Electrophilic addition of allylic carbocations to 2-cyclopropylidene-2- arylethanols: A strategy to 3-oxabicyclo[3.2.0]heptanes

Article abstract of DOI:10.1002/adsc.201201073

We have developed an electrophilic addition of allylic carbocations to 2-cyclopropylidene-2-arylethanols constructing carbon-carbon bonds with excellent regio- and stereoselectivities. The reaction affords 3-oxabicyclo[3.2.0]heptanes in moderate to good y

Full text of DOI:10.1002/adsc.201201073

FULL PAPERS
DOI: 10.1002/adsc.201201073
Electrophilic Addition of Allylic Carbocations to 2-Cyclopropyli-
dene-2-arylethanols: A Strategy to 3-Oxabicyclo[3.2.0]heptanes
U
Bo Meng,a Xian Huang,+, a,b and Luling Wua,*
a
Department of Chemistry, Zhejiang University (Xixi Campus), Hangzhou 310028, Peopleꢀs Republic of China
Fax : (+86)-571-8880-7077; e-mail: wululing@zju.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032, Peopleꢀs Republic of China
b
+
Prof. Huang passed away on March 6, 2010. He had been fully in charge of this project. At this moment, Prof. Luling Wu
is finishing all the projects with help from Prof. Shengming Ma.
Received: December 6, 2012; Revised: May 6, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201201073.
Abstract: We have developed an electrophilic addi- ing/vinyl group shift/intramolecular cyclization se-
tion of allylic carbocations to 2-cyclopropylidene-2- quence.
arylethanols constructing carbon-carbon bonds with
excellent regio- and stereoselectivities. The reaction Keywords: C C bond formation; 2-cyclopropyli-
À
affords 3-oxabicyclo
N
good yields via the electrophilic addition/ring-open- oxabicyclo
N
Introduction
ciency of carbon-carbon bond formation and the po-
tential utility of the products. In 2007, the electrophil-
The electrophilic addition of methylenecyclopropanes ic addition of acyl carbocation to MCPs was success-
(MCPs)[1] is rather attractive since the possible ring- fully realized in our laboratory [Scheme 1, Eq. (1)].[3]
opening may lead to the construction of interesting Later, Shiꢀs group employed propargylic/allenic car-
and complex structures of synthetic or pharmaceutical bocation as the electrophile [Scheme 1, Eq. (2)].[4]
importance.[2] During the last decades, the direct elec- However, the electrophilic addition of MCPs utilizing
trophilic additions of MCPs have been widely investi- allylic carbocations as electrophiles has not been
gated, employing a variety of electrophiles, such as documented well due to the difficulties in the intro-
H+,[2a–d] X+,[2e,f] ArSe+,[2g–i] and ArS+.[2h] Particularly, duction of carbocations with proper reactivity and the
the introduction of suitable carbocations as the elec- control of chemoselectivity. Recently, the electrophilic
trophile has attracted much attention due to the effi- reaction of allylic carbocation and allenes affording
Scheme 1. Previous work on the electrophilic additions of acyl and propargylic/allenic carbocations with MCPs.
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Scheme 2. The electrophilic addition of allylic carbocation.
indene derivatives has been also reported [Scheme 2,
Eq. (3)].[5] Since allylic carbocation intermediates
could be easily formed via the treatment of 1,3-diaryl-
ACHTUNGTRENNUNGprop-2-en-1-ols with Lewis acid, we were interested in
whether the allylic carbocation could be introduced as
the electrophile to react with MCPs.
Based on this knowledge, we envisioned that if a hy-
droxy group is equipped as an intramolecular nucleo-
phile, a cyclic product may be generated via an elec-
trophilic addition/ring-opening/intramolecular nucleo-
philic cyclization sequence [Scheme 2, Eq. (4)].
Herein, we wish to report the ZnCl2-promoted elec-
trophilic addition of 1,3-diarylprop-2-en-1-ols to 2-cy-
clopropylidene-2-arylethanols to furnish 3-oxabicyclo-
Figure 1. ORTEP representation of one enantiomer of 3a.
A
and the phenyl group (from 2a) on the same side of
the tetrahydrofuran ring.
The cyclobutane[8] and tetrahydrofuran[9] units are
prominent structural features of many bioactive natu-
ral products and pharmaceutical molecules. Moreover,
Results and Discussion
Initially, the reaction was carried out utilizing 2-cyclo- the structural skeleton of 3a, 3-oxabicyclo-
propylidene-2-phenylethanol 1a, 1,3-diphenyl-prop-2- [3.2.0]heptane, has been proved to be active scaffold
AHCTUNGTRENNUNG
en-1-ol 2a and ZnCl2 in CH2Cl2 at room temperature. in novel bicyclic nucleosides A–E with anti-HIV activ-
Interestingly, the reaction did not form the precon- ity (Figure 2).[10] Synthetic methods have been devel-
ceived 3,6-dihydro-2H-pyran derivative [Scheme 2, oped to approach 3-oxabicyclo
ACHTUNGTRENNUNG
Eq. (4)].[6] Instead, an unexpected new product 3a
was obtained (Scheme 3). The structure of 3a was de-
termined by the X-ray diffraction analysis, namely
(1S*,2R*,5R*,E)-2,5-diphenyl-1-styryl-3-oxabicyclo-
ACHTUNGTRENNUNG
[3.2.0]heptane (Figure 1).[7] Apparently, the 1,3-diphe-
nylallyl group from 2a no longer existed in the prod-
uct, being transformed to the phenyl group and the
styryl group. The reaction showed excellent stereose-
lectivity, giving the product 3a with the cyclobutane
Scheme 3. The trial reaction for the electrophilic addition of
1a and 2a in the presence of ZnCl2.
Figure 2. Anti-HIV agent dT and the novel class of nucleo-
sides A–E built on a 3-oxabicycloACTHNUGTRNEUNG[3.2.0]heptane scaffold.
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Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
Table 1. Optimization of the conditions for the electrophilic
addition reaction of 2-cyclopropylidene-2-phenylethanol 1a
and 1,3-diphenylprop-2-en-1-ol 2a.[a]
tives via the [2+2]photocycloaddition or the Pd-cata-
lyzed [2+2]cycloaddition of olefins.[11] However, in
most of the known procedures, the irradiation with
high energy UV light, the employment of transition
metal catalyst, and the unsatisfactory stereoselectivity
are inevitable disadvantages. Therefore, an efficient
strategy to synthesize 3-oxabicycloACTHNUTRGNEUNG[3.2.0]heptane ana-
logues is still of significant importance. Thus, we tried
to optimize the conditions of this electrophilic addi-
tion (Table 1). Several Lewis acids were tested first.
FeCl3·6H2O and FeCl3 barely gave any product 3a
(Table 1, entries 2 and 3) and ZrCl4 resulted in a very
low yield (21%, Table 1, entry 4). The solvent effect
was also examined (Table 1, entries 5–8). It is demon-
strated that the reaction can also proceed smoothly in
toluene and 1,2-dichloroethane, yielding 3a in moder-
ate yields (Table 1, entries 5 and 8). Reactions con-
ducted in THF or CHCl3 gave 3a in merely 26% and
36% yields, respectively (Table 1, entries 6 and 7). Di-
chloromethane was an even better choice. When the
reaction was carried out at 08C, the yield of 3a was
raised to 79% (Table 1, entry 9). However, the reac-
tion did not yield 3a in higher yield when the reaction
temperature was À408C (71%, Table 1, entry 10). By
Entry Solvent Temperature Lewis Acid Time Yield of
[oC]
[h]
3a
[%][b]
1
DCM r.t.
ZnCl2
5
74
2
3
4
5
6
7
8
9
DCM r.t.
DCM r.t.
DCM r.t.
toluene r.t.
FeCl3·6H2O 10.5
0
FeCl3
ZrCl4
ZnCl2
ZnCl2
ZnCl2
ZnCl2
ZnCl2
ZnCl2
ZnCl2
24
2.5
2.5
12.2 26
6.2
1
6.7
9.3
2.5
trace
21
67
THF
r.t.
CHCl3 r.t.
36
69
79
71
86
DCE
DCM
r.t.
0
10
DCM À40
11[c]
DCM
0
[a]
Unless otherwise specified, the reactions were conducted
using 0.3 mmol of 1a, 0.3 mmol of 2a, and 0.3 mmol of
Lewis acid in 3 mL of solvent under a nitrogen atmos- utilizing 2.0 equiv. of 2a and ZnCl2, the yield of 3a
phere in a Schlenk tube.
Isolated yield.
The reaction was conducted utilizing 0.3 mmol of 1a,
0.6 mmol of 2a, and 0.6 mmol of ZnCl2.
could be further improved to 86% (Table 1, entry 11).
With the optimal conditions in hand, we explored
the scope of this electrophilic addition of a series of
1,3-diarylprop-2-en-1-ols 2 with 2-cyclopropylidene-2-
[b]
[c]
arylethanols
1
to
synthesize
3-oxabicyclo-
AHCTUNGTREG[NNUN 3.2.0]heptanes 3 (Table 2). It is demonstrated that
Table 2. Reactions of 2-cyclopropylidene-2-arylethanols 1 with 1,3-diarylprop-2-en-1-ols 2 for the synthesis of 3-oxabicyclo-
ACHTUNGTRENNUNG
[3.2.0]heptane derivatives 3.[a]
Entry
1 (R1)
2 (R2)
Time [h]
Yield of 3 [%][b]
1
2
3
4
5
6
7
8
1a (R1 =H)
1a
1a
1a
2a (R2 =H)
2b (R2 =Cl)
2c (R2 =Br)
2d (R2 =Me)
2e (R2 =OMe)
2a (R2 =H)
2c (R2 =Br)
2e (R2 =OMe)
2a (R2 =H)
2a (R2 =H)
2c (R2 =Br)
2.5
3
2.9
2.8
3
4.3
5.1
3.7
2.3
2.6
2.5
86 (3a)
71 (3b)
73 (3c)
61 (3d)
63 (3e)
77 (3f)
75 (3g)
49 (3h)
64 (3i)
65 (3j)
77 (3k)
1a
1b (R1 =Me)
1b
1b
9
10
11
1c (R1 =OMe)
1d (R1 =Cl)
1d
[a]
The reactions were conducted using 0.3 mmol of 1, 0.6 mmol of 2, and 0.6 mmol of ZnCl2 in 3 mL of CH2Cl2 under nitro-
gen atmosphere in a Schlenk tube.
Isolated yield of 3 based on 1.
[b]
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Scheme 4. Reactions of 1a or 1b with non-symmetrical 1,3-diarylprop-2-en-1-ols 2f and 2g.
both 1,3-diarylprop-2-en-1-ols 2b and 2c bearing elec-
Furthermore, when 1,3-diarylprop-2-en-1-ol 2f with
tron-deficient aryl rings could be employed smoothly two differently substituted aryl rings was employed to
to yield products 3b and 3c in 71% and 73% yields, react with 1b, two regioisomers 3l-a and 3l-b were iso-
respectively (Table 2, entries 2 and 3). When an aryl lated in 12% and 58% yields (Scheme 4). Similarly,
ring with an electron-donating group Me or OMe was the reaction of 1a and non-symmetrical 2g gave the
introduced, i.e., 2d or 2e, products 3d and 3e were regioisomers 3m-a and 3m-b in 11% and 67% yields,
generated in relatively lower yields (61% and 63%, respectively. The relative configurations of major
Table 2, entries 4 and 5). Moreover, 2-cyclopropyli- isomer 3l-b and 3m-b were determined by the
dene-2-arylethanols 1b, 1c and 1d with substituents NOESY study (Figure 3).
Me, OMe and Cl on the aryl ring were also applied
Interestingly, when 2h equipped with a strong elec-
successfully and gave corresponding products 3f–k in tron-withdrawing group, NO2, and a strong electron-
moderate to good yields (Table 2, entries 6–11).
donating group, OMe, was employed, the reaction
Figure 3. NOESY studies of 3l-b, 3m-b, and 3n.
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Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
Scheme 5. Reactions of 1a with isomeric non-symmetrical 1,3-diarylprop-2-en-1-ols 2h and 2i.
showed excellent regioselectivity, giving isomer 3n in successfully, and the product 5a bearing a conjugated
64% yield as the sole product (Scheme 5). The reac- 1,3-dienyl group, namely, (1S*,2R*,5R*)-2,5-diphenyl-
tion with isomeric non-symmetrical 1,3-diarylprop-2- 1-[(1E,3E)-4-phenylbuta-1,3-dienyl]-3-oxabicyclo-
en-1-ol 2i also gave the same product 3n as the only
ACHTUNGTREN[NGNU 3.2.0]heptane, was isolated in 62% yield (Table 3,
product in 70% yield, which indicates that 2h and 2i entry 1). (1E,4E)-1,5-Diarylpenta-1,4-dien-3-ols 4b
give the same allylic carbocation intermediate with and 4c with a p-Me or p-Cl substituent could be em-
the electron-rich aryl group stabilizing the carbocat- ployed smoothly, affording corresponding products 5b
ionic center.
and 5c in 51% and 59% yields, respectively (Table 3,
Furthermore, (E)-4-phenylbut-3-en-2-ol 2j with an entries 2 and 3). Also, the reactions of 2-cyclopropyli-
alkyl group and a phenyl group could also be em- dene-2-p-tolylethanol 1b with 4a and 4d yielded 5d
ployed to react with 1a, affording two regioisomers and 5e in moderate yields (Table 3, entries 4 and 5).
3o-a and 3o-b in 36% and 32% yields, respectively
Moreover, the reaction of (E)-1,3-diphenylprop-2-
(Scheme 6). The structures of the isomers 3o-a and enyl amine 6 with 1b under the optimal conditions led
1
3o-b were established by the analysis of the H NMR to an unidentified mixture (Scheme 7).
spectrum.
To shed light on the possible mechanism, some con-
Equipped with two allylic groups sharing the same trol experiments were conducted. By employing 2.0
CH(OH) unit, (1E,4E)-1,5-diarylpenta-1,4-dien-3-ols or 4.0 equiv. of HCl (solution in anhydrous CH2Cl2),
4 may also act as a precursor of an allylic carbocation the reaction of 1d with 2a afforded product 3j in 19%
and undergo a similar electrophilic addition reaction and 22% yields, respectively, indicating that ZnCl2 is
with 2-cyclopropylidene-2-arylethanols 1. With this vital in the reaction (compare Scheme 8 with Table 2,
notion in mind, we tested the reaction of (1E,4E)-1,5- entry 10).
diphenylpenta-1,4-dien-3-ol 4a and 2-cyclo-propyli-
Based on these experimental facts, a plausible
dene-2-phenylethanol 1a under the optimized reaction mechanism for this reaction is proposed (Scheme 9).
conditions (Table 3, entry 1). The reaction proceeded Allylic carbocation intermediate A would be formed
via the interaction of ZnCl2 with the allylic alcohol 2.
Electrophilic addition of the in-situ generated cation
A with the C=C bond on the C-1 position of the MCP
1 affords the cation intermediate B. Notably, when
the two aryl rings of the allylic alcohol 2 are different-
ly substituted, the electrophilic addition could occur
on both C-1 and C-3 atoms of carbocation A, and the
electrophilic addition on the carbon atom near the
relatively electron-rich aryl group is favored
(Scheme 4 and Scheme 5). The cyclobutane inter-
mediate C is formed via the ring-opening 1,2-carbon
shift process. The observation of the highly stereose-
Scheme 6. Reaction of 1a with 2j.
lective formation of product 3 may suggest that the
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Table 3. Reactions of 2-cyclopropylidene-2-arylethanols 1 with (1E,4E)-1,5-diarylpenta-1,4-dien-3-ols 4 for the synthesis of 3-
oxabicyclo
ACHTUNGTRENNUNG
Entry
1 (R1)
4 (R3)
Time [h]
Yield of 5 [%][b]
1
2
3
4
5
1a (R1 =H)
1a
4a (R3 =H)
4b (R3 =Me
4c (R3 =Cl)
4a (R3 =H)
4d (R3 =Br)
3.8
4.8
3
4.8
4.3
62 (5a)
51 (5b)
59 (5c)
53 (5d)
57 (5e)
1a
1b (R1 =Me)
1b
[a]
The reactions were conducted using 0.3 mmol of 1, 0.6 mmol of 4, and 0.6 mmol of ZnCl2 in 3 mL of CH2Cl2 under nitro-
gen atmosphere in a Schlenk tube.
Isolated yield of 5 based on 1.
[b]
Scheme 7. Reaction of 1b with (E)-1,3-diphenylprop-2-enylamine 6.
Scheme 8. Experiment with HCl replacing ZnCl2.
subsequent vinyl migration/intramolecular cyclization H’.[13] Subsequent ring-opening/vinyl group shift/intra-
process occurs in a concerted manner. The transient molecular cyclization sequence affords product 5
intermediate D bearing the benzylic carbocation is bearing the conjugated 1,3-dienyl group.
more stable than E with the allylic carbocation,[12]
which may explain the exclusive migration of vinyl
group forming 3, not F. The cis-orientation of the Conclusions
vinyl group and the Ar3 is determined by the rigid bi-
cyclic skeleton while the trans-orientation of that and In conclusion, we have disclosed the first electrophilic
the Ar2 may be explained by avoiding the steric inter- addition of allylic carbocation with MCPs. 3-
action of these two groups. Similarly, (1E,4E)-1,5-di- OxabicycloACHTUNGTRNE[NUNG 3.2.0]heptanes, the skeleton of novel nu-
ACHTUNGTRENNUNGarylpenta-1,4-dien-3-ol 4 affords cation G in the pres- cleosides, have been constructed in moderate to good
ence of ZnCl2. The electrophilic addition occurs on yields. In contrast to the conventional synthetic meth-
the C-3 position with perfect regioselectivity due to ods, this electrophilic reaction strategy showed excel-
the higher stability of intermediate H as compared to lent regio- and stereoselectivities. In addition, the uti-
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Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
Scheme 9. Proposed mechanism.
6[17] were prepared according to the known procedures.
lization of high energy UV light and transition metal
catalysts was avoided, affording the desirable prod-
ucts in an economical and environmentally friendly
manner. Due to the high efficiency of the carbon-
carbon bond formation, the excellent selectivity of
the reaction and the potential utility of the products,
this methodology may be of high interest for organic
and pharmaceutical chemistry.
Other commercially available chemicals were purchased and
used without additional purification unless noted otherwise.
1H NMR experiments of compounds 3f, 3h, 3i, 3j, 3k, 3l-a,
3o-a, 5c and 5e were measured with tetramethylsilane
(0 ppm) in C6D6 or the signal of residual benzene
1
(7.16 ppm) as the internal reference. Other H NMR experi-
ments were measured with tetramethylsilane (0 ppm) in
CDCl3 or the signal of residual chloroform (7.26 ppm) as
the internal reference. 13C NMR experiments were mea-
sured in relative to the signal of residual chloroform
(77.0 ppm) in CDCl3.
Experimental Section
Materials
Typical Experimental Procedure for 1[14a]
All reactions were conducted under an N2 atmosphere and
in oven-dried glassware. Anhydrous solvents were distilled
before use: THF and toluene were distilled from sodium
benzophenone; CH2Cl2, CHCl3 and ClCH2CH2Cl were dis-
tilled from P2O5. Petroleum ether refers to the fraction with
boiling point in the range 60–908C. 2-Cyclopropylidene-2-ar-
ylethanols 1,[14] (E)-1,3-diphenyl-prop-2-en-1-ols 2a–i,[15b–i]
(E)-4-phenylbut-3-en-2-ol 2j,[15a,j] (1E,4E)-1,5-diarylpenta-
1,4-dien-3-ols 4[16] and (E)-1,3-diphenylprop-2-en-1-amine
To a stirred suspension of NaH (2.0 g, 51 mmol) in anhy-
drous THF (50 mL) was added cyclopropyltriphenylphos-
phonium bromide (20.3 g, 53 mmol) at room temperature.
After being stirred for 10 h at 658C, a solution of 2-(tert-bu-
tyldiphenylsilyloxy)-1-arylethanone (22.3 mmol) in THF
(10 mL) was added, followed by stirring for 3 h at the same
temperature. Then the resulting mixture was quenched with
water (50 mL) and extracted with Et2O (40 mLꢂ3). The
combined extracts were washed with brine and dried over
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FULL PAPERS
Na2SO4. Filtration, evaporation, and purification by column
chromatography on silica gel (eluent: petroleum ether/ethyl
acetate=50/1) afforded cyclopropylideneethyl silyl ether. To
a stirred solution of the silyl ether (0.5 mmol) in THF
(10 mL) was added a 1M solution of Bu4NF in THF
(1.0 mL, 1.0 mmol). After being stirred for 3 h at room tem-
perature, the resulting mixture was diluted with water and
extracted with Et2O. The combined extracts were washed
with brine. The organic layer was dried over Na2SO4, fil-
tered, concentrated, and purified by column chromatogra-
phy on silica gel (eluent: petroleum ether/ethyl acetate=
5/1) to afford 1.
(E)-1,3-Di-p-tolylprop-2-en-1-ol
(400 MHz, CDCl3): d=7.40–7.04 (m, 8H, Ar-H), 6.64 (d, J=
16.0 Hz, 1H, CH=), 6.32 (dd, J=6.4, 15.6 Hz, 1H, CH=),
5.33 (d, J=6.4 Hz, 1H, ArCH), 2.35 (brs, 7H, CH3 ꢂ2+
OH).
(E)-1,3-Bis(4-methoxyphenyl)prop-2-en-1-ol
(2e):[15g]
1H NMR (400 MHz, CDCl3): d=7.40–7.13 (m, 4H, Ar-H),
6.93–6.70 (m, 4H, Ar-H), 6.52 (d, J=16.0 Hz, 1H, CH=),
6.19 (dd, J=6.6, 15.8 Hz, 1H, CH=), 5.23 (d, J=6.0 Hz,
1H, ArCH), 3.73 (s, 6H, OCH3 ꢂ2), 3.04 (brs, 1H, OH).
(E)-1-(4-Methoxyphenyl)-3-p-tolylprop-2-en-1-ol (2f):[15g]
1H NMR (400 MHz, CDCl3): d=7.44–7.20 (m, 4H, Ar-H),
7.10 (d, J=7.6 Hz, 2H, Ar-H), 6.88 (d, J=8.4 Hz, 2H, Ar-
H), 6.61 (d, J=16.0 Hz, 1H, CH=), 6.31 (dd, J=6.2,
15.8 Hz, 1H, CH=), 5.30 (d, J=6.0 Hz, 1H, ArCH), 3.79 (s,
3H, OCH3), 2.32 (s, 3H, CH3), 2.15 (brs, 1H, OH).
(E)-3-(4-Chlorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-
ol (2g):[15g] 1H NMR (400 MHz, CDCl3): d=7.39–7.18 (m,
6H, Ar-H), 6.81 (d, J=8.4 Hz, 2H, Ar-H), 6.52 (d, J=
15.6 Hz, 1H, CH=), 6.13 (dd, J=7.0, 15.8 Hz, 1H, CH=),
5.25 (d, J=6.8 Hz, 1H, ArCH), 3.76 (s, 3H, OCH3), 2.78
(brs, 1H, OH).
2-Cyclopropylidene-2-phenylethanol (1a):[6,14b,c] 1H NMR
(400 MHz, CDCl3): d=7.66 (d, J=8.0 Hz, 2H, Ar-H), 7.33
(t, J=7.5 Hz, 2H, Ar-H), 7.22 (t, J=7.5 Hz, 1H, Ar-H), 4.66
(s, 2H, CH2), 2.75 (brs, 1H, OH), 1.52–1.26 (m, 2H, CH2),
1.25–1.14 (m, 2H, CH2).
2-Cyclopropylidene-2-p-tolylethanol (1b):[6,14b,c] 1H NMR
(400 MHz, CDCl3): d=7.56 (d, J=7.6 Hz, 2H, Ar-H), 7.16
(t, J=7.6 Hz, 2H, Ar-H), 4.66 (s, 2H, CH2), 2.34 (s, 3H,
CH3), 1.93 (brs, 1H, OH), 1.44–1.36 (m, 2H, CH2), 1.25–1.18
(m, 2H, CH2).
2-Cyclopropylidene-2-(4-methoxyphenyl)ethanol (1c):[6,14c]
1H NMR (400 MHz, CDCl3): d=7.60 (d, J=8.0 Hz, 2H, Ar-
H), 6.86 (d, J=8.4 Hz, 2H, Ar-H), 4.63 (s, 2H, CH2), 3.77 (s,
3H, OCH3), 2.01 (brs, 1H, OH), 1.43–1.33 (m, 2H, CH2),
1.24–1.10 (m, 2H, CH2).
(E)-1-(4-Methoxyphenyl)-3-(4-nitrophenyl)prop-2-en-1-ol
(2h):[15h] 1H NMR (400 MHz, CDCl3): d=8.12 (d, J=8.0 Hz,
2H, Ar-H), 7.46 (d, J=8.4 Hz, 2H, Ar-H), 7.32 (d, J=
8.4 Hz, 2H, Ar-H), 6.89 (d, J=8.8 Hz, 2H, Ar-H), 6.73 (d,
J=16.4 Hz, 1H, CH=), 6.53 (dd, J=5.4, 15.8 Hz, 1H,
CH=), 5.35 (d, J=4.8 Hz, 1H, ArCH), 3.79 (s, 3H, OCH3),
2.58 (brs, 1H, OH).
2-(4-Chlorophenyl)-2-cyclopropylideneethanol
(1d):[6]
1H NMR (400 MHz, CDCl3): d=7.63 (d, J=8.4 Hz, 2H, Ar-
H), 7.32 (d, J=8.4 Hz, 2H, Ar-H), 4.69 (s, 2H, CH2), 1.88
(brs, 1H, OH), 1.55–1.38 (m, 2H, CH2), 1.27–1.18 (m, 2H,
CH2).
(E)-3-(4-Methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-ol
(2i):[15h,i] 1H NMR (400 MHz, CDCl3): d=8.26–8.00 (m, 2H,
Ar-H), 7.54 (d, J=8.4 Hz, 2H, Ar-H), 7.26 (d, J=8.8 Hz,
2H, Ar-H), 6.81 (d, J=8.8 Hz, 2H, Ar-H), 6.59 (d, J=
16.0 Hz, 1H, CH=), 6.11 (dd, J=7.0, 15.8 Hz, 1H, CH=),
5.40 (d, J=6.8 Hz, 1H, ArCH), 3.76 (s, 3H, OCH3), 3.50
(brs, 1H, OH).
Typical Experimental Procedure for 2 and 4[15a]
To a solution of (E)-1,3-diarylprop-2-en-1-one (or (1E,4E)-
1,5-diarylpenta-1,4-dien-3-one) (5 mmol) in 15 mL of
CH3OH was added NaBH4 (209 mg, 5.5 mmol). The reaction
mixture was stirred at room temperature. When the reaction
was complete as monitored by TLC, water was added to
quench the reaction. CH3OH was removed under reduced
pressure, and the residue was extracted with Et2O (20 mL ꢂ
3). The combined organic layer was dried over Na2SO4, fil-
tered, concentrated, and purified by column chromatogra-
phy on silica gel (eluent: petroleum ether/ethyl acetate=
5/1) to afford 2 (or 4).
(E)-4-Phenylbut-3-en-2-ol (2j):[15a,j] 1H NMR (400 MHz,
CDCl3): d=7.40–7.12 (m, 5H, Ar-H), 6.53 (d, J=15.6 Hz,
1H, CH=), 6.23 (dd, J=6.6, 15.8 Hz, 1H, CH=), 4.50–4.40
(m, 1H, CH), 2.29 (brs, 1H, OH), 1.34 (d, J=6.0 Hz, 3H,
CH3).
AHCTUNGTRENNUNG
(1E,4E)-1,5-Diphenylpenta-1,4-dien-3-ol (4a):[16a] 1H NMR
(400 MHz, CDCl3): d=7.50–7.16 (m, 10H, Ar-H), 6.67 (d,
J=16.0 Hz, 2H, CH=ꢂ2), 6.31 (dd, J=6.2, 15.8 Hz, 2H,
CH=ꢂ2), 5.04–4.95 (m, 1H, CH), 1.90 (brs, 1H, OH).
(1E,4E)-1,5-Di-p-tolylpenta-1,4-dien-3-ol
(4b):[16a,b]
(E)-1,3-Diphenylprop-2-en-1-ol
(2a):[15b]
1H NMR
1H NMR (400 MHz, CDCl3): d=7.30 (d, J=8.0 Hz, 4H, Ar-
H), 7.12 (d, J=7.6 Hz, 4H, Ar-H), 6.62 (d, J=16.4 Hz, 2H,
CH= ꢂ 2), 6.26 (dd, J=6.4, 16.0 Hz, 2H, CH= ꢂ 2), 5.00–
4.90 (m, 1H, CH), 2.33 (s, 6H, CH3 ꢂ2), 1.86 (brs, 1H, OH).
(400 MHz, CDCl3): d=7.44–7.16 (m, 10H, Ar-H), 6.70 (d,
J=16.0 Hz, 1H, CH=), 6.39 (dd, J=6.6, 15.8 Hz, 1H,
CH=), 5.39 (d, J=6.4 Hz, 1H, PhCH), 2.04 (brs, 1H, OH).
(E)-1,3-Bis(4-chlorophenyl)prop-2-en-1-ol
(2b):[15c,d]
AHCTUNGTREG(NNNU 1E,4E)-1,5-Bis(4-chlorophenyl)penta-1,4-dien-3-ol
1H NMR (400 MHz, CDCl3): d=7.41–7.15 (m, 8H, Ar-H),
6.60 (d, J=15.6 Hz, 1H, CH=), 6.28 (dd, J=6.4, 16.0 Hz,
1H, CH=), 5.33 (d, J=6.4 Hz, 1H, ArCH), 2.20 (brs, 1H,
OH).
(4c):[13a,16a,b] 1H NMR (400 MHz, CDCl3): d=7.30–7.20 (m,
8H, Ar-H), 6.56 (d, J=16.0 Hz, 2H, CH= 2), 6.22 (dd, J=
6.6, 15.8 Hz, 2H, CH=ꢂ2), 4.96–4.89 (m, 1H, CH), 2.02
(brs, 1H, OH).
(E)-1,3-Bis(4-bromophenyl)prop-2-en-1-ol
(2c):[15d,e]
1H NMR (400 MHz, CDCl3) d 7.43 (d, J=8.8 Hz, 2H, Ar-
H), 7.38 (d, J=8.4 Hz, 2H, Ar-H), 7.22 (d, J=8.0 Hz, 2H,
Ar-H), 7.15 (d, J=8.4 Hz, 2H, Ar-H), 6.51 (d, J=16.0 Hz,
1H, CH=), 6.23 (dd, J=6.2, 15.8 Hz, 1H, CH=), 5.23 (d,
J=6.0 Hz, 1H, ArCH), 2.85 (brs, 1H, OH).
AHCTUNGTREG(NNNU 1E,4E)-1,5-Bis(4-bromophenyl)penta-1,4-dien-3-ol
(4d):[16a,b] 1H NMR (400 MHz, CDCl3): d=7.43 (d, J=
7.6 Hz, 4H, Ar-H), 7.24 (d, J=8.4 Hz, 4H, Ar-H), 6.59 (d,
J=16.0 Hz, 2H, CH= ꢂ 2), 6.27 (dd, J=6.2, 16.2 Hz, 2H,
CH= ꢂ 2), 4.99–4.92 (m, 1H, CH), 2.05 (brs, 1H, OH).
8
asc.wiley-vch.de
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
proton of CH2), 2.03–1.90 (m, 2H, CH2); 13C NMR
Typical Experimental Procedure for the Synthesis of
6[17]
(100 MHz, CDCl3): d=141.0, 135.74, 135.70, 133.1, 130.0,
131.7, 130.2, 128.7, 128.2, 128.0, 127.8, 127.4, 127.3, 126.5,
87.2, 79.6, 59.7, 59.0, 27.4, 20.4; IR (neat): n=3025, 2955,
2862, 1715, 1600, 1492, 1452, 1073, 1027 cmÀ1; MS (EI, 70
To a solution of (E)-1,3-diphenylallyl acetate (760 mg,
3.0 mmol) in aqueous NH3/1,4-dioxane (1/2 v/v, 75 mL) was
added PdACHTUNGTRENNUNG(PPh3)4 (350 mg, 0.3 mmol). After stirring for 18 h
eV): m/z (%)=424 [M
+A 37,37Cl), 6.32], 422 [M+A 37,35Cl),
CTHUNGTRENNUN(G CHTUNGTRENNUNG(
+A 35,35Cl), 40.46], 139 (100); HR-MS (EI):
at room temperature, the reaction mixture was diluted with
a saturated aqueous NaHCO3 solution. The resulting mix-
ture was extracted with CH2Cl2 and the combined organic
layer was dried over MgSO4, filtered and concentrated
under reduced pressure. The crude mixture was purified by
preparative TLC on silica gel (eluent: petroleum ether/i-
PrNH2 =19/1) to afford 6.
28.79], 420 [M CHUTGNRETNNUG(
m/z=420.1042, calcd. for C26H2235,35Cl2O (M+): 420.1048.
(1S*,2R*,5R*,E)-2-(4-Bromophenyl)-1-(4-bromostyryl)-5-
phenyl-3-oxabicycloACTHNUTRGNE[NUG 3.2.0]heptane (3c): The reaction of an-
hydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol), and
2c (222 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3c
(eluent: petroleum ether/ethyl acetate=100/1) as an oil;
(E)-1,3-Diphenylprop-2-en-1-amine
(6):[17]
1H NMR
1
yield: 112 mg (73%). H NMR (400 MHz, CDCl3): d=7.44
(400 MHz, CDCl3): d=7.46–7.11 (m, 10H, Ar-H), 6.58 (d,
J=16.0 Hz, 1H, CH=), 6.35 (dd, J=6.6, 15.8 Hz, 1H,
CH=), 4.68 (d, J=6.0 Hz, 1H, PhCH), 1.73 (brs, 2H, NH2).
(d, J=8.0 Hz, 2H, Ar-H), 7.40–7.15 (m, 9H, Ar-H), 7.02 (d,
J=8.0 Hz, 2H, Ar-H), 6.16 (d, J=16.0 Hz, 1H, CH=), 6.07
(d, J=16.4 Hz, 1H, CH=), 4.89 (s, 1H, OCH), 4.31 (d, J=
9.6 Hz, 1H, one proton of OCH2), 4.23 (d, J=9.6 Hz, 1H,
one proton of OCH2), 2.54–2.43 (m, 1H, one proton of
CH2), 2.31–2.19 (m, 1H, one proton of CH2), 2.05–1.88 (m,
2H, CH2); 13C NMR (100 MHz, CDCl3): d=140.9, 136.2,
136.1, 131.8, 131.6, 130.9, 130.3, 128.2, 128.1, 127.6, 127.3,
126.5, 121.3, 121.1, 87.1, 79.5, 59.6, 58.9, 27.4, 20.3; IR
(neat): n=3027, 2947, 2856, 1722, 1594, 1487, 1448, 1068,
Typical Experimental Procedures for 3 and 5
Under a nitrogen atmosphere, anhydrous ZnCl2 (0.6 mmol)
was added to a Schlenk tube. A solution of 1 (0.3 mmol)
and 2 (or 4) (0.6 mmol) in 3 mL of CH2Cl2 was then added
at 08C. The reaction mixture was stirred at 08C and the re-
action was monitored by TLC. When the reaction was com-
plete, the mixture was eluted with 10 mL of CH2Cl2 and fil-
tered through a short column of silica gel (eluent: CH2Cl2
10 mLꢂ3). The organic phase was concentrated under re-
duced pressure and purified by chromatography on silica gel
1009 cmÀ1; MS (EI, 70 eV): m/z (%)=508 [M
21.95], 510 [M
+A 79,81Br), 43.17], 512 [M+A 81,81Br), 22.70], 117
(100); HR-MS (EI): m/z=508.0033, calcd. for
C26H2279,79Br2O (M+): 508.0037.
(1S*,2R*,5R*,E)-1-(4-Methylstyryl)-5-phenyl-2-p-tolyl-3-
oxabicyclo[3.2.0]heptane (3d): The reaction of anhydrous
+A 79,79Br),
CHTUNGTRENNUNG(
C
CHTUNGTRENNUNG(
to afford 3-oxabicycloACTHNUGRTENUNG[3.2.0]heptane derivatives 3 (or 5).
AHCTUNGTRENNUNG
ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol), and 2d
(143 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3d (eluent:
petroleum ether/ethyl acetate=100/1) as an oil; yield: 70 mg
Spectroscopic Data of the Products 3 and 5
(1S*,2R*,5R*,E)-2,5-Diphenyl-1-styryl-3-oxabicyclo-
ACHTUNGTRENNUNG[3.2.0]heptane (3a): The reaction of anhydrous ZnCl2
1
(61%). H NMR (400 MHz, CDCl3): d=7.36–7.23 (m, 5H,
Ar-H), 7.22–7.00 (m, 8H, Ar-H), 6.16 (d, J=16.0 Hz, 1H,
CH=), 6.11 (d, J=16.0 Hz, 1H, CH=), 4.94 (s, 1H, OCH),
4.29 (d, J=9.2 Hz, 1H, one proton of OCH2), 4.21 (d, J=
9.6 Hz, 1H, one proton of OCH2), 2.52–2.40 (m, 1H, one
proton of CH2), 2.36–2.18 (m, 7H, CH3 ꢂ2 and one proton
of CH2), 2.10–1.92 (m, 2H, CH2); 13C NMR (100 MHz,
CDCl3): d=141.5, 137.0, 136.7, 134.7, 134.2, 130.8, 130.3,
129.1, 128.5, 128.1, 127.4, 126.4, 126.2, 126.0, 87.8, 79.6, 59.6,
58.7, 27.5, 21.14, 21.11, 20.4; IR (neat): n=3024, 2924, 2862,
1716, 1608, 1512, 1448, 1178, 1061, 1020 cmÀ1; MS (EI, 70
eV): m/z (%)=380 (M+, 16.91), 119 (100); HR-MS (EI):
m/z=380.2148, calcd. for C28H28O (M+): 380.2140.
(82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol), and 2a (126 mg,
0.6 mmol) in CH2Cl2 (3 mL) afforded 3a (eluent: petroleum
ether/ethyl acetate=100/1) as a solid; yield: 91 mg (86%);
mp 120.0–120.58C (hexane/ethyl acetate). 1H NMR
(400 MHz, CDCl3): d=7.40 (d, J=7.2 Hz, 2H, Ar-H), 7.36–
7.10 (m, 13H, Ar-H), 6.21 (d, J=16.0 Hz, 1H, CH=), 6.14
(d, J=16.0 Hz, 1H, CH=), 4.98 (s, 1H, OCH), 4.30 (d, J=
9.2 Hz, 1H, one proton of OCH2), 4.23 (d, J=9.2 Hz, 1H,
one proton of OCH2), 2.53–2.42 (m, 1H, one proton of
CH2), 2.32–2.20 (m, 1H, one proton of CH2), 2.08–1.95 (m,
2H, CH2); 13C NMR (100 MHz, CDCl3): d=141.3, 137.4,
137.3, 131.3, 131.1, 128.4, 128.1, 127.8, 127.4, 127.20, 127.18,
126.5, 126.3, 126.1, 87.8, 79.6, 59.7, 58.9, 27.4, 20.5; IR (neat)
n (cmÀ1) 3026, 2941, 2854, 1720, 1600, 1495, 1448, 1177,
1058, 1025; MS (EI, 70 ev) m/z (%) 352 (M+, 90.0), 91
(100); HR-MS (EI): m/z=352.1830, calcd. for C26H24O
(M+): 352.1827.
(1S*,2R*,5R*,E)-2-(4-Methoxyphenyl)-1-(4-methoxystyr-
yl)-5-phenyl-3-oxabicycloACHTNUTRGNE[NUG 3.2.0]heptane (3e): The reaction
of anhydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg,
0.3 mmol), and 2e (162 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 3e (eluent: petroleum ether/ethyl acetate=60/1) as
1
an oil; yield: 78 mg (63%). H NMR (400 MHz, CDCl3): d=
(1S*,2R*,5R*,E)-2-(4-Chlorophenyl)-1-(4-chlorostyryl)-5-
7.37–7.28 (m, 6H, Ar-H), 7.22–7.15 (m, 1H, Ar-H), 7.11 (d,
J=8.8 Hz, 2H, Ar-H), 6.85 (d, J=8.8 Hz, 2H, Ar-H), 6.78
(d, J=9.2 Hz, 2H, Ar-H), 6.09 (d, J=16.0 Hz, 1H, CH=),
6.04 (d, J=16.0 Hz, 1H, CH=), 4.92 (s, 1H, OCH), 4.28 (d,
J=9.2 Hz, 1H, one proton of OCH2), 4.20 (d, J=10.0 Hz,
1H, one proton of OCH2), 3.78 (s, 3H, OCH3), 3.76 (s, 3H,
OCH3), 2.53–2.40 (m, 1H, one proton of CH2), 2.30–2.19
(m, 1H, one proton of CH2), 2.10–1.93 (m, 2H, CH2);
13C NMR (100 MHz, CDCl3): d=158.9, 158.8, 141.6, 130.4,
130.3, 129.5, 129.2, 128.1, 127.7, 127.5, 127.2, 126.2, 113.9,
phenyl-3-oxabicycloACTHNUTRGNE[NUG 3.2.0]heptane (3b): The reaction of an-
hydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol), and
2b (168 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3b
(eluent: petroleum ether/ethyl acetate=100/1) as an oil;
1
yield: 90 mg (71%). H NMR (400 MHz, CDCl3): d=7.38–
7.17 (m, 11H, Ar-H), 7.08 (d, J=8.4 Hz, 2H, Ar-H), 6.15 (d,
J=16.0 Hz, 1H, CH=), 6.08 (d, J=16.0 Hz, 1H, CH=), 4.91
(s, 1H, OCH), 4.30 (d, J=9.2 Hz, 1H, one proton of
OCH2), 4.23 (d, J=9.2 Hz, 1H, one proton of OCH2), 2.54–
2.43 (m, 1H, one proton of CH2), 2.31–2.19 (m, 1H, one
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
ÞÞ
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Bo Meng et al.
FULL PAPERS
113.2, 87.6, 79.7, 59.6, 58.7, 55.2, 55.1, 27.5, 20.5; IR (neat):
135 (100); HR-MS (EI): m/z=426.2199, calcd. for C29H30O3
(M+): 426.2195.
(1S*,2R*,5R*,E)-5-(4-Methoxyphenyl)-2-phenyl-1-styryl-
n=3024, 2930, 2852, 1714, 1607, 1511, 1460, 1174, 1033 cmÀ1
;
MS (EI, 70 eV): m/z (%)=352 (M+, 4.0), 199 (100); HR-
MS (EI): m/z=412.2032, calcd. for C28H28O3 (M+): 412.2038.
(1S*,2R*,5R*,E)-2-Phenyl-1-styryl-5-p-tolyl-3-oxabicyclo-
3-oxabicycloACTHNUGTRNEUNG[3.2.0]heptane (3i): The reaction of anhydrous
ZnCl2 (82 mg, 0.6 mmol), 1c (57 mg, 0.3 mmol), and 2a
(125 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3i (eluent:
petroleum ether/ethyl acetate=70/1) as an oil; yield: 73 mg
ACHTUNGTRENNUNG[3.2.0]heptane (3f): The reaction of anhydrous ZnCl2
(85 mg, 0.6 mmol), 1b (52 mg, 0.3 mmol), and 2a (126 mg,
0.6 mmol) in CH2Cl2 (3 mL) afforded 3f (eluent: petroleum
ether/ethyl acetate=100/1) as an oil; yield: 85 mg (77%).
1H NMR (400 MHz, C6D6): d=7.58 (d, J=7.6 Hz, 2H, Ar-
H), 7.23–7.15 (m, 2H, Ar-H), 7.15–6.90 (m, 10H, Ar-H),
6.19 (d, J=16.0 Hz, 1H, CH=), 6.11 (d, J=16.0 Hz, 1H,
CH=), 4.90 (s, 1H, OCH), 4.16 (d, J=9.6 Hz, 1H, one
proton of OCH2), 4.13 (d, J=9.2 Hz, 1H, one proton of
OCH2), 2.36–2.24 (m, 1H, one proton of CH2), 2.21–2.04
(m, 5H, CH3 and CH2), 1.98–1.85 (m, 1H, one proton of
CH2); 13C NMR (100 MHz, CDCl3): d=138.3, 137.5, 137.3,
135.8, 131.4, 131.0, 128.9, 128.4, 127.8, 127.3, 127.2, 127.1,
126.5, 126.2, 87.8, 79.7, 59.5, 58.6, 27.5, 21.0, 20.4; IR (neat):
1
(64%). H NMR (600 MHz, CDCl3): d=7.38 (d, J=7.2 Hz,
2H, Ar-H), 7.34–7.15 (m, 10H, Ar-H), 6.87 (d, J=8.4 Hz,
2H, Ar-H), 6.20 (d, J=16.2 Hz, 1H, CH=), 6.15 (d, J=
16.2 Hz, 1H, CH=), 4.95 (s, 1H, OCH), 4.26 (d, J=9.0 Hz,
1H, one proton of OCH2), 4.20 (d, J=9.6 Hz, 1H, one
proton of OCH2), 3.77 (s, 3H, OCH3), 2.48–2.38 (m, 1H,
one proton of CH2), 2.28–2.19 (m, 1H, one proton of CH2),
2.05–1.93 (m, 2H, CH2); 13C NMR (100 MHz, CDCl3): d=
157.9, 137.45, 137.36, 133.3, 131.5, 131.1, 128.5, 128.4, 127.8,
127.2, 126.5, 126.1, 113.5, 87.8, 79.5, 59.4, 58.3, 55.2, 27.6,
20.4; IR (neat): n=3024, 2933, 2852, 1700, 1609, 1513, 1453,
1181, 1059, 1031 cmÀ1; MS (EI, 70 eV): m/z (%)=382 (M+,
4.0), 84 (100); HR-MS (EI): m/z=382.1933, calcd. for
C27H26O2 (M+): 382.1933.
n=3026, 2943, 2855, 1721, 1601, 1494, 1449, 1059, 1026 cmÀ1
;
MS (EI, 70 eV): m/z (%)=366 (M+, 27.29), 105 (100); HR-
MS (EI): m/z=366.1989, calcd. for C27H26O (M+): 366.1984.
(1S*,2R*,5R*,E)-2-(4-Bromophenyl)-1-(4-bromostyryl)-5-
(1S*,2R*,5R*,E)-5-(4-Chlorophenyl)-2-phenyl-1-styryl-3-
oxabicycloACTHNUGRTNEUNG[3.2.0]heptane (3j): The reaction of anhydrous
ZnCl2 (82 mg, 0.6 mmol), 1d (59 mg, 0.3 mmol), and 2a
(125 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3j (eluent:
petroleum ether/ethyl acetate=100/1) as an oil; yield: 75 mg
(65%). 1H NMR (500 MHz, C6D6): d=7.55 (d, J=8.0 Hz,
2H, Ar-H), 7.21–7.17 (m, 2H, Ar-H), 7.13–6.92 (m, 8H, Ar-
H), 6.80 (d, J=8.5 Hz, 2H, Ar-H), 6.07 (d, J=16.5 Hz, 1H,
CH=), 5.99 (d, J=16.5 Hz, 1H, CH=), 4.80 (s, 1H, OCH),
4.02 (d, J=9.5 Hz, 1H, one proton of OCH2), 3.90 (d, J=
9.5 Hz, 1H, one proton of OCH2), 2.10–1.99 (m, 3H, one
proton of CH2 and CH2), 1.86–1.73 (m, 1H, one proton of
CH2); 13C NMR (100 MHz, CDCl3): d=139.9, 137.1, 137.0,
132.0, 131.5, 130.7, 128.7, 128.5, 128.2, 127.8, 127.34, 127.26,
126.4, 126.1, 87.7, 79.2, 59.6, 58.3, 27.5, 20.4; IR (neat): n=
3029, 2937, 2855, 1728, 1600, 1464, 1448, 1095, 1061,
p-tolyl-3-oxabicycloACHTUNGTRENNUNG[3.2.0]heptane (3g): The reaction of an-
hydrous ZnCl2 (82 mg, 0.6 mmol), 1b (52 mg, 0.3 mmol), and
2c (223 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3g
(eluent: petroleum ether/ethyl acetate=100/1) as an oil;
1
yield: 118 mg (75%). H NMR (400 MHz, CDCl3): d=7.48–
7.34 (m, 4H, Ar-H), 7.30–7.10 (m, 6H, Ar-H), 7.04 (d, J=
8.0 Hz, 2H, Ar-H), 6.18 (d, J=16.0 Hz, 1H, CH=), 6.06 (d,
J=16.0 Hz, 1H, CH=), 4.87 (s, 1H, OCH), 4.27 (d, J=
9.2 Hz, 1H, one proton of OCH2), 4.19 (d, J=9.2 Hz, 1H,
one proton of OCH2), 2.54–2.10 (m, 5H, CH3 and CH2),
2.03–1.86 (m, 2H, CH2); 13C NMR (100 MHz, CDCl3): d=
137.8, 136.2, 136.1, 136.0, 131.9, 131.6, 130.9, 130.1, 128.9,
128.1, 127.6, 127.2, 121.2, 121.0, 87.1, 79.6, 59.5, 58.6, 27.5,
21.0, 20.3; IR (neat): n=3025, 2943, 2856, 1721, 1590, 1486,
1449, 1067, 1009 cmÀ1; MS (EI, 70 eV): m/z (%)=526 [M+-
1013 cmÀ1; MS (EI, 70 eV): m/z (%)=388 [M
386 [M
+A(35Cl), 8.53], 105 (100); HR-MS (EI): m/z=
386.1437, calcd. for C26H2335ClO (M+): 386.1437.
(1S*,2R*,5R*,E)-2-(4-Bromophenyl)-1-(4-bromostyryl)-5-
(4-chlorophenyl)-3-oxabicyclo[3.2.0]heptane (3k): The reac-
+A(37Cl), 3.36],
CHTUNGTRENNUNG
CTHUNGTRENNUNG
ACHTUNGTRENNUNG( CHTUGNRETNNUNG( CHUNTGTRENNUN(G
81,81Br), 16.72], 524 [M+A 79,81Br), 31.35], 522 [M+A 79,79Br),
15.95], 131 (100); HR-MS (EI): m/z=522.0197, calcd. for
C27H2479,79Br2O (M+): 522.0194.
AHCTUNGTRENNUNG
(1S*,2R*,5R*,E)-2-(4-Methoxyphenyl)-1-(4-methoxystyr-
yl)-5-p-tolyl-3-oxabicycloACHTNUTRGNE[UNG 3.2.0]heptane (3h): The reaction
tion of anhydrous ZnCl2 (82 mg, 0.6 mmol), 1d (59 mg,
0.3 mmol), and 2c (199 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 3k (eluent: petroleum ether/ethyl acetate=100/1) as
of anhydrous ZnCl2 (82 mg, 0.6 mmol), 1b (52 mg,
0.3 mmol), and 2e (163 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 3h (eluent: petroleum ether/ethyl acetate=60/1) as
1
an oil; yield: 126 mg (77%). H NMR (400 MHz, C6D6): d=
7.29 (d, J=8.4 Hz, 2H, Ar-H), 7.16–7.09 (m, 6H, Ar-H),
6.75 (d, J=8.4 Hz, 2H, Ar-H), 6.61 (d, J=8.4 Hz, 2H, Ar-
H), 5.79 (d, J=16.0 Hz, 1H, CH=), 5.74 (d, J=16.0 Hz, 1H,
CH=), 4.54 (s, 1H, OCH), 3.95 (d, J=9.6 Hz, 1H, one
proton of OCH2), 3.84 (d, J=9.2 Hz, 1H, one proton of
OCH2), 2.08–1.92 (m, 2H, CH2), 1.88–1.78 (m, 1H, one
proton of CH2), 1.74–1.64 (m, 1H, one proton of CH2);
13C NMR (100 MHz, CDCl3): d=139.5, 136.0, 135.8, 132.3,
131.7, 131.2, 131.0, 130.7, 128.7, 128.4, 128.0, 127.6, 121.4,
121.3, 87.1, 79.2, 59.6, 58.4, 27.5, 20.3; IR (neat): n=3026,
2953, 2855, 1717, 1589, 1488, 1178, 1067, 1008 cmÀ1; MS (EI,
70 eV): m/z (%)=548 [M+(37Cl81,81Br), 4.49], 546
[M+(37Cl79,81Br, 35Cl81,81Br), 22.32], 544 [M+(37Cl79,79Br,
35Cl79,81Br), 31.42], 542 [M+(35Cl79,79Br), 14.51], 183 (100);
HR-MS (EI): m/z=541.9646, calcd. for C26H2179,79Br235ClO
(M+): 541.9648.
1
an oil; yield: 63 mg (49%). H NMR (400 MHz, C6D6): d=
7.55 (d, J=7.6 Hz, 2H, Ar-H), 7.13 (d, J=8.0 Hz, 2H, Ar-
H), 7.06 (d, J=8.4 Hz, 2H, Ar-H), 7.02 (d, J=7.6 Hz, 2H,
Ar-H), 6.82 (d, J=8.0 Hz, 2H, Ar-H), 6.67 (d, J=8.0 Hz,
2H, Ar-H), 6.17 (d, J=16.4 Hz, 1H, CH=), 6.11 (d, J=
16.0 Hz, 1H, CH=), 4.94 (s, 1H, OCH), 4.21 (d, J=9.2 Hz,
1H, one proton of OCH2), 4.17 (d, J=8.8 Hz, 1H, one
proton of OCH2), 3.29 (s, 3H, OCH3), 3.24 (s, 3H, OCH3),
2.41–2.30 (m, 1H, one proton of CH2), 2.27–2.15 (m, 2H,
CH2), 2.11 (s, 3H, CH3), 2.05–1.92 (m, 1H, one proton of
CH2); 13C NMR (100 MHz, CDCl3): d=158.9, 158.7, 138.5,
135.6, 130.33, 130.25, 129.5, 129.2, 128.8, 127.6, 127.3, 127.2,
113.8, 113.1, 87.6, 79.7, 59.4, 58.3, 55.2, 55.1, 27.5, 20.9, 20.4;
IR (neat): n=3025, 2933, 2836, 1714, 1608, 1510, 1460, 1174,
1059, 1032 cmÀ1; MS (EI, 70 eV): m/z (%)=426 (M+, 19.1),
10
asc.wiley-vch.de
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
1
(1S*,2R*,5R*,E)-1-(4-Methoxystyryl)-2,5-di-p-tolyl-3-
oxabicyclo[3.2.0]heptane (3l-a) and (1S*,2R*,5R*,E)-2-(4-
methoxyphenyl)-1-(4-methylstyryl)-5-p-tolyl-3-oxa-bicyclo-
[3.2.0]heptane (3l-b): The reaction of anhydrous ZnCl2
(82 mg, 0.6 mmol), 1b (52 mg, 0.3 mmol), and 2f (154 mg,
0.6 mmol) in CH2Cl2 (3 mL) afforded 3l-a (yield: 15 mg,
12%) and 3l-b (yield: 72 mg, 58%) (eluent: petroleum
ether/ethyl acetate=90/1).
3m-b: Oil; H NMR (400 MHz, CDCl3): d=7.37–7.26 (m,
G
6H, Ar-H), 7.25–7.15 (m, 3H, Ar-H), 7.08 (d, J=8.4 Hz,
2H, Ar-H), 6.85 (d, J=8.0 Hz, 2H, Ar-H), 6.17 (d, J=
16.0 Hz, 1H, CH=), 6.08 (d, J=16.0 Hz, 1H, CH=), 4.92 (s,
1H, OCH), 4.29 (d, J=9.2 Hz, 1H, one proton of OCH2),
4.21 (d, J=9.6 Hz, 1H, one proton of OCH2), 3.78 (s, 3H,
OCH3), 2.54–2.43 (m, 1H, one proton of CH2), 2.34–2.19
(m, 1H, one proton of CH2), 2.11–1.92 (m, 2H, CH2);
13C NMR (100 MHz, CDCl3): d=158.8, 141.3, 135.9, 132.8,
132.2, 129.9, 129.2, 128.6, 128.2, 127.6, 127.4, 127.3, 126.3,
113.3, 87.5, 79.6, 59.6, 58.9, 55.2, 27.4, 20.5; IR (neat): n=
3025, 2929, 2855, 1713, 1605, 1492, 1455, 1172, 1092,
ACHTUNGTRENNUNG
3l-a: Oil; 1H NMR (600 MHz, C6D6): d=7.56 (d, J=
7.8 Hz, 2H, Ar-H), 7.12 (d, J=7.8 Hz, 2H, Ar-H), 7.09–6.95
(m, 6H, Ar-H), 6.66 (d, J=8.4 Hz, 2H, Ar-H), 6.15 (d, J=
16.2 Hz, 1H, CH=), 6.10 (d, J=16.2 Hz, 1H, CH=), 4.95 (s,
1H, OCH), 4.20 (d, J=9.0 Hz, 1H, one proton of OCH2),
4.17 (d, J=9.0 Hz, 1H, one proton of OCH2), 3.25 (s, 3H,
OCH3), 2.40–2.30 (m, 1H, one proton of CH2), 2.24–2.16
(m, 2H, CH2) 2.13–2.07 (m, 6H, CH3 ꢂ2), 2.02–1.90 (m, 1H,
one proton of CH2); 13C NMR (100 MHz, CDCl3): d=158.8,
138.5, 136.6, 135.7, 134.4, 130.4, 130.2, 129.2, 128.8, 128.4,
127.32, 127.25, 126.4, 113.8, 87.8, 79.7, 59.4, 58.4, 55.2, 27.5,
21.1, 21.0, 20.4; IR (neat): n=3025, 2950, 2857, 1607, 1512,
1458, 1177, 1061, 1036 cmÀ1; MS (EI, 70 eV): m/z (%)=410
(M+, 5.31), 49 (100); HR-MS (EI): m/z=410.2250, calcd. for
C29H30O2 (M+): 410.2246.
1032 cmÀ1; MS (EI, 70 eV): m/z (%)=418 [M
416 [M
+A(35Cl), 3.0], 135 (100); HR-MS (EI): m/z=416.1548,
calcd. for C27H2535ClO2 (M+): 416.1543.
(1S*,2R*,5R*,E)-2-(4-Methoxyphenyl)-1-(4-nitrostyryl)-5-
phenyl-3-oxabicyclo[3.2.0]heptane (3n): The reaction of an-
+A(37Cl), 1.0],
CHTUNGTRENNUNG
CTHUNGTRENNUNG
AHCTUNGTRENNUNG
hydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol), and
2h (172 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3n
(eluent: petroleum ether/ethyl acetate=60/1) as an oil;
yield: 82 mg (64%). 1H NMR (400 MHz, CDCl3): d=8.09
(d, J=8.8 Hz, 2H, Ar-H), 7.38–7.18 (m, 9H, Ar-H), 6.87 (d,
J=8.4 Hz, 2H, Ar-H), 6.39 (d, J=16.4 Hz, 1H, CH=), 6.19
(d, J=16.0 Hz, 1H, CH=), 4.96 (s, 1H, OCH), 4.31 (d, J=
9.2 Hz, 1H, one proton of OCH2), 4.24 (d, J=9.2 Hz, 1H,
one proton of OCH2), 3.79 (s, 3H, OCH3), 2.58–2.47 (m,
1H, one proton of CH2), 2.34–2.24 (m, 1H, one proton of
CH2), 2.16–2.07 (m, 1H, one proton of CH2), 2.06–1.94 (m,
1H, one proton of CH2); 13C NMR (100 MHz, CDCl3): d=
159.0, 146.7, 143.8, 140.9, 136.8, 129.2, 129.0, 128.3, 127.6,
127.3, 126.53, 126.50, 123.9, 113.4, 87.4, 79.6, 59.9, 59.5, 55.2,
27.3, 20.6; IR (neat): n=3025, 2936, 2851, 1715, 1598, 1514,
1448, 1342, 1178, 1109, 1034 cmÀ1; MS (EI, 70 eV): m/z
(%)=427 (M+, 22.37), 133 (100); HR-MS (EI): m/z=
427.1786, calcd. for C27H25O4 (M+): 427.1784.
Alternatively, the reaction of anhydrous ZnCl2 (83 mg,
0.6 mmol), 1a (48 mg, 0.3 mmol), and 2i (171 mg, 0.6 mmol)
in CH2Cl2 (3 mL) afforded 3n (eluent: petroleum ether/ethyl
acetate=60/1) as an oil; yield: 90 mg (70%). 1H NMR
(400 MHz, CDCl3): d=8.09 (d, J=8.8 Hz, 2H, Ar-H), 7.37–
7.17 (m, 9H, Ar-H), 6.87 (d, J=8.4 Hz, 2H, Ar-H), 6.39 (d,
J=16.0 Hz, 1H, CH=), 6.19 (d, J=16.0 Hz, 1H, CH=), 4.96
(s, 1H, OCH), 4.31 (d, J=9.6 Hz, 1H, one proton of
OCH2), 4.24 (d, J=9.6 Hz, 1H, one proton of OCH2), 3.79
(s, 3H, OCH3), 2.59–2.47 (m, 1H, one proton of CH2), 2.34–
2.23 (m, 1H, one proton of CH2), 2.17–2.06 (m, 1H, one
proton of CH2), 2.06–1.94 (m, 1H, one proton of CH2);
13C NMR (100 MHz, CDCl3): d=158.9, 146.6, 143.7, 140.9,
136.8, 129.2, 128.9, 128.3, 127.6, 127.3, 126.5, 123.9, 113.3,
87.4, 79.5, 59.9, 59.4, 55.2, 27.3, 20.5; IR (neat): n=3025,
2932, 2852, 1724, 1596, 1514, 1447, 1342, 1177, 1109,
1033 cmÀ1; MS (EI, 70 eV): m/z (%)=427 (M+, 21.52), 133
(100); HR-MS (EI): m/z=427.1782, calcd. for C27H25O4
(M+): 427.1784.
3l-b: Oil; 1H NMR (400 MHz, CDCl3): d=7.30 (d, J=
8.8 Hz, 2H, Ar-H), 7.20 (d, J=8.0 Hz, 2H, Ar-H), 7.16–7.01
(m, 6H, Ar-H), 6.84 (d, J=8.4 Hz, 2H, Ar-H), 6.17 (d, J=
16.0 Hz, 1H, CH=), 6.10 (d, J=16.0 Hz, 1H, CH=), 4.91 (s,
1H, OCH), 4.26 (d, J=9.6 Hz, 1H, one proton of OCH2),
4.18 (d, J=9.2 Hz, 1H, one proton of OCH2), 3.78 (s, 3H,
OCH3), 2.50–2.38 (m, 1H, one proton of CH2), 2.35–2.18
(m, 7H, CH3 ꢂ2 and one proton of CH2), 2.07–1.93 (m, 2H,
CH2); 13C NMR (100 MHz, CDCl3): d=158.7, 138.4, 136.9,
135.7, 134.7, 130.7, 130.4, 129.4, 129.1, 128.8, 127.6, 127.3,
126.1, 113.1, 87.6, 79.7, 59.4, 58.4, 55.1, 27.6, 21.1, 20.9, 20.4;
IR (neat): n=3025, 2931, 2856, 1611, 1512, 1458, 1176, 1061,
1035 cmÀ1; MS (EI, 70 eV): m/z (%)=410 (M+, 46.72), 135
(100); HR-MS (EI): m/z=410.2244, calcd. for C29H30O2
(M+): 410.2246.
(1S*,2R*,5R*,E)-2-(4-Chlorophenyl)-1-(4-methoxystyryl)-
5-phenyl-3-oxabicyclo
(1S*,2R*,5R*,E)-1-(4-chlorostyryl)-2-(4-methoxyphenyl)-5-
phenyl-3-oxabicyclo[3.2.0]heptane (3m-b): The reaction of
A
(3m-a)
and
AHCTUNGTRENNUNG
anhydrous ZnCl2 (85 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol),
and 2g (165 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 3m-
a (yield: 14 mg, 11%) and 3m-b (84 mg, 67%) (eluent: pe-
troleum ether/ethyl acetate=100/1).
1
3m-a: Oil; H NMR (400 MHz, CDCl3): d=7.38–7.26 (m,
8H, Ar-H), 7.24–7.17 (m, 1H, Ar-H), 7.12 (d, J=8.4 Hz,
2H, Ar-H), 6.79 (d, J=8.4 Hz, 2H, Ar-H), 6.09 (d, J=
16.4 Hz, 1H, CH=), 6.03 (d, J=16.0 Hz, 1H, CH=), 4.91 (s,
1H, OCH), 4.30 (d, J=9.6 Hz, 1H, one proton of OCH2),
4.23 (d, J=9.6 Hz, 1H, one proton of OCH2), 3.78 (s, 3H,
OCH3), 2.52–2.42 (m, 1H, one proton of CH2), 2.29–2.19
(m, 1H, one proton of CH2), 2.04–1.88 (m, 2H, CH2);
13C NMR (100 MHz, CDCl3): d=159.1, 141.3, 136.0, 133.0,
130.8, 130.1, 128.7, 128.2, 127.9, 127.8, 127.4, 127.3, 126.3,
114.0, 87.3, 79.7, 59.7, 58.7, 55.3, 27.4, 20.4; IR (neat): n=
3024, 2935, 2855, 1713, 1607, 1492, 1456, 1171, 1094,
(1S*,2R*,5R*,E)-2-Methyl-5-phenyl-1-styryl-3-oxabicyclo-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
tion of anhydrous ZnCl2 (84 mg, 0.6 mmol), 1a (48 mg,
0.3 mmol), and 2j (90 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 3o-a (yield: 31 mg, 36%) and 3o-b (yield: 28 mg,
32%) (eluent: petroleum ether/ethyl acetate=100/1).
1031 cmÀ1; MS (EI, 70 eV): m/z (%)=418 [M
416 [M
+A(35Cl), 8.96], 135 (100); HR-MS (EI): m/z=
416.1552, calcd. for C27H2535ClO2 (M+): 416.1543.
+A(37Cl), 3.32],
CHTUNGTRENNUNG
CHTUNGTRENNUNG
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
11
ÞÞ
These are not the final page numbers!

Bo Meng et al.
FULL PAPERS
3o-a: Oil; 1H NMR (400 MHz, C6D6): d=7.14–6.95 (m,
10H, Ar-H), 6.24 (d, J=16.8 Hz, 1H, CH=), 6.02 (d, J=
16.0 Hz, 1H, CH=), 4.03 (d, J=9.2 Hz, 1H, one proton of
OCH2), 3.93–3.84 (m, 2H, OCH and one proton of OCH2),
2.43–2.26 (m, 2H, CH2), 2.10–2.01 (m, 1H, one proton of
CH2), 1.97–1.87 (m, 1H, one proton of CH2), 1.26 (d, J=
6.4 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=142.1,
137.4, 131.2, 129.8, 128.4, 128.1, 127.3, 127.1, 126.1, 126.0,
82.0, 81.0, 59.0, 58.2, 27.3, 20.3, 13.2; IR (neat): n=3026,
2930, 2853, 1600, 1495, 1448, 1380, 1086, 1053 cmÀ1; MS (EI,
70 eV): m/z (%)=290 (M+, 32.43), 129 (100); HR-MS (EI):
m/z=290.1674, calcd. for C21H22O (M+): 290.1671.
z (%)=406 (M+, 6.85), 105 (100); HR-MS (EI): m/z=
406.2295, calcd. for C30H30O (M+): 406.2297.
(1S*,2R*,5R*)-2-(4-Chlorophenyl)-1-[(1E,3E)-4-(4-
chloro-
phenyl)buta-1,3-dienyl]-5-phenyl-3-oxabicycloACTHNUTRGNE[NUG 3.2.0]heptane
(5c): The reaction of anhydrous ZnCl2 (81 mg, 0.6 mmol), 1a
(48 mg, 0.3 mmol), and 4c (182 mg, 0.6 mmol) in CH2Cl2
(3 mL) afforded 5c (eluent: petroleum ether/ethyl acetate=
100/1) as an oil; yield: 79 mg (59%). 1H NMR (400 MHz,
C6D6): d=7.30 (d, J=8.4 Hz, 2H, Ar-H), 7.23–7.16 (m, 4H,
Ar-H), 7.12–7.01 (m, 5H, Ar-H), 6.78 (d, J=8.8 Hz, 2H, Ar-
H), 6.37 (dd, J=15.8, 10.2 Hz, 1H, CH=), 5.98 (d, J=
15.2 Hz, 1H, CH=), 5.80 (dd, J=15.4, 10.6 Hz, 1H, CH=),
5.58 (d, J=15.2 Hz, 1H, CH=), 4.68 (s, 1H, OCH), 4.08 (d,
J=9.6 Hz, 1H, one proton of OCH2), 4.04 (d, J=9.6 Hz,
1H, one proton of OCH2), 2.34–2.21 (m, 1H, one proton of
CH2), 2.11–2.00 (m, 1H, one proton of CH2), 1.99–1.88 (m,
1H, one proton of CH), 1.83–1.72 (m, 1H, one proton of
CH); 13C NMR (100 MHz, CDCl3): d=141.1, 135.8, 135.7,
135.4, 133.1, 132.9, 131.9, 130.2, 129.2, 128.7, 128.2, 128.0,
127.8, 127.4, 126.4, 87.2, 79.9, 60.0, 59.1, 27.3, 20.4; IR
(neat): n=3027, 2937, 2857, 1720, 1598, 1491, 1448, 1091,
1
3o-b: Oil; H NMR (400 MHz, CDCl3): d=7.52–7.15 (m,
10H, Ar-H), 5.46 (d, J=15.2 Hz, 1H, CH=), 5.31–5.19 (m,
1H, CH=), 4.85 (s, 1H, OCH), 4.25 (d, J=9.2 Hz, 1H, one
proton of OCH2), 4.13 (d, J=9.6 Hz, 1H, one proton of
OCH2), 2.50–2.36 (m, 1H, one proton of CH2), 2.24–2.14
(m, 1H, one proton of CH2), 1.96–1.76 (m, 2H, CH2), 1.61
(d, J=6.4 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=
141.9, 137.6, 131.7, 127.9, 127.7, 127.6, 127.1, 126.5, 126.0,
87.8, 79.9, 59.3, 58.0, 27.1, 20.3, 18.2; IR (neat): n=3027,
2934, 2855, 1601, 1495, 1449, 1376, 1060, 1026 cmÀ1; MS (EI,
70 eV): m/z (%)=290 (M+, 30.86), 91 (100); HR-MS (EI):
m/z=290.1667, calcd. for C21H22O (M+): 290.1671.
1062, 1013 cmÀ1; MS (EI, 70 eV): m/z (%)=450 [M
2.10], 448 [M
+A 35,37Cl), 10.97], 446 [M+A 35,35Cl), 15.50], 139
(100); HR-MS (EI): m/z=446.1202, calcd. for
C28H2435,35Cl2O (M+): 446.1204.
(1S*,2R*,5R*)-2-Phenyl-1-[(1E,3E)-4-phenylbuta-1,3-
dienyl]-5-p-tolyl-3-oxabicyclo[3.2.0]heptane (5d): The reac-
+A 35,35Cl),
CHTUNGTRENNUNG(
C
CHTUNGTRENNUNG(
(1S*,2R*,5R*)-2,5-Diphenyl-1-[(1E,3E)-4-phenylbuta-1,3-
dienyl]-3-oxabicycloACHTNUTGRNEUNG
[3.2.0]heptane (5a):[18] The reaction of
anhydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg, 0.3 mmol),
and 4a (144 mg, 0.6 mmol) in CH2Cl2 (3 mL) afforded 5a
(eluent: petroleum ether/ethyl acetate=100/1) as an oil;
AHCTUNGTRENNUNG
tion of anhydrous ZnCl2 (84 mg, 0.6 mmol), 1b (52 mg,
0.3 mmol), and 4a (142 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 5d (eluent: petroleum ether/ethyl acetate=100/1) as
1
yield: 70 mg (62%). H NMR (400 MHz, CDCl3): d=7.45–
7.15 (m, 15H, Ar-H), 6.71 (dd, J=15.4, 10.6 Hz, 1H, CH=),
6.38 (d, J=15.6 Hz, 1H, CH=), 6.01 (dd, J=15.6, 10.4 Hz,
1H, CH=), 5.82 (d, J=15.2 Hz, 1H, CH=), 4.93 (s, 1H,
OCH), 4.28 (d, J=9.2 Hz, 1H, one proton of OCH2), 4.19
(d, J=9.6 Hz, 1H, one proton of OCH2), 2.52–2.42 (m, 1H,
CH), 2.30–2.19 (m, 1H, CH), 2.07–1.87 (m, 2H, CH2);
13C NMR (100 MHz, CDCl3): d=141.4, 137.3, 137.2, 135.2,
131.9, 131.3, 128.9, 128.5, 128.2, 127.8, 127.44, 127.35, 127.2,
126.5, 126.3, 126.2, 87.8, 79.8, 60.0, 59.1, 27.3, 20.5; IR
(neat): n=3026, 2924, 2853, 1720, 1600, 1494, 1449, 1177,
1061, 1026 cmÀ1; MS (EI, 70 eV): m/z (%)=378 (M+, 45.99),
105 (100); HR-MS (EI): m/z=378.1980, calcd. for C28H26O
(M+): 378.1984.
1
an oil; yield: 62 mg (53%). H NMR (400 MHz, CDCl3): d=
7.43–7.10 (m, 14H, Ar-H), 6.71 (dd, J=15.2, 10.0 Hz, 1H,
CH=), 6.37 (d, J=16.0 Hz, 1H, CH=), 6.00 (dd, J=15.4,
10.2 Hz, 1H, CH=), 5.82 (d, J=15.2 Hz, 1H, CH=), 4.91 (s,
1H, OCH), 4.25 (d, J=9.2 Hz, 1H, one proton of OCH2),
4.17 (d, J=9.2 Hz, 1H, one proton of OCH2), 2.49–2.39 (m,
1H, one proton of CH2), 2.32 (s, 3H, CH3), 2.27–2.15 (m,
1H, one proton of CH2), 2.04–1.86 (m, 2H, CH2); 13C NMR
(100 MHz, CDCl3): d=138.3, 137.4, 137.2, 135.7, 135.4,
131.8, 131.1, 128.9, 128.8, 128.5, 127.8, 127.3, 127.2, 126.4,
126.2, 87.7, 79.8, 59.8, 58.8, 27.4, 21.0, 20.5; IR (neat): n=
3026, 2940, 2857, 1718, 1600, 1493, 1450, 1059, 1026 cmÀ1
;
MS (EI, 70 eV): m/z (%)=392 (M+, 7.7), 51 (100); HR-MS
(EI): m/z=392.2134, calcd. for C29H28O (M+): 392.2140.
(1S*,2R*,5R*)-2-(4-Bromophenyl)-1-[(1E,3E)-4-(4-bro-
mophenyl)buta-1,3-dienyl]-5-p-tolyl-3-oxabicyclo [3.2.0]hep-
tane (5e): The reaction of anhydrous ZnCl2 (84 mg,
0.6 mmol), 1b (53 mg, 0.3 mmol), and 4d (235 mg, 0.6 mmol)
in CH2Cl2 (3 mL) afforded 5e (eluent: petroleum ether/ethyl
acetate=100/1) as an oil; yield: 94 mg (57%). 1H NMR
(400 MHz, C6D6): d=7.32 (d, J=8.0 Hz, 2H, Ar-H), 7.24 (d,
J=8.0 Hz, 2H, Ar-H), 7.22–7.16 (m, 2H, Ar-H), 7.10–7.00
(m, 4H, Ar-H), 6.70 (d, J=8.0 Hz, 2H, Ar-H), 6.39 (dd, J=
15.6, 10.4 Hz, 1H, CH=), 5.96 (d, J=16.0 Hz, 1H, CH=),
5.81 (dd, J=15.4, 10.6 Hz, 1H, CH=), 5.61 (d, J=15.2 Hz,
1H, CH=), 4.67 (s, 1H, OCH), 4.14–4.03 (m, 2H, OCH2),
2.41–2.24 (m, 1H, one proton of CH2), 2.20–2.00 (m, 4H,
CH3 and one proton of CH2), 2.00–1.88 (m, 1H, one proton
of CH2), 1.85–1.71 (m, 1H, one proton of CH2); 13C NMR
(100 MHz, CDCl3): d=137.9, 136.3, 136.1, 135.9, 135.7,
131.7, 131.6, 130.9, 130.1, 129.4, 128.9, 128.1, 127.7, 127.2,
(1S*,2R*,5R*)-5-Phenyl-2-p-tolyl-1-[(1E,3E)-4-p-tolylbu-
ta-1,3-dienyl]-3-oxabicycloACHTNUTRGNE[UNG 3.2.0]heptane (5b): The reaction
of anhydrous ZnCl2 (82 mg, 0.6 mmol), 1a (48 mg,
0.3 mmol), and 4b (158 mg, 0.6 mmol) in CH2Cl2 (3 mL) af-
forded 5b (eluent: petroleum ether/ethyl acetate=100/1) as
1
an oil; yield: 62 mg (51%). H NMR (400 MHz, CDCl3): d=
7.42–7.18 (m, 9H, Ar-H), 7.17–7.02 (m, 4H, Ar-H), 6.66 (dd,
J=16.0, 10.2 Hz, 1H, CH=), 6.34 (d, J=15.6 Hz, 1H,
CH=), 5.99 (dd, J=15.2, 10.0 Hz, 1H, CH=), 5.78 (d, J=
15.2 Hz, 1H, CH=), 4.90 (s, 1H, OCH), 4.27 (d, J=9.2 Hz,
1H, one proton of OCH2), 4.17 (d, J=9.6 Hz, 1H, one
proton of OCH2), 2.51–2.40 (m, 1H, one proton of CH2),
2.40–2.15 (m, 7H, CH3 ꢂ2 and one proton of CH2), 2.06–
1.86 (m, 2H, CH2); 13C NMR (100 MHz, CDCl3): d=141.6,
137.2, 136.8, 134.6, 134.5, 134.3, 131.9, 131.1, 129.3, 128.5,
128.1, 128.0, 127.5, 126.4, 126.2, 126.1, 87.8, 79.8, 59.9, 58.9,
27.4, 21.2, 21.1, 20.5; IR (neat): n=3023, 2922, 2854, 1723,
1604, 1511, 1448, 1182, 1062, 1021 cmÀ1; MS (EI, 70 eV): m/
12
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Electrophilic Addition of Allylic Carbocations to 2-Cyclopropylidene-2-arylethanols
121.2, 121.0, 87.1, 79.8, 59.8, 58.8, 27.4, 21.0, 20.3; IR (neat):
n=3026, 2942, 2857, 1720, 1589, 1485, 1400, 1066, 1008 cmÀ1
MS (EI, 70 eV): m/z (%)=552 [M
+A 81,81Br), 23.21], 550 [M+
2004, 69, 2805–2808; i) L. Yu, J. Meng, L. Xia, R. Guo,
J. Org. Chem. 2009, 74, 5087–5089.
;
CTHUNGTRENNUNG(
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[6] W. Fu, X. Huang, Y. Lin, Synlett 2007, 321–323.
[7] Crystal data for compound 3a: C26H24O, MW =352.45,
monoclinic, space group P21/n, final R indices [I>
2s(I)], R1=0.0406, wR2=0.0809, R indices (all data)
R1=0.1025, wR2=0.0908, a=10.6062(5) ꢃ, b=
9.3855(4) ꢃ, c=20.1820(10) ꢃ, a=908, b=96.479(4)8,
g=908, V=1996.18(17) ꢃ3, T=293(2) K, Z=4, reflec-
tions collected/unique: 9615/3649 (Rint =0.0398),
number of observations [> 2s(I)] 1709, parameters:
244. CCDC 892249 contains the supplementary crystal-
lographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
(
79,81Br), 43.42], 548 [M+ 79,79Br), 22.05], 131 (100); HR-MS
(
(EI): m/z= 548.0350, calcd. for C29H2679,79Br2O (M+):
548.0350.
Reaction of 1b with (E)-1,3-Diphenylprop-2-enyl
amine 6
Under a nitrogen atmosphere, anhydrous ZnCl2 (0.6 mmol)
was added to a Schlenk tube. A solution of 1b (0.3 mmol)
and 6 (0.6 mmol) in 3 mL of CH2Cl2 was then added at 08C.
The reaction mixture was stirred at 08C. When the reaction
was complete as monitored by TLC, the mixture was eluted
with 10 mL of CH2Cl2 and filtered through a short column
of silica gel (eluent: CH2Cl2 10 mL ꢂ 3). The organic phase
was concentrated under reduced pressure and the crude
1
product was analyzed by H NMR measurement.
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Control Experiments with HCl Replacing ZnCl2
Under s nitrogen atmosphere, a solution of 1d (0.3 mmol)
and 2a (0.6 mmol) in 2 mL of CH2Cl2 was added to a Schlenk
tube. A CH2Cl2 solution of HCl (0.2956m), prepared by bub-
bling HCl (gas) into anhydrous CH2Cl2, was then added at
08C. The reaction mixture was stirred at 08C. When the re-
action was complete as monitored by TLC, the mixture was
eluted with 10 mL of CH2Cl2 and filtered through a short
column of silica gel (eluent: CH2Cl2 10 mL ꢂ 3). The organic
phase was concentrated under reduced pressure and the
1
crude product was analyzed by H NMR measurement.
Acknowledgements
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We are grateful to the National Basic Research Program of
China (973 Program, 2009CB825300) and National Natural
Science Foundation of China (Project Nos. 20872127 and
J0830431) and CAS Academician Foundation of Zhejiang
Province and the Fundamental Research Funds for the Cen-
tral Universities for financial support. We thank Mr. Jian Cao
for reproducing the results presented in entry 9 of Table 2,
Scheme 4, Scheme 6 and entry 1 of Table 3.
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14
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Adv. Synth. Catal. 0000, 000, 0 – 0
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FULL PAPERS
Electrophilic Addition of Allylic Carbocations to 2-
Cyclopropylidene-2-arylethanols: A Strategy to 3-
15
OxabicycloACHTUNGTRENNUNG[3.2.0]heptanes
Adv. Synth. Catal. 2013, 355, 1 – 15
Bo Meng, Xian Huang, Luling Wu*
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
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