 4 H,
=CH), 6.43 (s, 3 H, Ar), 6.54 (d, J = 8.4 Hz, 2 H, Ar), 6.56 (d, J
= 8.4 Hz, 2 H, Ar), 6.65 (d, J = 8.4 Hz, 2 H, Ar), 6.70 (d, J =
8.4 Hz, 2 H, Ar), 6.82–7.01 (m, 9 H, Ar), 7.12 (d, J = 8.4 Hz, 2 H,
Ar), 7.17 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz, TMS): δ = 41.5, 52.1, 53.0, 55.0, 55.2, 68.1, 68.3, 68.5,
68.7, 112.0, 112.5, 113.5, 113.6, 113.9, 114.3, 117.4, 117.5, 117.6,
128.7, 129.5, 129.7, 129.9, 130.2, 130.7, 131.0, 131.2, 132.1, 133.1,
133.2, 133.3, 133.4, 136.0, 136.5, 136.7, 138.4, 143.9, 156.3, 156.5,
156.7, 157.1, 157.2, 158.0 ppm. IR (CH Cl ): ν = 3034, 2995, 2932,
˜
2
2
2835, 2533, 2051, 1884, 1648, 1606, 1581, 1508, 1461, 1442, 1424,
1361, 1294, 1247, 1179, 1115, 1032, 997, 926, 830, 787, 740, 623,
568, 546 cm–1. C56H54O6 (823.04): calcd. C 81.72, H 6.61; found C
81.47, H 6.66. ESI-MS (%): m/z = 822 [M + Na]+. HRMS (ESI):
calcd. for C55H54O6Na+ 845.3801; found 845.3813.
[3]
[4]
5e: A white solid (95 mg, 57%), m.p. 188–190 °C. 1H NMR
(CDCl3, 400 MHz, TMS): δ = 2.39 (dd, J = 10.4, 16.0 Hz, 1 H,
CH2), 2.43–2.49 (m, 4 H, CH), 2.56 (dd, J = 7.6, 16.0 Hz, 1 H,
CH2), 3.22 (d, J = 10.4 Hz, 1 H, CH), 3.71 (s, 3 H, OCH3), 3.87
(s, 3 H, OCH3), 4.24–4.31 (m, 1 H, CH), 4.49 (d, J = 2.8 Hz, 2 H,
CH2), 4.54 (d, J = 2.8 Hz, 2 H, CH2), 4.59 (d J = 2.8 Hz, 2 H,
CH2), 4.60 (d, J = 2.8 Hz, 2 H, CH2), 6.43–6.50 (m, 4 H, Ar), 6.56
(d, J = 8.8 Hz, 2 H, Ar), 6.59 (d, J = 8.8 Hz, 2 H, Ar), 6.72 (d, J
= 8.8 Hz, 2 H, Ar), 6.76 (d, J = 8.8 Hz, 2 H, Ar), 6.83 (d, J =
8.8 Hz, 2 H, Ar), 6.92 (d, J = 8.8 Hz, 2 H, Ar), 6.98 (d, J = 8.8 Hz,
2 H, Ar), 7.01 (d, J = 8.8 Hz, 2 H, Ar), 7.09 (d, J = 8.8 Hz, 2 H,
Ar), 7.15 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz, TMS): δ = 41.6, 52.1, 53.1, 55.1, 55.2, 55.6, 55.7, 55.8,
58.4, 68.2, 75.2, 75.30, 75.33, 75.5, 78.5, 78.60, 78.67, 78.72, 112.1,
112.6, 113.8, 113.9, 114.2, 114.6, 128.8, 129.5, 129.9, 130.4, 130.7,
130.9, 131.06, 131.11, 132.1, 136.3, 136.6, 136.8, 139.0, 144.1,
[5]
[6]
155.4, 155.6, 155.9, 156.2, 157.2, 158.1 ppm. IR (CH Cl ): ν =
˜
2
2
3291, 3036, 2999, 2931, 2864, 2836, 2121, 2048, 1888, 1605, 1584,
1510, 1455, 1418, 1373, 1216, 1178, 1115, 1075, 1028, 925, 832, 739,
680, 643, 586, 543 cm–1. 3(C56H46O6)·CH2Cl2 (2526.9417): calcd. C
80.24, H 5.58; found C 80.14, H 5.70. ESI-MS (%): m/z = 837 [M
+ Na]+. HRMS (ESI): calcd. for C56H46O6Na+ 837.3168; found
837.3187.
[7]
[8]
a) L. P. Liu, M. Shi, J. Org. Chem. 2004, 69, 2805–2808; b)
L. F. Yao, M. Shi, Org. Lett. 2007, 9, 5187–5189; c) M. Shi,
M. Jiang, L.-P. Liu, Org. Biomol. Chem. 2007, 5, 438–440.
Compound 4ab was determined to be (E)-configured based on
the following two reasons: 1) no interaction between Ha and
Hb was detected from the NOE spectroscopy and 2) the inter-
actions between Ha and the aromatic ring and between Hb and
the aromatic ring could be recognized by NOE spectroscopy.
Supporting Information (see also the footnote on the first page of
this article): The spectroscopic data (1H and 13C spectroscopic
data), HRMS of the compounds shown in Tables 1– 5 and
Schemes 1–5, the X-ray crystal structures of 3a, 4aB, 5a and 5b
along with the detailed description of experimental procedures are
included in the Supporting Information.
Acknowledgments
We thank the Shanghai Municipal Committee of Science and Tech-
nology (06XD14005 and 08dj1400100-2), National Basic Research
Program of China (grant no. 973-2009CB825300) and the National
Natural Science Foundation of China (20872162, 20672127,
20872162, 20821002 and 20732008) for financial support.
Eur. J. Org. Chem. 2009, 4971–4982
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4981

L.-F. Yao, M. Shi
FULL PAPER
[9] CCDC-675136 (for 3a), -712669 (for 4aB), -684691 (for 5a),
-720536 (for 5b) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[10] a) A. W. Schrecker, L. Y. Greenberg, L. L. Hartwell, J. Am.
Chem. Soc. 1952, 74, 5669–5671; b) E. L. Jackson, L. Pastiut,
J. Am. Chem. Soc. 1928, 50, 2249–2260; c) D. J. Cram, J. Am.
Chem. Soc. 1949, 71, 3863–3870; d) D. J. Cram, J. Am. Chem.
Soc. 1952, 74, 2129–2137.
Received: May 18, 2009
Published Online: September 1, 2009
4982
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 4971–4982