Synthesis of substituted benzenes and phenols by ring-closing olefin metathesis

Article abstract of DOI:10.1002/chem.200800484

New synthetic approaches to substituted aromatic compounds are reported. Ring-closing olefin metathesis (RCM)/dehydration and RCM/tautomerization are the key processes in the synthesis of substituted benzenes 3 and phenols 6, respectively. Readily accessible 1,5,7-trien-4-ols 7, which are the precursors of benzenes, were prepared from β-halo-α, β-unsaturated aldehydes 11 or β-halo-α,β-unsaturated esters 19 by utilizing reliable transformations in which cross-coupling with vinylic metal reagents 12 and allylation with allylic metal reagents 13 were employed as carbon-carbon bond forming reactions. RCM of 7, followed by dehydration, afforded a wide variety of substituted benzenes 3. In addition, RCM of 1,5,7trien-4-ones 9, which were prepared by oxidation of 7, furnished various substituted phenols 6 by automatic tautomerization.

Full text of DOI:10.1002/chem.200800484

DOI: 10.1002/chem.200800484
Synthesis of Substituted Benzenes and Phenols by Ring-Closing Olefin
Metathesis
Kazuhiro Yoshida,* Hidetoshi Takahashi, and Tsuneo Imamoto*[a]
Abstract: New synthetic approaches to
substituted aromatic compounds are re-
ported. Ring-closing olefin metathesis
(RCM)/dehydration and RCM/tauto-
merization are the key processes in the
synthesis of substituted benzenes 3 and
phenols 6, respectively. Readily accessi-
ble 1,5,7-trien-4-ols 7, which are the
precursors of benzenes, were prepared
from b-halo-a,b-unsaturated aldehydes
11 or b-halo-a,b-unsaturated esters 19
by utilizing reliable transformations in
which cross-coupling with vinylic metal
reagents 12 and allylation with allylic
metal reagents 13 were employed as
carbon–carbon bond forming reactions.
RCM of 7, followed by dehydration, af-
forded a wide variety of substituted
benzenes 3. In addition, RCM of 1,5,7-
trien-4-ones 9, which were prepared by
oxidation of 7, furnished various substi-
tuted phenols 6 by automatic tautomer-
Keywords: arenes · cyclization ·
ization.
dehydration
·
metathesis
·
tautomerization
Introduction
(RCM), which has seen much improvement with the devel-
opment of readily available ruthenium carbene complexes,
has begun to be applied in this strategy.[3–5] RCM is one of
the most powerful reactions to form carbon-carbon double
bonds of cyclic compounds due to its operational simplicity,
high chemoselectivity, and remarkable functional group tol-
erance.[6,7] Therefore, it seems quite reasonable to apply this
reaction to the synthesis of aromatic compounds.
In the last few years, we have focused our efforts on the
development of a new method for the synthesis of aromatic
compounds with RCM,[8] and found that substituted ben-
zenes 3 and phenols 6 can be obtained from tandem RCM/
dehydration of 1,4,7-trien-3-ols 1 and RCM/tautomerization
of 1,4,7-trien-3-ones 4, respectively (Scheme 1). The key
point of these processes is the adoption of cyclohexa-2,5-di-
The demand for functionalized aromatic compounds is
growing rapidly in many research fields. Therefore, the effi-
cient synthesis of the desired aromatic compounds is a criti-
cal issue in organic synthesis.[1] Electrophilic aromatic substi-
tution is predominantly used for the synthesis of substituted
aromatic compounds at both laboratory and industrial
levels. It is, however, quite difficult to synthesize the desired
aromatic compounds only with this transformation. The in-
troduction of a substituent to an existing aromatic ring,
which is one of the features of electrophilic aromatic substi-
tution, gives rise to induction of plural orientation on the ar-
omatic ring in most cases. Hence, it is often difficult to con-
trol substitution sites regioselectively with this reaction, as
required by synthetic chemists. The direct construction of ar-
omatic rings from acyclic precursors in which substituents
are arranged at predetermined positions presents a potential
advantage in terms of selective synthesis of complex aromat-
ic compounds.[2] Recently, ring-closing olefin metathesis
[a] Prof. Dr. K. Yoshida, H. Takahashi, Prof. Dr. T. Imamoto
Department of Chemistry, Graduate School of Science
Chiba University
Yayoi-cho, Inage-ku, Chiba 263–8522 (Japan)
Fax : (+81)43-290-2791
E-mail: kyoshida@faculty.chiba-u.jp
imamoto@faculty.chiba-u.jp
Scheme 1. Substituted benzenes 3 and phenols 6 from tandem RCM/de-
hydration of 1,4,7-trien-3-ols 1 and RCM/tautomerization of 1,4,7-trien-3-
ones 4.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200800484.
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Chem. Eur. J. 2008, 14, 8246 – 8261

FULL PAPER
enols 2 and cyclohexa-2,5-dienones 5 as target intermediates
of RCM. Although these processes yield various substituted
benzenes and phenols, they lack generality because precur-
sors 1 and 4 could not be readily prepared. On the other
hand, cyclohexa-2,4-dienols 8 and cyclohexa-2,4-dienones 10
are also regarded as precursors of benzenes and phenols
with these routes (Scheme 2). Therefore, it is anticipated
that the RCM/dehydration of 1,5,7-trien-4-ols 7 and the
RCM/tautomerization of 1,5,7-trien-4-ones 9 would give
benzenes 3 and phenols 6, respectively.
The synthetic route to 1-(1-hydroxy-3-butenyl)-2-vinylcy-
clopentene (7a) is given in Scheme 4 as a representative ex-
ample of the preparation of 7. We started with an examina-
tion of the preparation of 11a from cyclopentanone accord-
ing to a procedure in the literature.[9] Suzuki–Miyaura cou-
pling[10] between 11a and potassium trifluorovinylborate
(12a) in the presence of 5 mol% Pd(OAc)2 as the precata-
G
lyst, PPh3 as the ligand, and Cs2CO3 as the base in THF/
H2O afforded dienal 14a in high yield. Then, the reaction of
14a with allyl Grignard reagent 13a in Et2O gave the de-
sired product 7a.
Scheme 2. 1,5,7-Trien-4-ols 7 and 1,5,7-trien-4-ones 9 give benzenes 3
after RCM/dehydration and phenols 6 after RCM/tautomerization, re-
spectively.
Scheme 4. A representative example of the preparation of 7.
Herein we present the results of investigation of the syn-
thesis of substituted benzenes and phenols with these routes.
Because of the accessibility of 7 and 9, the synthetic routes
have great generality for the preparation of various aromatic
compounds. First, we will describe the preparation of pre-
cursors 7 and 9. Then, we will discuss in detail the synthesis
of benzenes 3 and phenols 6 with RCM.
In this work, we employed the following ruthenium car-
bene catalysts for RCM: Grubbs first-generation catalyst
15,[11] Grubbs second-generation catalyst 16,[12] Hoveyda–
Grubbs catalyst 17,[13] and substituted Hoveyda–Grubbs cat-
alyst 18.[14]
Results and Discussion
Our retrosynthetic analysis revealed that substrates 7 and 9
could be synthesized from three basic segments (Scheme 3).
A combination of the cross-coupling reaction of b-halo-a,b-
unsaturated aldehydes 11 with vinylic metal reagents 12 and
the allylation of the resulting coupling products with allylic
metal reagents 13 would lead to trienes 7, which are the pre-
cursors of benzenes. In addition, oxidation of 7 at the alco-
hol position would be expected to furnish 9 for the synthesis
of phenols. If the three basic segments containing various
substituents are employed with this route, it is predicted
that a wide variety of compounds 7 and 9 would be pre-
pared.
To our delight, when we carried out RCM of 7a using
Grubbs first-generation catalyst 15 at room temperature fol-
lowed by dehydration with a catalytic amount of p-toluene-
sulfonic acid, the corresponding benzene 3a was quantita-
tively obtained (Table 1, entry 1). Then, we prepared a vari-
ety of methyl-substituted compounds 7 (7b–f) using the
above-mentioned route and conducted RCM/dehydration
reactions to examine the effect of substituents in the vicinity
of the RCM-reactive double bonds on the reactivity
(Table 1, entries 2–11). Under the same reaction conditions,
introduction of a methyl group at the R1 or R3 position re-
tarded the conversion of the reaction to approximately half
that of 7a (Table 1, entry 1 vs. entries 2 and 4), whereas in-
Scheme 3. Retrosynthetic analysis of substrates 7 and 9.
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K. Yoshida, T. Imamoto et al.
Table 1. Synthesis of benzenes 3 by RCM/dehydration.[a]
used at 408C (Table 1, entry 10) and a high reaction temper-
ature (1008C) was required to complete the reaction
(Table 1, entry 11).
After acquiring basic data, we next examined the general-
ity of this synthetic route. The results of cross-coupling be-
tween 11 and 12, and allylation of coupled products 14 with
13 to yield 7 are summarized in Table 2. For the cross-cou-
pling, we employed Suzuki–Miyaura coupling. The reaction
proceeded cleanly under standard conditions by using Pd-
Entry
Substrate
Product
Catalyst
T
[8C]
Yield
[%][b]
(OAc)2, PPh3, and Cs2CO3 in THF/H2O to furnish various
products 14 in good to excellent yields. Coupled products
14c–e were used directly without isolation for the subse-
quent allylation, because we were concerned about their sta-
bility during the purification step. For the subsequent allyla-
tion, readily available allylborane, allyl Grignard, and allyl-
stannane reagents were employed. In the reaction with allyl-
borane, solvent-free conditions could be utilized to obtain
the corresponding homoallylic alcohols 7 in high yields.[15]
We examined only one example of the allylation with allyl-
stannane, which requires the addition of a Lewis acid to pro-
mote the reaction (Table 2, entry 8). When we used MgBr2
as the Lewis acid for the reaction of 14g with 13e, a mixture
of 7n and 7n substituted with bromide at the allylic chloride
position was obtained. After screening for the optimal con-
ditions, we found that BF3·Et2O was the optimal Lewis acid
for this reaction, affording pure 7n in good yield.
1
15
RT
>99
2
3
15
16
RT
RT
48
96
4
5
15
16
RT
RT
44
97
6
7
15
16
RT
RT
trace
94
a,b-Unsaturated esters 19 can be used instead of alde-
hydes 11 and are also good candidates for the starting mate-
rial for the preparation of 7. Table 3 shows the results of the
conversion of 19 to 7. This synthetic route employs the fol-
lowing reactions: the Suzuki–Miyaura coupling between 19
and 12, the reduction of esters 20 to alcohols 21 with diiso-
butylaluminum hydride (DIBAL-H), the oxidation of the re-
sulting alcohols 21 to aldehydes 14 with MnO2, and the ally-
lation of 14 with allyl Grignard reagents to yield 7.[16] Al-
though various 1,5,7-trien-4-ols 7 were successfully prepared
with this route, it should be mentioned that E/Z isomeriza-
tion was observed in the cross-coupling reaction between al-
kenyl triflate 19d and potassium isopropenyltrifluoroborate
(12c). When the reaction of 12c and geometrically pure
(Z)-19d was carried out in the presence of a palladium cata-
lyst in THF/H2O at reflux temperature, a 1:4 E/Z mixture of
20d was obtained. Decreasing the temperature to room tem-
perature improved the E/Z ratio to 1:20 and the isomers
could be separated by silica-gel column chromatography
(Table 3, entry 4). Interestingly, no such E/Z isomerization
was observed in a similar reaction of alkenyl iodide 19b or
19c even at elevated temperatures (Table 3, entries 2 and 3).
With a wide variety of the desired precursors in hand, we
tried to synthesize substituted benzenes 3 by RCM/dehydra-
tion of 7. The results are presented in Table 4. All RCM re-
actions were conducted with Grubbs second-generation cat-
alyst 16. The formation of condensed benzenes containing
five- to eight-membered aliphatic rings was accomplished
without any problems (Table 4, entries 1–5). Likewise, sub-
stituted naphthalenes 3l–n were produced in high yields
under similar conditions (Table 4, entries 6–8). The construc-
8
9
15
16
RT
RT
24
92
10
16
16
40
100
0
91
11[c]
[a] Ring-closing olefin metathesis was carried out with 1,5,7-trien-4-ol 7
and ruthenium catalyst (15 or 16, 7.5 mol%) in CH2Cl2 for 2 h. The reac-
tion mixture was treated with p-toluenesulfonic acid (10 mol%) at room
temperature for 1 h. [b] NMR yield by 1H NMR analysis by using 1,4-
bis(trimethylsilyl)benzene as the internal standard. [c] The reaction was
carried out in toluene.
troduction of a methyl group at the R2 position further de-
creased the reactivity (Table 1, entry 6). More active Grubbs
second-generation catalyst 16 was, however, sufficient to
drive the reactions to completion under the same conditions
(Table 1, entries 3, 5, and 7). As we had anticipated, simulta-
neous introduction of two methyl groups at the R1 and R3
positions decreased the reactivity synergistically (Table 1,
entry 8), but catalyst 16 promoted the reaction at room tem-
perature (Table 1, entry 9). Substrate 7 f containing two
methyl groups at the R1 and R2 positions was an exception:
the reaction of 7 f did not proceed at all even when 16 was
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Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
Table 2. Preparation of 1,5,7-trien-4-ols 7, precursors of benzenes 3, from b-halo-a,b-unsaturated aldehydes 11 by Suzuki–Miyaura coupling and allylation.[a]
Entry
11
12
Conditions
14
Yield [%]
13
7
Yield [%]
of 14[b]
of 7[b]
1
508C, 3 h
92
78
91
88
2
3
508C, 3 h
508C, 2 h
n.i.[c]
31 (2 steps)
4
5
6
7
508C, 2 h
508C, 2 h
508C, 3 h
508C, 3 h
n.i.[c]
n.i.[c]
>99
96
67 (2 steps)
83 (2 steps)
90
88
8
9
–
–
–
–
–
84
82
78
>99
96
reflux, 3 h,
10 mol% Pd
10
508C, 3 h
[a] Suzuki–Miyaura coupling was carried out with halo-aldehyde 11 and vinylborane 12 in the presence of Pd(OAc)2 (5 mol%), PPh3 (10 mol%), and
G
Cs2CO3 (3 equiv) in THF/H2O (5:1). Allylation was carried out with 14 and allylic metal reagent 13 under various conditions (See Experimental Section
for details). [b] Yield of isolated product after silica-gel chromatography. [c] n.i.=Not isolated.
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K. Yoshida, T. Imamoto et al.
Table 3. Preparation of 1,5,7-trien-4-ols 7, precursors of benzenes 3, from a,b-unsaturated esters 19 by Suzuki–Miyaura coupling, reduction with DIBAL-
H, oxidation with MnO2, and allylation.[a]
Entry
19
12
Conditions
20
Yield
[%] of
20[b]
21
Yield
[%] of
21[b]
13
7
Yield
[%] of
7[b]
reflux,
12 h
72 (2
steps)
1
86
69
reflux,
24 h
67 (2
steps)
2
3
70
73
90
94
70 (2
steps)
608C, 12 h
73 (2
steps)
4
RT, 15 h
56[c]
95
[a] Suzuki–Miyaura coupling was carried out with halo-ester 19 and vinylborane 12 in the presence of Pd(OAc)2 (5 mol%), PPh3 (10 mol%), and
G
Cs2CO3 (3 equiv) in THF/H2O (5:1). Reduction of 20 to 21 was carried out with DIBAL-H (2 equiv) in THF at À788C for 30 min. Oxidation of 21 to 14
was carried out with MnO2 (20–30 equiv) in CH2Cl2 at RT for 0.5–1 h. Allylation was carried out with 14 and allylic Grignard reagent 13 under various
conditions (See Experimental Section for details). [b] Yield of isolated product after silica-gel chromatography. [c] An E/Z-mixture of 20d (1:20) was ob-
tained.
tion of two rings from 7o led to the formation of substituted
anthracene 3o (Table 4, entry 9). To demonstrate the func-
tional group tolerance of this synthesis, substrates 7p and
7q containing heteroatoms were converted into the corre-
sponding benzothiophene 3p and 1,2,3,4-tetrahydroisoqui-
noline 3q, respectively (Table 4, entries 10 and 11). In addi-
tion, single-ring benzenes 3r–t containing the benzyloxy, hal-
ogen, or olefin functionality were also prepared in satisfac-
tory yields (Table 4, entries 12–14).
Our attention was next turned to the formation of substi-
tuted phenols 6. First, we prepared 1,5,7-trien-4-one 9a as a
test precursor from 1,5,7-trien-4-ol 7a by Dess–Martin oxi-
dation (Scheme 5).
Table 5 summarizes the results of the synthesis of 6a from
9a by RCM/tautomerization by using various ruthenium car-
bene catalysts 15–18. A large difference in reactivity was
noted between 7a and 9a. Whereas the reaction of 1,5,7-
trien-4-ol 7a in the presence of 7.5 mol% Grubbs first-gen-
eration catalyst 15 at room temperature gave substituted
benzene 3a quantitatively, the reaction of 1,5,7-trien-4-one
9a under similar conditions gave the corresponding phenol
6a in only 3% yield (Table 1, entry 1 vs. Table 5, entry 1).
This result is consistent with the fact that electron-deficient
dienic systems are less reactive than normal dienic systems
in RCM reactions.[17] Although Grubbs second-generation
catalyst 16 could not improve the yield effectively at room
temperature (Table 5, entry 2), a satisfactory result was ob-
tained when the temperature was increased to 408C
(Table 5, entry 3). On the other hand, phosphine-free ruthe-
nium carbene catalysts 17 and 18 exhibited sufficient reac-
tivity even at room temperature (Table 5, entries 4–7). It
was, therefore, concluded that 17 and 18 are the most suita-
ble catalysts for precursors 7. When the loading of catalyst
18 was decreased to 5.0 or 2.5 mol%, the reaction still effi-
ciently furnished the product in good yield at 408C (Table 5,
entries 8 and 9). Because of the commercial availability and
remarkable stability of Hoveyda–Grubbs catalyst 17, we
chose to use it for the following RCM of 9.
The effect of introducing methyl substituents on the reac-
tivity was next examined by using substrates 9b–f (Table 6).
By analogy with the results for 1,5,7-trien-4-ols 7 in Table 1,
the reactivity of 9 was decreased by a larger extent when a
methyl group was introduced at the R2 position than when it
was introduced at the R1 or R3 position (Table 6, entries 1–
4). When methyl groups were introduced at the R1 and R2
positions at the same time, the reaction in the presence of
17 in dichloromethane at 408C did not occur at all (Table 6,
entry 6). However, increasing the temperature to 808C and
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Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
Table 4. Synthesis of benzenes 3 by RCM/dehydration.[a]
Table 4. (Continued)
Entry
Substrate
T [8C]
Product
Yield [%][b]
13
80
81
Entry
1
Substrate
T [8C]
Product
Yield [%][b]
14[c]
RT
75
80
82
[a] Ring-closing olefin metathesis was carried out with 1,5,7-trien-4-ol 7
and ruthenium catalyst (16, 7.5 mol%) in toluene for 2 h. The reaction
mixture was treated with p-toluenesulfonic acid (10 mol%) at room tem-
perature for 1 h. [b] Yield of isolated product after silica-gel chromatog-
raphy. [c] The reaction was carried out in CH2Cl2.
2
3
80
80
91
86
4
5
6
80
80
80
86
98
92
Scheme 5. Preparation of 9a from 7a by Dess–Martin oxidation.
Table 5. Synthesis of phenol 6a by RCM/tautomerization.[a]
Entry
Catalyst [mol%]
T [8C]
Yield [%][b]
1
2
3
4
5
6
7
8
9
15 (7.5)
16 (7.5)
16 (7.5)
17 (7.5)
17 (7.5)
18 (7.5)
18 (7.5)
18 (5.0)
18 (2.5)
RT
RT
40
RT
40
RT
40
40
3
19
81
82
88
84
95
85
83
7
100
82
8
9
80
88
78
40
[a] Ring-closing olefin metathesis was carried out with 1,5,7-trien-4-one
9a and ruthenium catalyst (15, 16, 17, or 18) in CH2Cl2 for 12 h. [b] Yield
of isolated product after silica-gel chromatography.
100
changing the solvent to toluene gave the corresponding
phenol 6 f in high yield (Table 6, entry 7).
10
11
80
80
73
82
Table 7 shows the results of the Dess–Martin oxidation of
1,5,7-trien-4-ols 7 to yield 1,5,7-trien-4-ones 9. All reactions
proceeded well and various trienones 9 were prepared. A
unique characteristic was found in 9k, containing a cyclooc-
tene ring, which existed in equilibrium with 2H-pyran 22k
(Scheme 6).[18] By integrating well-resolved signals in the
1H NMR spectra of the mixture, the equilibrium ratio of 9k
to 22k was determined to be 2.8:1 at room temperature. No
such equilibrium was observed in the other 1,5,7-trien-4-
ones 9.
12[c]
RT
91
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K. Yoshida, T. Imamoto et al.
Table 6. Synthesis of phenols 6 by RCM/tautomerization.[a]
Table 7. Preparation of 1,5,7-trien-4-ones 9, precursors of phenols 6,
from 1,5,7-trien-4-ols 7 by Dess–Martin oxidation.[a]
Entry
1
Substrate
Product
Yield [%][b]
Entry
1
Substrate
Product
T [8C]
Yield [%][b]
86
40
91
2
3
4
66
2
40
91
3
40
80
22
86
4[c]
68[c]
79
5
40
88
6
40
80
0
92
5
79
7[c]
[a] Ring-closing olefin metathesis was carried out with 1,5,7-trien-4-one 9
and ruthenium catalyst 17 (7.5 mol%) in CH2Cl2 for 12 h. [b] Yield of
isolated product after silica-gel chromatography. [c] The reaction was car-
ried out in toluene.
6
7
77
56
As the final experiment of this study, we conducted RCM/
tautomerization of the obtained compound 9 in the presence
of Hoveyda–Grubbs catalyst 17 (Table 8). A variety of
phenol derivatives 6 were successfully formed in high yields,
as expected. The reaction of the equilibrium mixture of 9k
and 22k furnished the corresponding product 6k cleanly
(Table 8, entry 3). Even when ester, allyl chloride, benzyl
chloride, or sulfur functionality was present in the substrate
or the product, the reaction proceeded without any prob-
lems, giving only the desired product. It should be noted
that tolerance of the catalyst to the phenol hydroxyl group
of the products contributes to the success of this RCM/tau-
tomerization process.
[a] Reaction was carried out with 1,5,7-trien-4-ol 7, Dess–Martin periodi-
nane (2 equiv), and pyridine (4 equiv) in CH2Cl2 at 08C for 30 min.
[b] Yield of isolated product after silica-gel chromatography. [c] Equilib-
rium mixture of 9k and 22k (2.8:1) was obtained.
Scheme 6. Equilibrium between 9k and 22k.
Conclusion
We have developed an efficient synthetic approach to substi-
tuted benzenes and phenols by utilizing ruthenium-catalyzed
RCM/dehydration and RCM/tautomerization as the respec-
tive key process. Because the presented synthetic routes in-
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Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
Table 8. Synthesis of phenols 6 by RCM/tautomerization.[a]
Therefore, the direct construction of aromatic rings from
acyclic precursors would provide one possible solution to
the difficulty of responding to the growing demand for com-
plex aromatic compounds. Combinations of the cyclization
of acyclic precursors prepared in a selective manner and
subsequent aromatization provide an effective means to
access the desired aromatic compounds without the forma-
tion of inseparable regioisomers. Because ruthenium-cata-
lyzed RCM has become one of the most powerful cycliza-
tion reactions, application of this reaction to the synthesis of
aromatic compounds is expected to increase its importance
in organic synthesis.
Entry
Substrate
T [8C]
Product
Yield
[%][b]
1
80
95
85
Experimental Section
2
3
80
80
40
General: All anaerobic and moisture-sensitive manipulations were car-
ried out by using standard Schlenk techniques under predried nitrogen or
by using glove box techniques under prepurified argon. NMR spectra
were recorded on a JEOL JNM LA-500 spectrometer (500 MHz for 1H
and 125 MHz for 13C) or a LA-400 spectrometer (400 MHz for 1H and
100 MHz for 13C). Chemical shifts are reported in d ppm referenced to
an internal SiMe4 standard for 1H NMR spectroscopy and CDCl3 (d=
77.0 ppm) for 13C NMR spectroscopy.
98
84
Materials: THF and Et2O were distilled from sodium benzophenone-
ketyl under nitrogen prior to use. Toluene was distilled from sodium ben-
zophenone-ketyl under nitrogen and stored in a glass flask with a Teflon
stopcock under nitrogen. Dichloromethane was distilled from CaH2
under nitrogen and stored in a glass flask with a Teflon stopcock under
nitrogen. Ruthenium complexes, Grubbs first-generation catalyst 15,[11b]
Grubbs second-generation catalyst 16,[12b] Hoveyda–Grubbs catalyst 17,[19]
and substituted Hoveyda–Grubbs catalyst 18[19] were prepared according
to the reported procedures. b-Halo-a,b-unsaturated aldehydes 11a–d,[9]
11g,[20] and a,b-unsaturated esters 19a,[21] 19b,[22] 19c,[23] and 19d[24] were
prepared according to the reported procedures. b-Halo-a,b-unsaturated
aldehydes 11e, 11 f, and 11h were used as received. Potassium vinyl tri-
fluoroborate 12a[10] and potassium isopropenyltrifluoroborate 12c[25] were
prepared according to the reported procedures. Vinylboronic acid pinacol
ester 12b was prepared according to the reported procedure.[26] Allylic
metal reagents 13a,[27] 13b,[15] 13c,[27] 13d,[28] 13e,[29] and 13 f[30] were pre-
pared according to the reported procedures. Dess–Martin periodinane[31]
4[c]
5
80
81
6
7
80
80
80
70
[32]
and activated MnO2 were prepared according to the reported proce-
dures. Palladium acetate, triphenylphosphine, cesium carbonate, pyridine,
and p-toluenesulfonic acid were used as received.
General procedure A: preparation of unsaturated aldehydes 14: A mix-
ture of potassium vinyl trifluoroborate (17.9 mmol), Pd(OAc)2
R
(0.70 mmol), PPh3 (1.40 mmol), Cs2CO3 (41.3 mmol), and b-halo-a,b-un-
saturated aldehyde 11 (13.8 mmol) in THF (40 mL) and water (8 mL)
was heated to 508C and stirred for 2–3 h. After cooling to room tempera-
ture, the mixture was diluted with water and extracted with ether three
times. The organic layers were combined, washed with brine, and dried
over Na2SO4. After filtration, the filtrate was evaporated under reduced
pressure. The residue was purified by silica-gel column chromatography
to give unsaturated aldehyde 14.
[a] Ring-closing olefin metathesis was carried out with 1,5,7-trien-4-one 9
and ruthenium catalyst 17 (7.5 mol%) in toluene for 12 h. [b] Yield of
isolated product after silica-gel chromatography. [c] The reaction was car-
ried out in CH2Cl2.
2-Vinylcyclopentene-1-carbaldehyde (14a): The reaction was carried out
by following the general procedure A and the product was purified by
silica-gel column chromatography (hexane/EtOAc 10:1) (92% yield).
1H NMR (CDCl3): d=1.91 (quint, J=7.6 Hz, 2H), 2.66 (t, J=7.6 Hz,
2H), 2.78 (t, J=7.6 Hz, 2H), 5.55 (d, J=11.0 Hz, 1H), 5.56 (d, J=
16.8 Hz, 1H), 7.27 (dd, J=16.8, 11.0 Hz, 1H), 10.21 ppm (s, 1H);
13C NMR (CDCl3): d=20.89, 30.77, 34.01, 121.99, 128.37, 139.61, 157.69,
187.56 ppm; HRMS (EI): m/z calcd for C8H10O: 122.0732 [M+]; found:
122.0731.
volve highly reliable and mild transformations at all steps, it
is possible to synthesize a wide variety of substituted ben-
zenes 3 and phenols 6 containing various functionalities with
these routes.
It is reasonable to say that modern synthetic organic
chemistry has sufficient flexibility to construct acyclic com-
pounds with more selectivity than aromatic compounds.
2-Isopropenylcyclopentene-1-carbaldehyde: The reaction was carried out
by following the general procedure A and the product was purified by
Chem. Eur. J. 2008, 14, 8246 – 8261
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8253

K. Yoshida, T. Imamoto et al.
silica-gel column chromatography (hexane/EtOAc 10:1) (73% yield).
1H NMR (CDCl3): d=1.90 (quint, J=7.7 Hz, 2H), 1.96 (s, 3H), 2.63 (tt,
J=8.0, 1.9 Hz, 2H), 2.73 (tt, J=7.7, 2.2 Hz, 2H), 5.08 (s, 1H), 5.21 (dq,
J=1.6, 1.5 Hz, 1H), 9.89 ppm (s, 1H); 13C NMR (CDCl3): d=21.36,
21.76, 30.55, 37.63, 76.68, 77.00, 77.32, 118.61, 139.89, 139.70, 164.29,
189.66 ppm; HRMS (EI): m/z calcd for C9H12O: 136.0888 [M+]; found:
136.0883.
1H), 5.13 (q, J=1.5 Hz, 1H), 7.24–7.28 (m, 1H), 7.31–7.37 ppm (m, 4H);
13C NMR (CDCl3): d=13.91, 32.78, 48.61, 52.92, 58.19, 60.19, 62.09,
74.61, 112.09, 124.79, 127.09, 128.22, 129.05, 137.75, 146.43, 147.33,
166.59 ppm; HRMS (FAB): m/z calcd for C19H26NO3: 316.1913 [M++H];
found: 316.1917.
3-Benzyloxymethyl-4-methylpenta-2,4-dienoic acid ethyl ester (20b): The
reaction was carried out at reflux temperature for 12 h by following gen-
eral procedure B, and the product was purified by silica-gel column chro-
matography (hexane/EtOAc 10:1) (70% yield); 1H NMR (CDCl3): d=
1.27 (t, J=7.0 Hz, 3H), 1.95 (dd, J=1.5, 0.9 Hz, 3H), 4.06 (d, J=1.9 Hz,
2H), 4.15 (q, J=7.4 Hz, 2H), 4.57 (s, 2H), 4.76 (dq, J=1.5, 0.9 Hz, 1H),
5.02 (quint, J=1.5 Hz, 1H), 5.97 (t, J=1.8 Hz, 1H), 7.28–7.38 ppm (m,
5H); 13C NMR (CDCl3): d=13.99, 22.00, 59.79, 72.19, 72.48, 113.32,
114.62, 127.45, 127.63, 128.30, 137.56, 142.51, 157.20, 165.67 ppm; HRMS
(FAB): m/z calcd for C16H21O3: 261.1491 [M++H]; found: 261.1500.
2-(1-Methoxymethylvinyl)cyclopentene-1-carbaldehyde (14b): The reac-
tion was carried out by following the general procedure A and the prod-
uct was purified by silica-gel column chromatography (hexane/EtOAc
20:1) (84% yield). 1H NMR (CDCl3): d=1.92 (quint, J=7.9 Hz, 2H),
2.65 (tt, J=7.6, 1.9 Hz, 2H), 2.76 (tt, J=7.6, 1.9 Hz, 2H), 3.34 (s, 3H),
4.07 (dd, J=1.2, 0.6 Hz, 2H), 5.29 (d, J=1.9 Hz, 1H), 5.42 (dd, J=3.1,
1.5 Hz, 1H), 9.90 ppm (s, 1H); 13C NMR (CDCl3): d=21.32, 30.53,
37.39, 57.94, 74.00, 119.63, 140.38, 141.66, 161.31, 189.50 ppm; HRMS
(EI): m/z: C10H14O2 166.0994 [M+]; found: 166.0991.
6-Chloro-3-vinyl-2-hexenoic acid methyl ester (20c): The reaction was
carried out at 608C for 12 h by following the general procedure B, and
the product was purified by silica-gel column chromatography (hexane/
2-Isopropenyl-4,5-dimethoxybenzaldehyde (14 f): The reaction was car-
ried out by following the general procedure A and the product was puri-
fied by silica-gel column chromatography (hexane/EtOAc 5:1) (>99%
yield). M.p. 50–518C; 1H NMR (CDCl3): d=2.17 (dd, J=1.4, 0.7 Hz,
3H), 3.94 (s, 3H), 3.97 (s, 3H), 4.92 (dq, J=1.7, 1.5 Hz, 1H), 5.42 (quint,
J=1.7 Hz, 1H), 6.75 (s, 1H), 7.44 (s, 1H), 10.07 ppm (s, 1H); 13C NMR
(CDCl3): d=25.26, 55.91, 56.01, 108.48, 110.05, 118.87, 126.51, 140.97,
143.22, 148.28, 153.35, 190.65 ppm; HRMS (FAB): m/z calcd for
C12H15O3: 207.1021 [M++H]; found: 207.1025.
1
EtOAc 20:1) (73% yield). H NMR (CDCl3): d=1.93–2.02 (m, 2H), 2.53
(t, J=7.7 Hz, 2H), 3.56 (t, J=6.5 Hz, 2H), 3.72 (s, 3H), 5.48 (d quint, J=
11.1, 0.6 Hz, 1H), 5.64 (dd, J=18.2, 0.6 Hz, 1H), 5.76 (d, J=0.9 Hz, 1H),
7.71 ppm (dd, J=17.9, 11.1 Hz, 1H); 13C NMR (CDCl3): d=30.37, 31.53,
44.18, 51.07, 117.61, 120.49, 132.50, 153.10, 166.24 ppm; HRMS (FAB):
m/z calcd for C9H14ClO2: 189.0682 [M++H]; found: 189.0679.
3-Isopropenyl-7-methyl-2,6-octadienoic acid ethyl ester (20d): The reac-
tion was carried out at room temperature for 15 h by following the gener-
al procedure B, and the product was purified by silica-gel column chro-
matography (hexane/EtOAc 20:1) (56% yield). 1H NMR (CDCl3): d=
1.26 (t, J=7.1 Hz, 3H), 1.60 (s, 3H), 1.68 (d, J=1.0 Hz, 3H), 1.93 (s,
3H), 2.07–2.16 (m, 2H), 2.21–2.25 (m, 2H), 4.13 (q, J=7.1 Hz, 2H), 4.69
(s, 1H), 4.96 (quint, J=1.6 Hz, 1H), 5.08 (t septet, J=7.1, 1.2 Hz, 1H),
5.61 ppm (s, 1H); 13C NMR (CDCl3): d=14.05, 17.61, 22.03, 25.55, 25.77,
38.31, 59.64, 111.87, 115.55, 122.92, 132.34, 144.96, 161.69, 165.89 ppm;
HRMS (FAB): m/z calcd for C14H23O2: 223.1698 [M++H]; found:
223.1691.
5-Vinylbenzo[1,3]dioxole-4-carbaldehyde (14g): The reaction was carried
G
out by following the general procedure A and the product was purified
by silica-gel column chromatography (hexane/EtOAc=10/1) (96%
yield). M.p. 94–968C; 1H NMR (CDCl3): d=5.37 (dd, J=11.2, 1.5 Hz,
1H), 5.56 (dd, J=17.6, 1.2 Hz, 1H), 6.13 (s, 2H), 6.96 (d, J=8.3 Hz, 1H),
7.02 (d, J=8.3 Hz, 1H), 7.37 (dd, J=17.4, 11.0 Hz, 1H), 10.36 ppm (s,
1H); 13C NMR (CDCl3): d=102.71, 113.10, 116.66, 117.66, 120.60, 133.53,
133.69, 148.12, 150.49, 188.64 ppm; HRMS (FAB): m/z calcd for
C10H9O3: 177.0552 [M++H]; found: 177.0553.
2,5-Diisopropenylbenzene-1,4-dicarbaldehyde (14h): The reaction was
carried out by following the general procedure A in the presence of 10
General procedure C: preparation of unsaturated alcohol 21: Diisobuty-
laluminum hydride (0.97m in hexane, 3.22 mmol) was added dropwise to
a solution of ester 20 (1.61 mmol) in dry THF (5 mL) at À788C. The mix-
ture was stirred at the same temperature for 30 min and then warmed up
to room temperature. It was treated with saturated potassium and
sodium tartrate (Rochelle salt) and stirred for 30 min. After extraction
with EtOAc three times, the combined organic layers were washed with
brine, dried over Na2SO4, and concentrated under reduced pressure. The
residue was purified by silica-gel column chromatography to give unsatu-
rated alcohol 21.
mol% Pd(OAc)2 and 20 mol% PPh3 at reflux temperature for 3 h and
A
the product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (84% yield). M.p. 64–658C; 1H NMR (CDCl3): d=2.22 (s,
6H), 4.95 (s, 2H), 5.50 (t, J=1.5 Hz, 2H), 7.90 (s, 2H), 10.25 ppm (s,
2H); 13C NMR (CDCl3): d=24.54, 119.95, 127.96, 136.39, 140.56, 145.79,
191.44 ppm; HRMS (FAB): m/z calcd for C14H15O2: 215.1072 [M++H];
found: 215.1081.
3-Vinylthiophene-2-carbaldehyde (14i): The reaction was carried out by
following the general procedure A and the product was purified by silica-
1
gel column chromatography (hexane/EtOAc 10:1) (82% yield); H NMR
[1-Benzyl-4-(1-methoxymethylvinyl)-1,2,5,6-tetrahydropyridin-3-yl]-meth-
anol (21a): The reaction was carried out by following the general proce-
dure C and the product was purified by silica-gel column chromatogra-
(CDCl3): d=5.58 (dd, J=12.2, 1.0 Hz, 1H), 5.83 (dd, J=17.6, 1.0 Hz,
1H), 7.25 (dd, J=17.6, 11.0 Hz, 1H), 7.33 (d, J=5.1 Hz, 1H), 7.64 (dt,
J=5.2, 0.7 Hz, 1H), 10.13 ppm (d, J=1.0 Hz, 1H); 13C NMR (CDCl3):
d=119.90, 126.65, 127.52, 134.12, 137.70, 146.84, 181.94 ppm; HRMS
(EI): m/z calcd for C7H6O3: 138.0139 [M+]; found: 138.0134.
1
phy (EtOAc) (69% yield); H NMR (CDCl3): d=2.22–2.23 (m, 2H), 2.56
(t, J=5.8 Hz, 2H), 2.67 (br s, 1H), 3.16 (t, J=2.2 Hz, 2H), 3.45 (s, 3H),
3.63 (s, 2H), 3.90 (s, 2H), 3.98 (s, 2H), 4.96 (d, J=2.1 Hz, 1H), 5.20 (d,
J=1.6 Hz, 1H), 7.24–7.39 ppm (m, 5H); 13C NMR (CDCl3): d=29.88,
49.28, 54.48, 58.33, 61.25, 62.55, 74.45, 115.67, 127.10, 128.20, 129.28,
132.13, 133.25, 137.58, 145.08 ppm; HRMS (FAB): m/z calcd for
C17H24NO2: 274.1807 [M++H]; found: 274.1805.
General procedure B: preparation of unsaturated esters 20: A mixture of
potassium vinyltrifluoroborate (2.60 mmol), Pd(OAc)2 (0.10 mmol), PPh3
A
(0.20 mmol), Cs2CO3 (6.00 mmol), a,b-unsaturated ester 19 (2.00 mmol)
in THF (15 mL), and water (3 mL) was heated to reflux temperature and
stirred for several hours. After cooling to room temperature, the mixture
was diluted with water and extracted with ether three times. The organic
layers were combined, washed with brine, and dried over Na2SO4. After
filtration, the filtrate was evaporated under reduced pressure and the res-
idue was purified by silica-gel column chromatography to give unsaturat-
ed ester 20.
3-Benzyloxymethyl-4-methyl-2,4-pentadien-1-ol (21b): The reaction was
carried out by following the general procedure C and the product was
purified by silica-gel column chromatography (hexane/EtOAc 3:1) (90%
yield). 1H NMR (CDCl3): d=1.36 (br s, 1H), 1.86 (dd, J=1.6, 1.0 Hz,
3H), 4.05 (d, J=0.9 Hz, 2H), 4.27 (d, J=6.5 Hz, 2H), 4.51 (s, 2H), 4.76
(dq, J=2.2, 0.9 Hz, 1H), 5.09 (dq, J=2.2, 1.6 Hz, 1H), 5.71 (tt, J=6.8,
1.2 Hz, 1H), 7.27–7.37 ppm (m, 5H); 13C NMR (CDCl3): d=21.87, 59.50,
71.64, 72.51, 115.81, 127.47, 127.76, 128.20, 137.95, 141.49 ppm; HRMS
(FAB): m/z calcd for C14H18KO2: 257.0994 [M++K]; found: 257.0952.
1-Benzyl-4-(1-methoxymethylvinyl)-1,2,5,6-tetrahydropyridine-3-carbox-
ylic acid ethyl ester (20a): The reaction was carried out at reflux temper-
ature for 12 h by following general procedure B, and the product was pu-
rified by silica-gel column chromatography (hexane/EtOAc 5:1) (86%
yield). 1H NMR (CDCl3): d=1.23 (t, J=7.0 Hz, 3H), 2.37 (tt, J=5.5,
5.5 Hz, 2H), 2.54 (t, J=5.5 Hz, 2H), 3.28 (t, J=2.5 Hz, 2H), 3.36 (s, 3H),
3.63 (s, 2H), 4.03 (s, 2H), 4.12 (q, J=7.1 Hz, 2H), 4.93 (d, J=0.6 Hz,
6-Chloro-3-vinyl-2-hexen-1-ol (21c): The reaction was carried out by fol-
lowing the general procedure C and the product was purified by silica-gel
column chromatography (hexane/EtOAc 3:1) (94% yield); 1H NMR
(CDCl3): d=1.25 (br s,1H), 1.92–1.98 (m, 2H), 2.39 (t, J=7.4 Hz, 2H),
8254
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 8246 – 8261

Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
3.56 (t, J=6.4 Hz, 2H), 4.32 (d, J=6.7 Hz, 2H), 5.22 (dt, J=11.0, 1.6 Hz,
1H), 5.33 (d, J=17.4 Hz, 1H), 5.62 (t, J=7.1 Hz, 1H), 6.61 ppm (ddd,
J=17.4, 11.0, 0.9 Hz, 1H); 13C NMR (CDCl3): d=30.20, 31.25, 44.61,
58.23, 115.64, 129.01, 131.71, 137.57 ppm; HRMS (FAB): m/z calcd for
C8H12Cl: 143.0628 [M+ÀOH]; found: 143.0629.
3-Isopropenyl-7-methylocta-2,6-dien-1-ol (21d): The reaction was carried
out by following the general procedure C and the product was purified
by silica-gel column chromatography (hexane/EtOAc 8:1) (95% yield);
1H NMR (CDCl3): d=1.20 (br s, 1H), 1.60 (s, 3H), 1.68 (d, J=1.0 Hz,
3H), 1.81 (t, J=0.9 Hz, 3H), 2.02–2.07 (m, 2H), 2.11–2.15 (m, 2H), 4.17
(d, J=6.8 Hz, 2H), 4.63 (dq, J=2.4, 0.9 Hz, 1H), 4.99 (dq, J=3.1, 1.5 Hz,
1H), 5.09 (t heptet, J=6.8, 1.2 Hz, 1H), 5.42 ppm (tt, J=6.8, 0.9 Hz,
1H); 13C NMR (CDCl3): d=17.67, 22.12, 25.63, 26.64, 36.00, 60.02,
114.46, 123.79, 124.34, 131.68, 143.21, 146.08 ppm; HRMS (FAB): m/z
calcd for C12H19: 163.1487 [M+ÀOH]; found: 163.1485.
and concentrated under reduced pressure and the residue was purified by
silica-gel column chromatography to give 1,5,7-trien-4-ol 7.
1-(1-Hydroxy-3-butenyl)-2-vinylcyclopentene (7a): The reaction was car-
ried out in Et2O by following the general procedure E and the product
was purified by silica-gel column chromatography (hexane/EtOAc 10:1)
(80% yield). 1H NMR (CDCl3): d=1.68 (br s, 1H), 1.79–1.91 (m, 2H),
2.27–2.33 (m, 1H), 2.38–2.44 (m, 2H), 2.52 (t, J=7.6 Hz, 2H), 2.59–2.65
(m, 1H), 4.72 (dd, J=6.4, 6.1 Hz, 1H), 5.08–5.17 (m, 4H), 5.76 (dddd,
J=17.1, 14.3, 7.6, 6.4 Hz, 1H), 6.72 ppm (dd, J=17.1, 10.7 Hz, 1H);
13C NMR (CDCl3): d=21.34, 31.91, 32.71, 40.21, 67.23, 114.54, 117.62,
130.17, 134.43, 136.76, 142.27 ppm; HRMS (FAB): m/z calcd for C11H15
:
147.1174 [M+ÀOH]; found: 147.1170.
1-(1-Hydroxy-3-butenyl)-2-isopropenylcyclopentene (7b): The reaction
was carried out in Et2O by following the general procedure E and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (80% yield); 1H NMR (CDCl3): d=1.60 (br s, 1H), 1.82
(quint, J=7.6 Hz, 2H), 1.84 (t, J=1.2 Hz, 3H), 2.20–2.30 (m, 1H), 2.32–
2.55 (m, 5H), 4.67 (dd, J=8.3, 5.4 Hz, 1H), 4.76 (d, J=1.7 Hz, 1H), 4.93
(dq, J=2.4, 1.5 Hz, 1H), 5.09 (ddt, J=11.5, 2.0, 1.0 Hz, 1H), 5.14 (dq, J=
17.4, 1.7 Hz, 1H), 5.78 ppm (dddd, J=16.8, 10.2, 7.8, 6.4 Hz, 1H);
13C NMR (CDCl3): d=21.78, 22.43, 31.25, 36.38, 40.50, 67.72, 113.39,
117.44, 134.82, 138.60, 141.08, 141.55 ppm; HRMS (FAB): m/z calcd for
C12H17O: 177.1279 [M+ÀH]; found: 177.1276.
General procedure D: preparation of unsaturated aldehydes: MnO2
(50.0 mmol) was added in one portion to a solution of 21 (1.73 mmol) in
dichloromethane (15 mL) under air. The mixture was stirred for 2.5 h at
room temperature and then was filtered through Celite. The residual
solid was washed thoroughly with dichloromethane and the filtrate was
concentrated under reduced pressure. The crude aldehyde was character-
1
ized by H NMR and used without further purification.
1-Benzyl-4-(1-methoxymethylvinyl)-1,2,5,6-tetrahydropyridine-3-carbal-
1-(1-Hydroxy-2-methyl-3-butenyl)-2-vinylcyclopentene (7c): The reaction
was carried out by following the general procedure E and the product
was purified by silica-gel column chromatography (hexane/EtOAc 10:1)
(diastereomeric mixture: 88% yield). The following data are for a mix-
ture of two diastereomers (0.5:0.5); 1H NMR (CDCl3): d=0.84 (d, J=
6.7 Hz, 1.5H), 1.11 (d, J=6.7 Hz, 1.5H), 1.65 (br s, 0.5H), 1.76–1.89 (m,
2.5H), 2.31–2.67 (m, 5H), 4.31 (d, J=9.5 Hz, 0.5H), 4.41 (d, J=8.2 Hz,
0.5H), 4.97 (ddd, J=10.4, 1.9, 0.9 Hz, 0.5H), 5.03 (dt, J=17.4, 1.6 Hz,
0.5H), 5.08–5.21 (m, 3H), 5.62 (ddd, J=18.0, 10.4, 7.7 Hz, 0.5H), 5.78
(ddd, J=18.6, 10.1, 8.5 Hz, 0.5H), 6.69 (dd, J=17.1, 2.5 Hz, 0.5H),
6.72 ppm (dd, J=17.4, 2.1 Hz, 0.5H); 13C NMR (CDCl3): d=16.04, 16.48,
21.51, 21.64, 31.92, 32.67, 32.72, 32.82, 42.80, 43.61, 71.00, 71.88, 114.49,
114.61, 114.69, 116.74, 130.41, 130.51, 137.58, 138.65, 140.01, 140.85,
141.34, 141.86 ppm; HRMS (FAB): m/z calcd for C12H17O: 177.1279 [M+
ÀH]; found: 177.1276.
1-(1-Hydroxy-3-methyl-3-butenyl)-2-vinylcyclopentene (7d): The reaction
was carried out by following the general procedure E and the product
was purified by silica-gel column chromatography (hexane/EtOAc 10:1)
(80% yield). 1H NMR (CDCl3): d=1.78 (s, 4H), 1.85 (quint, J=8.0 Hz,
2H), 2.19 (dd, J=13.7, 4.6 Hz, 1H), 2.37 (ddd, J=13.9, 9.0, 0.7 Hz, 1H),
2.44–2.66 (m, 4H), 4.80–4.84 (m, 2H), 4.87 (t, J=1.7 Hz, 1H), 5.09–5.15
(m, 2H), 6.73 ppm (dd, J=17.3, 10.8 Hz, 1H); 13C NMR (CDCl3): d=
21.38, 22.27, 31.94, 32.78, 44.28, 65.49, 113.53, 114.57, 130.15, 136.64,
142.16, 142.39 ppm; HRMS (FAB): m/z calcd for C12H17 O: 177.1279 [M+
ÀH]; found: 177.1276.
dehyde: The reaction was carried out by following the general procedure
D. H NMR (CDCl3): d=2.49–2.51 (m, 2H), 2.57 (t, J=5.2 Hz, 2H), 3.27
(t, J=2.5 Hz, 2H), 3.35 (s, 3H), 3.65 (s, 2H), 4.04 (t, J=0.6 Hz, 2H),
5.14–5.15 (m, 1H), 5.45 (q, J=1.2 Hz, 1H), 7.24–7.36 (m, 5H), 9.79 ppm
(s, 1H).
1
3-Benzyloxymethyl-4-methyl-2,4-pentadienal: The reaction was carried
out by following the general procedure D; 1H NMR (CDCl3): d=1.96
(dd, J=1.2, 1.0 Hz, 3H), 4.20 (d, J=1.4 Hz, 2H), 4.55 (s, 2H), 5.05 (dd,
J=1.7, 1.0 Hz, 1H), 5.30 (quint, J=1.5 Hz, 1H), 6.18 (dt, J=8.0, 1.5 Hz,
1H), 7.25–7.39 (m, 5H), 9.83 ppm (d, J=8.0 Hz, 1H).
6-Chloro-3-vinyl-2-hexenal: The reaction was carried out by following
1
the general procedure D; H NMR (CDCl3): d=1.94–2.04 (m, 2H), 2.56–
2.60 (m, 2H), 3.58 (t, J=6.1 Hz, 2H), 5.61 (dq, J=11.0, 0.7 Hz, 1H), 5.70
(dt, J=17.1, 0.6 Hz, 1H), 5.94 (d quint, J=8.0, 0.6 Hz, 1H), 7.19 (ddd,
J=17.4, 11.0, 0.6 Hz, 1H), 10.15 ppm (d, J=7.9 Hz, 1H).
3-Isopropenyl-7-methyl-2,6-octadienal: The reaction was carried out by
following the general procedure D; 1H NMR (CDCl3): d=1.60 (s, 3H),
1.68 (d, J=1.3 Hz, 3H), 1.94 (dd, J=1.6, 1.0 Hz, 3H), 2.14 (q, J=7.3 Hz,
2H), 2.33 (dd, J=9.5, 6.7 Hz, 2H), 4.94 (dq, J=1.8, 0.9 Hz, 1H), 5.07 (t
heptet, J=7.0, 1.5 Hz, 1H), 5.23 (quint, J=1.6 Hz, 1H), 5.88 (dt, J=8.0,
1.2 Hz, 1H), 9.75 ppm (d, J=7.9 Hz, 1H).
General procedure E: preparation of 1,5,7-trien-4-ols 7: To a stirred solu-
tion of 14 (6.93 mmol) in THF (20 mL) was added allyl Grignard reagent
(0.58m solution in THF, 13.9 mmol) at 08C. The reaction mixture was
warmed to room temperature and stirred for 30 min. The mixture was
then quenched by addition of saturated aqueous NH4Cl solution, extract-
ed with EtOAc three times, and washed with brine. The organic layer
was dried over Na2SO4 and concentrated under reduced pressure. The
residue was purified by silica-gel column chromatography to give 1,5,7-
trien-4-ols 7.
1-(1-Hydroxy-2-methyl-3-butenyl)-2-isopropenylcyclopentene (7e): The
reaction was carried out by following the general procedure E and the
products were purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (diastereomeric mixture: 86% yield); The following data
are for a mixture of two diastereomers (0.5:0.5); 1H NMR (CDCl3): d=
0.85 (d, J=6.8 Hz, 1.5H), 1.12 (d, J=6.8 Hz, 1.5H), 1.51 (br s, 0.5H),
1.75 (br s, 0.5H), 1.78–1.87 (m, 2H), 1.81(s, 1.5H), 1.85 (s, 1.5H), 2.28–
G
General procedure F: preparation of homoallylic alcohols 7 by allylbora-
tion: Allylboronic acid pinacol ester 13b (0.866 mmol) was added to 14
(0.722 mmol) with stirring at room temperature. The reaction mixture
was stirred for 48 h without solvent and then quenched by addition of
CHCl3 and the crude material was purified by silica-gel column chroma-
tography to give 1,5,7-trien-4-ols 7.
2.61 (m, 5H), 4.27 (dd, J=9.5, 2.2 Hz, 0.5H), 4.34 (dd, J=8.8, 4.2 Hz,
0.5H), 4.80 (dd, J=13.4, 1.7 Hz, 1H), 4.91–4.93 (m, 1H), 5.00 (dt, J=
10.5, 1.0 Hz, 0.5H), 5.02 (dt, J=17.6, 1.4 Hz, 0.5H), 5.14 (dd, J=10.2,
1.7 Hz, 0.5H), 5.17 (dd, J=17.4, 1.7 Hz, 0.5H), 5.62 (ddd, J=17.8, 10.5,
7.6 Hz, 0.5H), 5.76 ppm (ddd, J=17.3, 10.2, 8.8 Hz, 0.5H); 13C NMR
(CDCl3): d=16.21, 16.64, 21.85, 21.98, 22.46, 22.49, 30.90, 31.46, 36.31,
36.45, 42.37, 43.27, 71.30, 72.23, 113.20, 113.22, 114.03, 116.39, 136.78,
138.08, 140.38, 141.54, 141.70, 141.96, 143.22 ppm; HRMS (FAB): m/z
calcd for C13H19O: 191.1436 [M+ÀH]; found: 191.1440.
1-(1-Hydroxy-3-methyl-3-butenyl)-2-isopropenylcyclopentene (7 f): The
reaction was carried out by following the general procedure E and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (89% yield). 1H NMR (CDCl3): d=1.67 (br s, 1H), 1.77 (s,
General procedure G: preparation of homoallylic alcohols 7 by allylstan-
nation: BF3·OEt2 (1.47 mmol) was added to a stirred solution of 14
(1.05 mmol) in dichloromethane (5 mL) at À788C. 2-Chloromethyl-3-
tributylstannylpropene 13e was then added to the mixture. The resulting
mixture was stirred for 30 min and then quenched by addition of water at
À788C. The mixture was warmed to room temperature, extracted with
EtOAc, and washed with brine. The organic layer was dried over Na2SO4
Chem. Eur. J. 2008, 14, 8246 – 8261
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8255

K. Yoshida, T. Imamoto et al.
3H), 1.82 (quint, J=7.6 Hz, 2H), 1.85 (t, J=1.4 Hz, 3H), 2.18 (dd, J=
13.7, 3.9 Hz, 1H), 2.35–2.63 (m, 5H), 4.76–4.81 (m, 3H), 4.87 (dq, J=3.4,
1.7 Hz, 1H), 4.95 ppm (dq, J=2.9, 1.5 Hz, 1H); 13C NMR (CDCl3): d=
21.76, 22.20, 22.34, 22.38, 31.20, 36.35, 44.54, 65.84, 113.25, 113.28, 138.83,
140.77, 141.61, 142.54 ppm; HRMS (FAB): m/z calcd for C13H19O:
191.1436 [M+ÀH]; found: 191.1432.
and the product was purified by silica-gel column chromatography
(hexane/EtOAc 5:1) (83% yield (2 steps)); The following data are for a
mixture of two diastereomers (0.53:0.47); 1H NMR (CDCl3): d=0.89 (d,
J=6.8 Hz, 1.59H), 1.11 (d, J=6.6 Hz, 1.41H), 1.45–1.72 (m, 8.00H), 1.83
(d, J=3.2 Hz, 0.47H), 1.86 (d, J=2.2 Hz, 0.53H), 2.14–2.49 (m, 5.00H),
3.34 (s, 1.41H), 3.35 (s, 1.59H), 3.79 (d, J=12.3 Hz, 0.53H), 3.81 (dt, J=
13.0, 1.2 Hz, 0.47H), 3.85–3.89 (m, 1.00H), 4.11–4.17 (m, 1.00H), 4.71
(dt, J=2.2, 1.2 Hz, 0.47H), 4.73 (dt, J=2.2, 1.2 Hz, 0.53H), 4.89 (ddd, J=
10.4, 2.6, 1.0 Hz, 0.53H), 4.96 (dt, J=17.4, 1.5 Hz, 0.47H), 5.05 (dd, J=
10.2 Hz, 1.06H), 5.10 (d quint, J=14.5, 1.4 Hz, 0.94H), 5.60 (ddd, J=
17.4, 10.4, 7.2 Hz, 0.47H), 5.71 ppm (ddd, J=18.6, 10.1, 8.4 Hz, 0.53H);
13C NMR (CDCl3): d=17.17, 17.47, 25.39, 25.66, 26.00, 26.05, 26.80,
26.94, 27.99, 28.14, 30.25, 30.71, 30.94, 40.52, 41.91, 58.41, 74.71, 74.95,
75.68, 76.65, 76.70, 76.75, 77.03, 113.01, 113.45, 114.02, 115.59, 136.58,
137.39, 137.82, 138.53, 141.31, 142.18, 146.42, 146.60 ppm; HRMS (FAB):
m/z calcd for C17H27O: 247.2062 [M+ÀOH]; found: 247.2071.
1-(1-Hydroxy-3-methoxycarbonyl-3-butenyl)-2-vinylcyclopentene
(7g):
The reaction was carried out by following the general procedure F and
the product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1 to 3:1) (91% yield). 1H NMR (CDCl3): d=1.84 (quint, J=
7.7 Hz, 2H), 2.12 (br s, 1H), 2.42–2.67 (m, 6H), 3.77 (s, 3H), 4.88 (dd,
J=8.3, 4.9 Hz, 1H), 5.08 (d, J=4.0 Hz, 1H), 5.12 (d, J=10.8 Hz, 1H),
5.66 (d, J=1.0 Hz, 1H), 6.23 (d, J=1.5 Hz, 1H), 6.69 ppm (dd, J=17.3,
10.8 Hz, 1H); 13C NMR (CDCl3): d=21.41, 31.85, 32.72, 38.97, 52.05,
67.17, 114.70, 127.82, 130.17, 136.77, 136.95, 142.11, 167.83 ppm; HRMS
(FAB): m/z calcd for C13H17O2: 205.1229 [M+ÀOH]; found: 205.1229.
1-(1-Hydroxy-2-methyl-3-butenyl)-2-(1-methoxymethylvinyl)-cyclopen-
tene (7h): The reaction was carried out by following the general proce-
dure E and the product was purified by silica-gel column chromatogra-
phy (hexane/EtOAc 4:1) (diastereomeric mixture: 88% yield). The fol-
lowing data are for a mixture of two diastereomers (0.53:0.47); 1H NMR
(CDCl3): d=0.87 (d, J=6.7 Hz, 1.41H), 1.13 (d, J=6.7 Hz, 1.59H), 1.82
(quint, J=7.7 Hz, 1.06H), 1.86 (quint, J=7.6 Hz, 0.94H), 1.95 (br s,
1.00H), 2.32–2.62 (m, 5.00H), 3.32 (s, 1.41H), 3.33 (s, 1.59H), 3.92–3.99
(m, 2.00H), 4.19 (d, J=9.5 Hz, 0.47H), 4.23 (d, J=8.9 Hz, 0.53H), 4.96
(ddd, J=10.4, 1.9, 0.9 Hz, 0.47H), 4.99 (d, J=2.1 Hz, 0.53H), 5.04 (d, J=
2.2 Hz, 0.47H), 5.05 (dt, J=17.7, 1.3 Hz, 0.53H), 5.13 (ddd, J=10.1, 1.9,
0.6 Hz, 0.47H), 5.17 (ddd, J=17.7, 1.9, 0.9 Hz, 0.47H), 5.19 (dt, J=3.4,
1.2 Hz, 0.53H), 5.21 (dt, J=2.2, 1.2 Hz, 0.53H), 5.64 (ddd, J=17.7, 10.7,
7.6 Hz, 0.53H), 5.78 ppm (ddd, J=18.6, 10.1, 8.6 Hz, 0.47H); 13C NMR
(CDCl3): d=16.35, 16.63, 21.88, 21.98, 30.97, 31.50, 36.43, 36.50, 41.87,
42.82, 57.85, 57.88, 71.17, 71.78, 74.67, 74.84, 114.01, 114.64, 114.97,
115.95, 138.46, 139.78, 139.93, 140.45, 141.22, 141.59, 142.24, 142.30 ppm;
HRMS (FAB): m/z calcd for C14H21O: 205.1592 [M+ÀOH]; found:
205.1599.
1-(2-Isopropenyl-4,5-dimethoxyphenyl)-2-methyl-3-buten-1-ol (7l): The
reaction was carried out by following the general procedure E and the
products were purified by silica-gel column chromatography (hexane/
EtOAc 3:1) (diastereomeric mixture: 90% yield); The following data are
for a mixture of two diastereomers (0.5:0.5); 1H NMR (CDCl3): d=0.77
(d, J=6.8 Hz, 1.5H), 1.11 (d, J=6.6 Hz, 1.5H), 1.75 (br s, 0.5H), 2.03 (s,
1.5H), 2.05 (s, 1.5H), 2.06 (br s, 0.5H), 2.50 (sextet, J=7.1 Hz, 0.5H),
2.59 (sextet, J=6.8 Hz, 0.5H), 3.86 (s, 1.5H), 3.87 (s, 1.5H), 3.89 (s,
1.5H), 3.91 (s, 1.5H), 4.55 (d, J=8.8 Hz, 0.5H), 4.73 (d, J=7.1 Hz,
0.5H), 4.84 (dd, J=9.3 Hz, 1H), 4.95–5.00 (m, 1H), 5.18–5.27 (m, 2H),
5.68 (ddd, J=17.3, 10.5, 6.6 Hz, 0.5H), 5.85 (ddd, J=18.8, 10.3, 8.6 Hz,
0.5H), 6.59 (s, 0.5H), 6.61 (s, 0.5H), 6.96 (s, 0.5H), 7.01 ppm (s, 0.5H);
13C NMR (CDCl3): d=14.47, 17.03, 25.82, 25.89, 44.16, 46.42, 55.82,
55.93, 73.37, 73.63, 108.88, 109.39, 110.67, 110.78, 114.79, 115.85, 116.78,
130.84, 130.84, 131.56, 135.55, 136.46, 140.79, 141.39, 144.64, 144.76,
147.72, 147.90, 147.93, 148.27 ppm; HRMS (FAB): m/z calcd for
C16H22O3: 262.1569 [M+]; found: 262.1576.
1-(5-Vinyl-4-benzo[1,3]dioxolyl)-3-methoxycarbonyl-3-buten-1-ol (7m):
A
The reaction was carried out in CH2Cl2 (0.5 mL) by following the general
procedure F, and the product was purified by silica-gel column chroma-
tography (hexane/EtOAc=5:1 to 2:1) (88% yield); 1H NMR (CDCl3):
d=2.78 (ddd, J=13.9, 4.6, 0.9 Hz, 1H), 2.79 (d, J=8.0 Hz, 1H), 2.88
(ddd, J=14.2, 9.2, 0.9 Hz, 1H), 3.76 (s, 3H), 5.16 (ddd, J=8.0, 4.3,
4.3 Hz, 1H), 5.25 (dd, J=10.8, 1.2 Hz, 1H), 5.49 (dd, J=17.6, 1.5 Hz,
1H), 5.65 (dd, J=2.2, 0.9 Hz, 1H), 5.99 (dd, J=4.6, 1.6 Hz, 2H), 6.24 (d,
J=1.2 Hz, 1H), 6.73 (d, J=8.3 Hz, 1H), 6.98 (d, J=8.0 Hz, 1H),
6.98 ppm (dd, J=17.6, 10.8 Hz, 1H); 13C NMR (CDCl3): d=39.73, 51.80,
68.08, 100.97, 107.62, 115.44, 120.02, 122.96, 128.15, 130.50, 133.82, 136.44,
144.70, 146.99, 167.55 ppm; HRMS (FAB): m/z calcd for C15H16KO5:
315.0635 [M++K]; found: 315.0639.
1-[2-(1-Methoxymethylvinyl)-3,4-dihydronaphthalen-1-yl]-2-methyl-3-
buten-1-ol (7i): The reaction was carried out by following the general
procedure E and the products were purified by silica-gel column chroma-
tography (hexane/EtOAc 10:1) (diastereomeric mixture; 31% yield
(2 steps)). The following data are for a mixture of two diastereomers
1
(0.53:0.47); H NMR (CDCl3): d=0.71 (d, J=6.6 Hz, 1.59H), 1.19 (d, J=
6.6 Hz, 1.41H), 2.16–2.41 (m, 3.00H), 2.60–2.95 (m, 3.00H), 3.36 (s,
1.53H), 3.39 (s, 1.47H), 3.94 (s, 0.94H), 3.99 (s, 1.06H), 4.50 (d, J=
10.2 Hz, 0.47H), 4.51 (d, J=10.2 Hz, 0.53H), 4.60 (dt, J=17.6, 2.0 Hz,
0.47H), 4.73 (ddd, J=10.7, 2.0, 1.0 Hz, 0.53H), 5.01 (t, J=0.7 Hz,
0.47H), 5.08 (s, 0.53H), 5.15 (dd, J=10.2, 1.4 Hz, 0.47H), 5.21 (dq, J=
17.4, 1.0 Hz, 0.53H), 5.27 (q, J=2.0 Hz, 0.47H), 5.32 (q, J=1.7 Hz,
0.53H), 5.46 (ddd, J=17.6, 10.5, 7.6 Hz, 0.47H), 5.83 (ddd, J=17.4, 10.3,
8.3 Hz, 0.53H), 7.12 À7.22 (m, 3.00H), 7.97 (d, J=7.9 Hz, 0.47H),
8.03 ppm (d, J=7.6 Hz, 0.53H); 13C NMR (CDCl3): d=16.63, 17.03,
28.66, 28.81, 29.40, 29.46, 40.48, 41.55, 58.48, 74.89, 74.91, 75.65, 113.67,
114.66, 114.79, 115.86, 125.80, 125.95, 126.00, 126.13, 126.32, 126.48,
126.99, 127.09, 132.38, 133.26, 133.68, 133.86, 136.79, 139.43, 140.47,
141.10, 142.16, 146.61, 146.75 ppm; HRMS (FAB): m/z calcd for
C19H23O: 267.1749 [M+ÀOH]; found: 267.1751.
1-(5-Vinyl-4-benzo[1,3]dioxolyl)-3-chloromethyl-3-buten-1-ol (7n): The
E
reaction was carried out by following general procedure G and the prod-
uct was purified by silica-gel column chromatography (hexane/EtOAc
10:1 to 4:1) (78% yield); 1H NMR (CDCl3): d=2.48 (d, J=7.8 Hz, 1H),
2.68 (ddd, J=14.9, 4.9, 1.0 Hz, 1H), 2.78 (ddd, J=14.9, 9.3, 1.0 Hz, 1H),
4.11 (s, 2H), 5.10 (dd, J=2.2, 1.3 Hz, 1H), 5.15 (ddd, J=9.0, 7.6, 4.9 Hz,
1H), 5.25 (s, 1H), 5.25 (dd, J=9.8, 1.4 Hz, 1H), 5.48 (dd, J=17.3, 1.5 Hz,
1H), 6.00 (dd, J=3.4, 1.5 Hz, 2H), 6.75 (d, J=8.3 Hz, 1H), 6.96 (dd, J=
17.3, 11.0 Hz, 1H), 6.98 ppm (d, J=8.0 Hz, 1H); 13C NMR (CDCl3): d=
40.45, 48.13, 67.88, 101.13, 107.90, 116.01, 117.51, 120.44, 122.97, 130.57,
133.81, 141.73, 144.77, 147.15 ppm; HRMS (FAB): m/z calcd for
C14H15ClO3 266.0710 [M+]; found: 266.0716.
1-(1-Hydroxy-3-benzyloxymethyl-3-butenyl)-2-vinylcycloheptene
(7j):
The reaction was carried out by following the general Procedure E and
the product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (67% yield (2 steps)); 1H NMR (CDCl3): d=1.42–1.54 (m,
4H), 1.70–1.81 (m, 2H), 2.26 (dd, J=14.5, 3.4 Hz, 1H), 2.33–2.41 (m,
6H), 4.01 (dd, J=19.4, 2.0 Hz, 2H), 4.54 (d, J=1.2 Hz, 2H), 4.96–5.01
(m, 2H), 5.08 (s, 1H), 5.17–5.22 (m, 2H), 6.76 (dd, J=17.6, 11.1 Hz, 1H),
7.27–7.38 ppm (m, 5H); 13C NMR (CDCl3): d=26.00, 27.22, 27.38, 28.40,
32.42, 40.32, 68.75, 72.34, 73.40, 112.44, 116.05, 127.70, 127.79, 128.42,
133.86, 136.95, 137.86, 142.91, 142.93 ppm; HRMS (FAB): m/z calcd for
C21H28O2K: 351.1726 [M++K]; found: 351.1717.
1,4-Bis-(1-hydroxy-3-methyl-3-butenyl)-2,5-diisopropenylbenzene
(7o):
The reaction was carried out by following the general procedure E and
the products were purified by silica-gel column chromatography (hexane/
EtOAc 5:1) (>99% yield). The following data are for a mixture of two
diastereomers (0.5:0.5); 1H NMR (CDCl3): d=1.79 (s, 6H), 2.04 (br s,
1H), 2.08 (br s, 1H), 2.09 (s, 6H), 2.34 (t, J=7.1 Hz, 4H), 4.87–4.88 (m,
4H), 4.91 (t, J=1.2 Hz, 2H), 5.03 (t, J=6.2 Hz, 2H), 5.24 (t, J=1.8 Hz,
2H), 7.30 (s, 1H), 7.31 ppm (s, 1H); 13C NMR (CDCl3): d=21.91, 25.29,
47.90, 47.93, 67.36, 67.47, 77.20, 113.37, 113.48, 115.29, 124.96, 125.01,
1-(1-Hydroxy-2-methyl-3-butenyl)-2-(1-methoxymethylvinyl)-cyclooctene
(7k): The reaction was carried out by following the general procedure E
8256
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Chem. Eur. J. 2008, 14, 8246 – 8261

Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
139.10, 139.17, 140.89, 140.94, 142.46, 142.50, 144.44, 144.54 ppm; HRMS
5.13–5.16 (m, 1H), 5.18 (d, J=9.6 Hz, 0.5H), 5.72–5.85 ppm (m, 1.0H);
13C NMR (CDCl3): d=14.81, 16.49, 17.70, 22.58, 25.64, 26.39, 36.22,
36.25, 43.65, 44.96, 71.87, 71.96, 113.99, 115.11, 116.12, 123.83, 125.40,
125.83, 131.61, 131.62, 140.33, 140.88, 143.59, 143.63, 146.62, 147.08 ppm;
(FAB): m/z calcd for C22H30KO2: 365.1883 [M++K]; found: 365.1887.
2-(1-Hydroxy-3-methoxycarbonyl-3-butenyl)-3-vinylthiophene (7p): The
reaction was carried out by following the general procedure F and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 5:1) (96% yield). 1H NMR (CDCl3): d=2.75 (ddd, J=14.1, 8.6,
0.9 Hz, 1H), 2.79 (br s, 1H), 2.83 (ddd, J=14.1, 4.3, 0.9 Hz, 1H), 3.80 (s,
3H), 5.25 (dd, J=10.7, 1.2 Hz, 1H), 5.35–5.37 (m, 1H), 5.57 (dd, J=17.4,
1.3 Hz, 1H), 5.66 (q, J=1.2 Hz, 1H), 6.26 (d, J=1.5 Hz, 1H), 6.77 (dd,
J=17.4, 10.7 Hz, 1H), 7.16 ppm (s, 2H); 13C NMR (CDCl3): d=42.52,
52.04, 67.17, 114.22, 123.51, 124.92, 128.71, 128.97, 135.08, 135.99, 143.80,
167.80 ppm; HRMS (FAB): m/z calcd for C12H14O3S: 238.0664 [M+];
found: 238.0663.
HRMS (FAB): m/z calcd for C16H25
:
217.1956 [M+ÀOH]; found:
217.1948.
General procedure H: preparation of 1,5,7-trien-4-ones 9: 1,5,7-Trien-4-ol
7 (0.361 mmol) was added to a stirred suspension of Dess–Martin period-
inane (0.722 mmol) in dichloromethane (10 mL) and pyridine
(1.44 mmol) at 08C. The reaction mixture was warmed to room tempera-
ture and stirred for 30 min. The mixture was then diluted with Et2O and
filtered through Celite. The residual solid was washed with Et2O thor-
oughly and the filtrate was concentrated under reduced pressure. Purifi-
cation by silica-gel flash column chromatography gave the corresponding
1,5,7-trien-4-one 9.
1-[1-Benzyl-4-(1-methoxymethylvinyl)-1,2,5,6-tetrahydro-3-pyridinyl]-2-
methyl-3-buten-1-ol (7q): The reaction was carried out by following the
general procedure E and the product was purified by silica-gel column
chromatography (EtOAc) (diastereomeric mixture: 72% yield (2 steps)).
The following data are for a mixture of two diastereomers (0.53:0.47);
1H NMR (CDCl3): d=0.89 (d, J=6.8 Hz, 1.41H), 1.08 (d, J=6.6 Hz,
1.59H), 2.03–2.39 (m, 5.00H), 2.66–2.72 (m, 1.00H), 2.82–2.91 (m,
1.00H), 3.34 (t, J=14.9 Hz, 1.06H), 3.35 (s, 3.00H), 3.51 (t, J=13.9 Hz,
0.94H), 3.70 (d, J=4.1 Hz, 0.53H), 3.73 (d, J=4.2 Hz, 0.47H), 3.84 (t,
J=12.4 Hz, 1.06H), 3.91 (t, J=12.5 Hz, 0.94H), 4.12 (s, 0.53H), 4.15 (s,
0.47H), 4.90–4.99 (m, 2.00H), 5.06–5.14 (m, 1.00H), 5.19 (q, J=2.0 Hz,
0.53H), 5.21 (q, J=1.5 Hz, 0.47H), 5.61 (ddd, J=18.1, 10.5, 7.8 Hz,
0.53H), 5.75 (ddd, J=18.6, 10.2, 8.3 Hz, 0.47H), 7.20–7.37 ppm (m,
5.00H); 13C NMR (CDCl3): d=16.84, 17.10, ?30.46, 30.70, 40.32, 41.19,
49.30, 49.32, 50.42, 50.65, 58.36, 58.38, 62.57, 62.61, 73.38, 73.79, 74.58,
74.70, 114.25, 114.50, 115.17, 115.56, 126.96, 126.98, 128.12, 128.14, 129.07,
129.17, 131.74, 133.06, 133.14, 134.31, 137.80, 137.96, 140.39, 141.83,
145.62, 145.68 ppm; HRMS (FAB): m/z calcd for C21H30NO2: 328.2277
[M++H]; found: 328.2278.
1-(3-Butenoyl)-2-vinylcyclopentene (9a): The reaction was carried out by
following the general procedure H and the product was purified by silica-
gel flash column chromatography (hexane/EtOAc 20:1) (74% yield);
1H NMR (CDCl3): d=1.91 (quint, J=7.3 Hz, 2H), 2.68 (t, J=7.3 Hz,
2H), 2.78 (t, J=7.3 Hz, 2H), 3.31 (dt, J=7.1, 1.5 Hz, 2H), 5.12 (dq, J=
17.4, 1.5 Hz, 1H), 5.18 (dq, J=10.1, 1.5 Hz, 1H), 5.42 (d, J=10.7 Hz,
1H), 5.47 (ddt, J=17.4, 0.9, 0.6 Hz, 1H), 5.97 (ddt, J=17.4, 10.1, 7.1 Hz,
1H), 7.41 ppm (dd, J=17.4, 10.7 Hz, 1H); 13C NMR (CDCl3): d=21.51,
33.36, 34.64, 47.11, 118.25, 121.33, 130.86, 132.03, 136.80, 150.83,
198.38 ppm; HRMS (EI): m/z calcd for C11H14O: 162.1045 [M+]; found:
162.1043.
1-(3-Butenoyl)-2-isopropenylcyclopentene (9b): The reaction was carried
out by following the general procedure H and the product was purified
by silica-gel flash column chromatography (hexane/EtOAc 20:1) (82%
yield); 1H NMR (CDCl3): d=1.87 (quint, J=7.8 Hz, 2H), 1.90 (dd, J=
1.7, 1.0 Hz, 3H), 2.61–2.71 (m, 4H), 3.39 (dt, J=6.8, 1.5 Hz, 2H), 4.90
(dd, J=2.0, 1.0 Hz, 1H), 5.03 (quint, J=1.7 Hz, 1H), 5.08 (ddd, J=17.3,
3.2, 1.7 Hz, 1H), 5.14 (ddd, J=10.5, 2.9, 1.7 Hz, 1H), 5.93 ppm (ddt, J=
17.3, 13.9, 6.8 Hz, 1H); 13C NMR (CDCl3): d=21.57, 21.64, 34.75, 38.38,
46.03, 115.31, 117.71, 131.41, 137.54, 141.64, 152.65, 200.63 ppm; HRMS
(EI): m/z calcd for C12H16O: 176.1201 [M+]; found: 176.1196.
6-Benzyloxymethyl-3,7-dimethyl-1,5,7-octatrien-4-ol (7r): The reaction
was carried out by following the general procedure E and the product
was purified by silica-gel column chromatography (hexane/EtOAc 5:1)
(diastereomeric mixture: 67% yield (2 steps)). The following data are for
a mixture of two diastereomers (0.5:0.5); 1H NMR (CDCl3): d=0.99 (d,
J=6.8 Hz, 1.5H), 1.05 (d, J=6.8 Hz, 1.5H), 1.53 (br s, 1H), 1.87–1.911
(m, 3H), 2.23 (sextet, J=7.1 Hz, 0.5H), 2.36 (sextet, J=6.6 Hz, 0.5H),
4.03 (d, J=1.2 Hz, 1H), 4.05 (s, 1H), 4.16 (t, J=8.3 Hz, 0.5H), 4.26–4.41
(m, 0.5H), 4.49 (s, 1H), 4.51 (s, 1H), 4.86 (d, J=7.6 Hz, 1H), 5.08–5.18
(m, 3H), 5.49 (t, J=10.8 Hz, 1H), 5.73–5.85 (m, 1H), 7.28–7.35 ppm (m,
5H); 13C NMR (CDCl3): d=14.86, 16.47, 22.57, 43.71, 44.79, 71.55, 71.67,
71.70, 72.68, 115.44, 116.48, 127.54, 127.72, 127.94, 128.20, 128.31, 138.15,
140.07, 140.42, 141.94, 141.99, 143.00, 143.48 ppm; HRMS (FAB): m/z
calcd for C18H24KO2: 311.1413 [M++K]; found: 311.1418.
1-(2-Methyl-3-butenoyl)-2-vinylcyclopentene (9c): The reaction was car-
ried out by following the general procedure H and the product was puri-
fied by silica-gel flash column chromatography (hexane/EtOAc 20:1)
(73% yield); 1H NMR (CDCl3): d=1.19 (d, J=7.1 Hz, 3H), 1.90 (quint,
J=4.6 Hz, 2H), 2.66 (dd, J=8.0, 6.8 Hz, 2H), 2.64–2.90 (m, 2H), 3.48
(quint t, J=6.8, 1.0 Hz, 1H), 5.08–5.09 (m, 1H), 5.11–5.12 (m, 1H), 5.38
(d, J=10.8 Hz, 1H), 5.45 (ddt, J=17.8, 1.4, 0.7 Hz, 1H), 5.84 (ddd, J=
17.8, 10.0, 7.8 Hz, 1H), 7.35 ppm (dd, J=17.6, 10.8 Hz, 1H); 13C NMR
(CDCl3): d=16.25, 21.68, 33.20, 34.72, 48.99, 116.17, 120.85, 132.06,
137.35, 137.58, 150.77, 201.92 ppm; HRMS (EI): m/z calcd for C12H16O:
176.1201 [M+]; found: 176.1200.
2-Benzyloxymethyl-9-chloro-6-vinyl-1,5-nonadien-4-ol (7 s): The reaction
was carried out at -788C by following the general procedure E and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 3:1) (70% yield (2 steps)). 1H NMR (CDCl3): d=1.89–1.96 (m,
2H), 2.33–2.38 (m, 4H), 2.62 (br s, 1H), 3.53 (td, J=6.8, 0.5 Hz, 2H),
3.39–4.01 (m, 2H), 4.54 (s, 2H), 4.70–4.76 (m, 1H), 5.07 (s, 1H), 5.16 (dt,
J=11.0, 1.2 Hz, 1H), 5.19 (d, J=1.2 Hz, 1H), 5.31 (d, J=17.8 Hz, 1H),
5.42 (d, J=8.6 Hz, 1H), 6.61 (ddd, J=17.1, 11.2, 0.7 Hz, 1H), 7.32–
7.36 ppm (m, 5H); 13C NMR (CDCl3): d=30.18, 31.32, 42.80, 44.69,
66.17, 72.40, 73.55, 115.58, 116.90, 127.81, 127.85, 128.48, 132.08, 132.78,
136.66, 137.72, 142.29 ppm; HRMS (FAB): m/z calcd for C19H25ClO2K
359.1180 [M++K]; found: 359.1173.
1-(3-Methyl-3-butenoyl)-2-vinylcyclopentene (9d): The reaction was car-
ried out by following the general procedure H and the product was puri-
fied by silica-gel flash column chromatography (hexane/EtOAc 20:1)
(89% yield); 1H NMR (CDCl3): d=1.77 (s, 3H), 1.89 (quint, J=7.4 Hz,
2H), 2.67 (t, J=7.7 Hz, 2H), 2.79 (t, J=7.4 Hz, 2H), 3.24 (s, 2H), 4.76
(dq, J=1.9, 1.0 Hz, 1H), 4.93 (quint, J=1.5 Hz, 1H), 5.41 (d, J=10.8 Hz,
1H), 5.46 (ddq, J=17.0, 1.6, 1.0 Hz, 1H), 7.40 ppm (dd, J=17.9, 10.8 Hz,
1H); 13C NMR (CDCl3): d=21.48, 22.64, 33.22, 34.74, 51.19, 114.25,
121.10, 132.00, 137.18, 139.27, 150.64, 198.40 ppm; HRMS (EI): m/z calcd
for C12H16O [M+] 176.1201; found: 176.1199.
1-(2-Methyl-3-butenoyl)-2-isopropenylcyclopentene (9e): The reaction
was carried out by following the general procedure H and the product
was purified by silica-gel flash column chromatography (hexane/EtOAc
20:1) (75% yield). 1H NMR (CDCl3): d=1.17 (d, J=6.8 Hz, 3H), 1.84–
1.93 (m, 5H), 2.54–2.77 (m, 4H), 3.66 (quint t, J=6.8, 1.2 Hz, 1H), 4.89
(s, 1H), 4.99 (quint, J=1.8 Hz, 1H), 5.04 (dt, J=4.3, 1.5 Hz, 1H), 5.08
(sextet, J=1.0 Hz, 1H), 5.82 ppm (m, 1H); 13C NMR (CDCl3): d=16.44,
21.77, 21.97, 35.62, 37.76, 48.86, 115.49, 115.85, 137.97, 138.03, 141.49,
150.94, 205.19 ppm; HRMS (EI): m/z calcd for C13H18O [M+] 190.1358;
found: 190.1357.
6-Isopropenyl-3,10-dimethyl-1,5,9-undecatrien-4-ol (7t): The reaction was
carried out by following the general procedure E and the products were
purified by silica-gel column chromatography (hexane/EtOAc 20:1) (dia-
stereomeric mixture: 73% yield (two steps)). The following data are for
a mixture of two diastereomers (0.5:0.5); 1H NMR (CDCl3): d=0.96 (d,
J=7.1 Hz, 1.5H), 1.12 (d, J=7.1 Hz, 1.5H), 1.52 (br s, 0.5H), 1.55 (br s,
0.5H), 1.59 (s, 3H), 1.67 (d, J=1.2 Hz, 3H), 1.81 (quint, J=1.2 Hz, 3H),
1.90–2.24 (m, 4.5H), 2.31–2.36 (m, 0.5H), 4.07 (t, J=8.9 Hz, 0.5H), 4.21
(dd, J=9.6, 5.8 Hz, 0.5H), 4.69 (dt, J=2.4, 0.9 Hz, 0.5H), 4.70 (dq, J=
2.5, 0.9 Hz, 0.5H), 4.98 (dq, J=2.4, 1.2 Hz, 1H), 5.05–5.12 (m, 2.5H),
Chem. Eur. J. 2008, 14, 8246 – 8261
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8257

K. Yoshida, T. Imamoto et al.
1-(3-Methyl-3-butenoyl)-2-isopropenylcyclopentene (9 f): The reaction
was carried out by following the general procedure H and the product
was purified by silica-gel flash column chromatography (hexane/EtOAc
20:1) (77% yield). 1H NMR (CDCl3): d=1.75 (s, 3H), 1.87 (quint, J=
7.8 Hz, 2H), 1.91 (s, 3H), 2.63 (tt, J=7.6, 2.2 Hz, 2H), 2.69 (tt, J=7.6,
2.2 Hz, 2H), 3.34 (s, 2H), 4.72 (d, J=1.0 Hz, 1H), 4.90–4.91 (m, 2H),
5.02 ppm (quint, J=1.7 Hz, 1H); 13C NMR (CDCl3): d=21.69, 21.75,
22.69, 35.07, 38.43, 50.18, 114.24, 115.36, 137.87, 139.73, 141.77, 152.46,
200.87 ppm; HRMS (EI): m/z calcd for C13H18O: 190.1358 [M+]; found:
190.1362.
147.22, 166.74, 197.66 ppm; HRMS (FAB): m/z calcd for C15H14O5:
274.0841 [M+]; found: 274.0837.
1-(5-Vinyl-4-benzo[1,3]dioxolyl)-3-chloromethyl-3-buten-1-one (9n): The
A
reaction was carried out by following general procedure H and the prod-
uct was purified by silica-gel flash column chromatography (hexane/
1
EtOAc 10:1) (77% yield). H NMR (CDCl3): d=3.85 (d, J=0.9 Hz, 2H),
4.19 (d, J=1.0 Hz, 2H), 5.08 (d, J=0.9 Hz, 1H), 5.20 (dd, J=11.0,
1.2 Hz, 1H), 5.33 (d, J=0.9 Hz, 1H), 5.50 (dd, J=17.4, 11.9 Hz, 1H),
6.06 (s, 2H), 6.88 (d, J=8.0 Hz, 1H), 6.90 (ddd, J=16.8, 10.4, 0.6 Hz,
1H), 7.04 ppm (d, J=8.0 Hz, 1H); 13C NMR (CDCl3): d=47.62, 48.16,
101.70, 110.93, 115.32, 119.02, 119.94, 120.88, 131.77, 134.93, 138.87,
146.56, 147.34, 198.25 ppm; HRMS (FAB): m/z calcd for C14H14ClO3:
265.0631 [M++H]; found: 265.0636.
1-(3-Methoxycarbonyl-3-butenoyl)-2-vinylcyclopentene (9g): The reac-
tion was carried out by following the general procedure H and the prod-
uct was purified by silica-gel flash column chromatography (hexane/
EtOAc 5:1) (86% yield). 1H NMR (CDCl3): d=1.92 (quint, J=7.7 Hz,
2H), 2.69 (t, J=7.7 Hz, 2H), 2.82 (t, J=7.7 Hz, 2H), 3.54 (d, J=0.9 Hz,
2H), 3.75 (s, 3H), 5.41 (d, J=11.1 Hz, 1H), 5.47 (dd, J=17.9, 0.9 Hz,
1H), 5.61 (q, J=1.2 Hz, 1H), 6.34 (d, J=1.2 Hz, 1H), 7.41 ppm (dd, J=
17.6, 10.8 Hz, 1H); 13C NMR (CDCl3): d=21.40, 33.31, 34.55, 45.35,
51.85, 121.39, 127.95, 131.94, 134.41, 136.30, 151.08, 166.74, 196.79 ppm;
HRMS (FAB): m/z calcd for C13H17O3: 221.1178 [M++H]; found:
221.1172.
2-(3-Methoxycarbonyl-3-butenoyl)-3-vinylthiophene (9p): The reaction
was carried out by following the general procedure H and the product
was purified by silica-gel flash column chromatography (hexane/EtOAc
1
10:1) (56% yield). H NMR (CDCl3): d=3.76 (s, 3H), 3.88 (d, J=1.0 Hz,
2H), 5.55 (dd, J=11.0, 1.2 Hz, 1H), 5.71 (dd, J=5.1, 1.2 Hz, 1H), 5.76
(dd, J=17.8, 1.2 Hz, 1H), 6.40 (d, J=1.0 Hz, 1H), 7.36 (d, J=5.1 Hz,
1H), 7.44 (dd, J=5.1, 0.5 Hz, 1H), 7.57 ppm (dd, J=17.8, 11.2 Hz, 1H);
13C NMR (CDCl3): d=44.98, 52.06, 118.80, 127.30, 128.76, 129.91, 130.77,
134.10, 134.47, 145.20, 166.66, 190.10 ppm; HRMS (FAB): m/z calcd for
C12H13O3S: 237.0585 [M++H]; found: 237.0577.
1-(2-Methyl-3-butenoyl)-2-(1-methoxymethylvinyl)-cyclopentene
(9h):
The reaction was carried out by following the general procedure H and
the product was purified by silica-gel flash column chromatography
(hexane/EtOAc 15:1) (66% yield). 1H NMR (CDCl3): d=1.17 (d, J=
6.8 Hz, 3H), 1.86–1.93 (m, 2H), 2.6–2.8 (m, 4H), 3.33 (s, 3H), 3.63 (tt,
J=7.8, 1.0 Hz, 1H), 4.00 (dd, J=2.2, 1.2 Hz, 2H), 5.06 (d, J=1.2 Hz,
1H), 5.09–5.12 (m, 2H), 5.26 (dt, J=1.5, 1.5 Hz, 1H), 5.79–5.88 ppm (m,
1H); 13C NMR (CDCl3): d=16.35, 22.04, 35.80, 38.02, 48.88, 58.21, 74.22,
116.09, 116.40, 137.98, 139.52, 142.53, 147.91, 204.66 ppm; HRMS (FAB):
m/z calcd for C14H20O2 221.1542 [M++H]; found: 221.1547.
General procedure I: preparation of benzene derivatives 3: Catalyst 15
or 16 (7.5 mol%, 0.017 mmol) was added in one portion to a solution of
1,5,7-trien-4-ol 7 (0.232 mmol) in CH2Cl2 (23 mL, 0.01m) under nitrogen.
After stirring for 2 h at room temperature, the reaction mixture was
treated with p-toluenesulfonic acid (0.023 mmol) and stirred for 1 h at
room temperature. The mixture was concentrated under reduced pres-
sure and purified by silica-gel column chromatography or preparative
TLC on silica gel to give benzene 3.
1-(2-Methyl-3-butenoyl)-2-(1-methoxymethylvinyl)-cyclooctene (9k): The
reaction was carried out by following the general procedure H and the
products were purified by silica-gel flash column chromatography
(hexane/EtOAc 20:1) (Mixture of 1,5,7-trien-4-one (9k)/2H-pyran (22k):
4,6-Dimethylindan (3e): The reaction was carried out by following the
general procedure I and the product was purified by silica-gel column
1
chromatography (hexane) (92% NMR yield). H NMR (CDCl3): d=2.05
(quint, J=7.4 Hz, 2H), 2.22 (s, 3H), 2.29 (s, 3H), 2.79 (t, J=7.4 Hz, 2H),
2.88 (t, J=7.7 Hz, 2H), 6.79 (s, 1H), 6.89 ppm (s, 1H); 13C NMR
(CDCl3): d=19.01, 21.10, 24.89, 30.95, 32.96, 122.36, 127.71, 133.44,
135.78, 139.94, 144.01 ppm; HRMS (EI): m/z calcd for C11H14: 146.1096
[M+]; found: 146.1093.
68% yield). The following data are for
a mixture of 9k and 22k
1
(0.74:0.26); H NMR (CDCl3): d=1.12 (d, J=6.8 Hz, 2.22H), 1.19 (d, J=
7.1 Hz, 0.78H), 1.30–1.75 (m, 8.00H), 2.19–2.37 (m, 4.00H), 3.28 (s,
0.78H), 3.39 (s, 2.22H), 3.35 (quint, J=7.0 Hz, 0.26H), 3.65 (quint, J=
7.1 Hz, 0.74H), 4.01 (dd, J=12.7, 0.5 Hz, 0.74H), 4.05 (s, 0.52H), 4.06
(dd, J=12.0, 0.5 Hz, 0.74H), 4.36 (d, J=3.0 Hz, 0.52H), 4.86 (d, J=
1.0 Hz, 0.74H), 5.00 (dt, J=10.2, 1.2 Hz, 0.26H), 5.02–5.09 (m, 0.74H),
5.04 (m, 0.74H), 5.07 (dt, J=17.6, 1.6 Hz, 0.26H), 5.15 (q, J=1.5 Hz,
0.74H), 5.72 (ddd, J=17.9, 10.2, 8.0 Hz, 0.26H), 5.91 ppm (ddd, J=16.7,
8.1, 6.5 Hz, 0.74H); 13C NMR (CDCl3): d=17.06, 17.86, 24.53, 24.63,
25.52, 25.92, 26.09, 26.51, 28.76, 30.34, 31.19, 31.65, 38.11, 50.96, 57.69,
58.77, 67.25, 69.98, 73.97, 113.62, 113.87, 116.09, 116.96, 117.29, 136.44,
138.56, 140.88, 141.44, 143.38, 146.61, 153.78, 211.06 ppm; HRMS (FAB):
m/z calcd for C17H26O2: 262.1933 [M+]; found: 262.1942.
4,5-Dimethylindan (3 f): The reaction was carried out in toluene at 1008C
by following the general procedure I and the product was purified by
silica-gel column chromatography (hexane) (91% NMR yield). 1H NMR
(CDCl3): d=2.05 (quint, J=7.8 Hz, 2H), 2.17 (s, 3H), 2.25 (s, 3H), 2.85
(t, J=7.6 Hz, 2H), 2.91 (t, J=7.6 Hz, 2H), 6.93 (d, J=7.8 Hz, 1H),
6.97 ppm (d, J=7.8 Hz, 1H); 13C NMR (CDCl3): d=15.94, 19.60, 25.11,
31.90, 33.06, 121.33, 127.77, 132.30, 133.90, 141.41, 143.23 ppm; HRMS
(EI): m/z calcd for C11H14: 146.1096 [M+]; found: 146.1091.
5-Methoxycarbonylindan (3g): The reaction was carried out in toluene at
808C by following the general procedure I, and the product was purified
by preparative TLC (hexane/EtOAc 10:1) (82% yield). 1H NMR
(CDCl3): d=2.10 (quint, J=7.6 Hz, 2H), 2.94 (t, J=7.6 Hz, 4H), 3.89 (s,
3H), 7.26 (d, J=8.0 Hz, 1H), 7.82 (dd, J=7.8, 1.5 Hz, 1H), 7.88 ppm (s,
1H); 13C NMR (CDCl3): d=25.34, 32.49, 32.97, 51.89, 124.13, 125.45,
127.84, 128.15, 144.49, 149.92, 167.50 ppm; The 1H and 13C NMR spectra
were consistent with those reported previously.[33]
1-(2-Isopropenyl-4,5-dimethoxyphenyl)-2-methyl-3-buten-1-one (9l): The
reaction was carried out by following general procedure H and the prod-
uct was purified by silica-gel flash column chromatography (hexane/
EtOAc 5:1) (79% yield). 1H NMR (CDCl3): d=1.23 (d, J=7.1 Hz, 3H),
2.13 (d, J=0.7 Hz, 3H), 3.81 (quint, J=6.8 Hz, 1H), 3.89 (s, 3H), 3.92 (s,
3H), 4.84 (s, 1H), 5.02 (d, J=8.6 Hz, 1H), 5.06 (s, 1H), 5.16 (s, 1H), 5.83
(ddd, J=17.8, 10.8, 7.8 Hz, 1H), 6.75 (s, 1H), 6.95 ppm (s, 1H); 13C NMR
(CDCl3): d=17.13, 23.99, 49.65, 55.91, 56.00, 110.58, 111.51, 116.03,
116.71, 131.23, 136.31, 138.22, 144.60, 147.73, 150.44, 206.76 ppm; HRMS
(FAB): m/z calcd for C16H20O3: 260.1412 [M+]; found: 260.1402.
4-Methoxymethyl-6-methylindan (3h): The reaction was carried out in
toluene at 808C by following the general procedure I, and the product
was purified by silica-gel column chromatography (hexane/EtOAc 20:1)
1
(91% NMR ). H NMR (CDCl3): d=2.07 (quint, J=7.6 Hz, 2H), 2.32 (s,
1-(5-Vinyl-4-benzo[1,3]dioxolyl)-3-methoxycarbonyl-3-buten-1-one (9m):
G
3H), 2.85 (t, J=7.3 Hz, 2H), 2.88 (t, J=7.3 Hz, 2H), 3.39 (s, 3H), 4.38 (s,
2H), 6.97 (s, 1H), 6.99 ppm (s, 1H); 13C NMR (CDCl3): d=21.09, 25.11,
30.35, 32.63, 58.10, 72.95, 124.41, 126.33, 133.30, 135.83, 139.59,
144.62 ppm; HRMS (EI): m/z calcd for C12H16O: 176.1201 [M+]; found:
176.1207.
The reaction was carried out by following the general procedure H and
the product was purified by silica-gel flash column chromatography
(hexane/EtOAc 3:1) (79% yield). 1H NMR (CDCl3): d=3.74 (s, 3H),
3.92 (d, J=0.9 Hz, 2H), 5.19 (dd, J=11.1, 1.6 Hz, 1H), 5.51 (dd, J=17.6,
1.2 Hz, 1H), 5.70 (dd, J=2.5, 1.2 Hz, 1H), 6.05 (s, 2H), 6.36 (d, J=
1.2 Hz, 1H), 6.88 (d, J=8.0 Hz, 1H), 6.91 (dd, J=17.6, 11.1 Hz, 1H).
7.07 ppm (d, J=8.3 Hz, 1H); 13C NMR (CDCl3): d=47.23, 52.02, 101.63,
110.84, 114.92, 119.89, 120.65, 128.74, 131.79, 134.26, 134.95, 146.47,
1-Methoxymethyl-3-methyl-9,10-dihydrophenanthrene (3i): The reaction
was carried out in toluene at 808C by following the general procedure I
and the product was purified by preparative TLC (hexane/EtOAc 10:1)
8258
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Chem. Eur. J. 2008, 14, 8246 – 8261

Synthesis of Arenes by Ring-Closing Metathesis
FULL PAPER
(86% yield). 1H NMR (CDCl3): d=2.39 (s, 3H), 2.83 (s, 4H), 3.40 (s,
3H), 4.50 (s, 2H), 7.11 (s, 1H), 7.19–7.24 (m, 2H), 7.27–7.31 (m, 1H),
7.55 (s, 1H), 7.72 ppm (d, J=7.8 Hz, 1H); 13C NMR (CDCl3): d=21.25,
23.85, 28.81, 58.09, 73.08, 123.90, 124.42, 126.80, 127.18, 127.80, 129.17,
133.33, 134.76, 134.85, 135.68, 137.31 ppm; HRMS (FAB): m/z calcd for
C17H18O: 238.1358 [M+]; found: 238.1355.
2-Benzyl-5-methoxymethyl-7-methyl-1,2,3,4-tetrahydroisoquinoline (3q):
The reaction was carried out in toluene at 808C by following the general
procedure I and the product was purified by preparative TLC (hexane/
EtOAc 3:1) (82% yield). 1H NMR (CDCl3): d=2.27 (s, 3H), 2.78 (t, J=
5.8 Hz, 2H), 2.80 (t, J=5.2 Hz, 2H), 3.38 (s, 3H), 3.62 (s, 2H), 3.69 (s,
2H), 4.38 (s, 2H), 6.76 (s, 1H), 6.99 (s, 1H), 7.26–7.35 (m, 3H), 7.39–
7.41 ppm (m, 2H); 13C NMR (CDCl3): d=21.02, 25.46, 50.71, 56.33,
58.33, 62.66, 72.65, 126.98, 127.30, 127.47, 128.42, 129.27, 135.08,
135.76 ppm; HRMS (FAB): m/z calcd for C19H24NO: 282.1858 [M++H];
found: 282.1860.
2-Benzyloxymethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene (3j): The
reaction was carried out in toluene at 808C by following the general pro-
cedure I and the product was purified by preparative TLC (hexane/
EtOAc 10:1) (86% yield). 1H NMR (CDCl3): d=1.60–1.66 (m, 4H),
1.83–1.85 (m, 2H), 2.76–2.80 (m, 4H), 4.49 (s, 2H), 4.55 (s, 2H), 7.07 (s,
2H), 7.10 (s, 1H), 7.23–7.38 ppm (m, 5H); 13C NMR (CDCl3): d=28.24,
28.30, 32.72, 36.38, 36.67, 72.05, 125.45, 127.54, 127.77, 128.34, 128.69,
129.03, 135.65, 138.40, 142.95, 143.52 ppm; HRMS (FAB): m/z calcd for
C19H22O: 266.1671 [M+]; found: 266.1674.
1-Benzyloxymethyl-2,4-dimethylbenzene (3r): The reaction was carried
out by following the general procedure I and the product was purified by
preparative TLC (hexane/EtOAc 11:1) (91% yield). 1H NMR (CDCl3):
d=2.30 (s, 6H), 4.51 (s, 2H), 4.54 (s, 2H), 6.98 (d, J=7.6 Hz, 1H), 6.99
(s, 1H), 7.21 (d, J=6.8 Hz, 1H), 7.24–7.39 ppm (m, 5H); 13C NMR
(CDCl3): d=18.76, 21.04, 70.42, 72.02, 126.30, 127.53, 127.76, 128.33,
128.94, 131.10, 133.05, 136.75, 137.50, 138.41 ppm; HRMS (FAB): m/z
calcd for C16H18OK: 265.0995 [M++K]; found: 265.0999.
1-Methoxymethyl-3-methyl-5,6,7,8,9,10-hexahydrobenzocyclooctene (3k):
The reaction was carried out in toluene at 808C by following the general
procedure I and the product was purified by preparative TLC (hexane/
EtOAc 10:1) (98% yield). 1H NMR (CDCl3): d=1.28–1.41 (m, 4H),
1.63–1.69 (m, 4H), 2.29 (s, 3H), 2.73 (dd, J=6.3, 6.1 Hz, 2H), 2.80 (dd,
J=6.3, 6.4 Hz, 2H), 3.39 (s, 3H), 4.45 (s, 2H), 6.89 (s, 1H), 7.01 ppm (s,
1H); 13C NMR (CDCl3): d=20.89, 25.99, 26.18, 26.33, 30.79, 32.39, 32.86,
58.06, 73.23, 127.96, 129.83, 135.08, 135.10, 136.06, 142.14 ppm; HRMS
(FAB): m/z calcd for C14H19: 187.1487 [M+ÀOMe]; found: 187.1482.
6,7-Dimethoxy-1,3-dimethylnaphthalene (3l): The reaction was carried
out by following the general procedure I and the product was purified by
preparative TLC (hexane/EtOAc 5:1) (92% yield). M.p. 103–1048C;
1H NMR (CDCl3): d=2.43 (s, 3H), 2.61 (s, 3H), 3.99 (s, 3H), 4.01 (s,
3H), 7.05 (s, 1H), 7.06 (s, 1H), 7.16 (s, 1H), 7.35 ppm (s, 1H); 13C NMR
(CDCl3): d=19.44, 21.39, 55.71, 102.86, 106.39, 123.93, 126.10, 127.26,
129.49, 132.45, 133.35, 148.53, 149.11 ppm; HRMS (FAB): m/z calcd for
C14H16O2: 216.1150 [M+]; found: 216.1142.
1-Benzyloxymethyl-3-(3-chloropropyl)-benzene (3 s): The reaction was
carried out in toluene at 808C by following the general procedure I and
the product was purified by preparative TLC (hexane/EtOAc 10:1) (81%
yield). 1H NMR (CDCl3): d=2.09 (quint, J=6.6 Hz, 2H), 2.78 (t, J=
7.6 Hz, 2H), 3.52 (t, J=6.6 Hz, 2H), 4.53 (s, 2H), 4.57 (s, 2H), 7.12 (d,
J=7.6 Hz, 1H), 7.21 (d, J=6.1 Hz, 2H), 7.24–7.39 ppm (m, 6H);
13C NMR (CDCl3): d=32.68, 33.96, 44.22, 72.07, 72.20, 125.61, 127.63,
127.79, 127.84, 127.92, 128.39, 128.53, 138.20, 138.47, 140.85 ppm; HRMS
(FAB): m/z calcd for C17H19ClKO: 313.0762 [M++K]; found: 313.0767.
2,4-Dimethyl-1-(4-methyl-3-pentenyl)-benzene (3t): The reaction was
carried out by following the General procedure I and the product was
1
purified by preparative TLC (hexane/EtOAc 30:1) (75% yield). H NMR
(CDCl3): d=1.59 (s, 3H), 1.70 (s, 3H), 2.22 (q, J=7.6 Hz, 2H), 2.28 (d,
J=2.8 Hz, 6H), 2.57 (t, J=8.6 Hz, 2H), 5.18–5.23 (m, 1H), 6.94 (d, J=
7.7 Hz, 1H), 6.96 (s, 1H), 7.02 ppm (d, J=7.4 Hz, 1H); 13C NMR
(CDCl3): d=17.60, 19.20, 20.89, 25.68, 28.99, 33.05, 124.01, 126.48, 128.70,
130.87, 131.97, 135.19, 135.69, 137.47 ppm; HRMS (FAB): m/z calcd for
C14H19: 187.1487 [M+ÀH]; found: 187.1490.
General procedure J: preparation of phenol derivatives 6: Catalyst 18
(7.5 mol%, 0.019 mmol) was added to a solution of 1,5,7-trien-4-one 9
(0.247 mmol) in CH2Cl2 (25 mL, 0.01m) in one portion under nitrogen
and the solution was stirred for 12 h at 408C. The mixture was concen-
trated under reduced pressure and purified by silica-gel column chroma-
tography or preparative TLC on silica gel to give phenol 6.
Naphtho
N
N
action was carried out in toluene at 1008C by following the general pro-
cedure I and the product was purified by silica-gel column chromatogra-
phy (hexane/EtOAc 4:1) (82% yield). M.p. 103–1058C; 1H NMR
(CDCl3): d=3.96 (s, 3H), 6.20 (s, 2H), 7.24 (d, J=8.9 Hz, 1H), 7.55 (d,
J=8.6 Hz, 1H), 7.81 (ddd, J=9.0, 1.5, 0.9 Hz, 1H), 8.00 (dd, J=1.6 Hz,
1H), 8.56 ppm (s, 1H); 13C NMR (CDCl3): d=52.13, 101.99, 111.14,
119.79, 121.34, 123.84, 125.34, 128.81, 131.82, 141.17, 145.34, 167.14 ppm;
HRMS (FAB): m/z calcd for C13H10O4: 230.0579 [M+]; found: 230.0573.
7-Chloromethylnaphtho
N
N
out in toluene at 808C by following the general procedure I and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 10:1) (88% NMR yield). M.p. 93–958C; 1H NMR (CDCl3): d=
4.72 (s, 2H), 6.17 (s, 2H), 7.20 (d, J=8.5 Hz, 1H), 7.40 (d, J=8.6 Hz,
1H), 7.46 (d, J=8.9 Hz, 1H), 7.77 (s, 1H), 7.81 ppm (d, J=8.6 Hz, 1H);
13C NMR (CDCl3): d=46.85, 101.75, 110.93, 119.31, 120.56, 121.91,
126.62, 128.09, 129.58, 132.75, 141.24, 143.88 ppm; HRMS (FAB): m/z
calcd for C12H9ClO2: 220.0291 [M+]; found: 220.0283.
4-Indanol (6a): The reaction was carried out by following the general
procedure J and the product was purified by preparative TLC (hexane/
EtOAc 5:1) (83% yield). 1H NMR (CDCl3): d=2.11 (quint, J=7.7 Hz,
2H), 2.85 (t, J=7.7 Hz, 2H), 2.93 (t, J=7.7 Hz, 2H), 4.54 (s, 1H), 6.61
(dd, J=8.0, 0.6 Hz, 1H), 6.83 (d, J=7.1 Hz, 1H), 7.05 ppm (t, J=7.7 Hz,
1H); 13C NMR (CDCl3): d=24.99, 28.67, 33.19, 112.51, 116.95, 127.69,
1
129.29, 146.72, 151.87 ppm; The H and 13C NMR spectra were consistent
with those reported previously.[34]
1,2,5,6-Tetramethylanthracene (3o): The reaction was carried out in tolu-
ene at 1008C by following the general procedure I and the product was
purified by preparative TLC (hexane/CH2Cl2 10:1) (78% yield). M.p.
200–2038C; 1H NMR (CDCl3): d=2.52 (s, 6H), 2.71 (s, 6H), 7.26 (d, J=
9.8 Hz, 2H), 7.81 (d, J=8.5 Hz, 2H), 8.49 ppm (s, 2H); 13C NMR
(CDCl3): d=14.67, 20.68, 122.52, 122.59, 126.32, 129.02, 130.08, 130.66,
130.88, 131.61 ppm; HRMS (FAB): m/z calcd for C18H18: 234.1409 [M+];
found: 234.1403.
7-Methyl-4-indanol (6b): The reaction was carried out by following gen-
eral procedure J and the product was purified by preparative TLC
(hexane/EtOAc 5:1) (91% yield). M.p. 86–878C; 1H NMR (CDCl3): d=
2.11 (quint, J=3.9 Hz, 2H), 2.18 (s, 3H), 2.84 (t, J=7.6 Hz, 2H), 2.86 (t,
J=7.6 Hz, 2H), 4.46 (s, 1H), 6.54 (d, J=8.3 Hz, 1H), 6.84 ppm (d, J=
8.0 Hz, 1H); 13C NMR (CDCl3): d=18.41, 24.58, 29.00, 31.94, 112.64,
125.95, 128.24, 128.80, 145.04, 149.90 ppm; HRMS (FAB): m/z calcd for
C10H12O: 148.0888 [M+]; found: 148.0881.
Benzo[b]thiophene-5-carboxylic acid methyl ester (3p): The reaction was
carried out in toluene at 808C by following the general procedure I and
the product was purified by silica-gel column chromatography (hexane/
5-Methyl-4-indanol (6c): The reaction was carried out by following the
general procedure J and the product was purified by preparative TLC
(hexane/EtOAc 5:1) (91% yield). 1H NMR (CDCl3): d=2.11 (quint, J=
7.6 Hz, 2H), 2.23 (s, 3H), 2.82 (t, J=7.6 Hz, 2H), 2.90 (t, J=7.6 Hz, 2H),
4.48 (s, 1H), 6.73 (d, J=7.6 Hz, 1H), 6.92 ppm (d, J=7.6 Hz, 1H);
13C NMR (CDCl3): d=15.30, 25.40, 28.66, 33.00, 116.40, 120.72, 128.81,
1
EtOAc 5:1) (73% yield). H NMR (CDCl3): d=3.96 (s, 3H), 7.42 (d, J=
5.6 Hz, 1H), 7.51 (d, J=5.4 Hz, 1H), 7.92 (d, J=8.5 Hz, 1H), 8.0 (dd, J=
8.5, 1.5 Hz, 1H), 8.54 ppm (d, J=1.0 Hz, 1H); 13C NMR (CDCl3): d=
52.29, 122.47, 124.54, 124.74, 125.66, 126.53, 127.77, 139.43, 144.23,
167.51 ppm; HRMS (FAB): m/z calcd for C10H9O2S: 193.0323 [M++H];
found: 193.0317.
1
129.14, 144.03, 150.12 ppm; The H and 13C NMR spectra were consistent
with those reported previously.[34]
Chem. Eur. J. 2008, 14, 8246 – 8261
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8259

K. Yoshida, T. Imamoto et al.
6-Methyl-4-indanol (6d): The reaction was carried out in toluene at 808C
by following general procedure J and the product was purified by prepa-
rative TLC (hexane/EtOAc 5:1) (86% yield). 1H NMR (CDCl3): d=2.08
(quint, J=4.0 Hz, 2H), 2.27 (s, 3H), 2.79 (t, J=7.4 Hz, 2H), 2.87 (t, J=
7.7 Hz, 2H), 4.60 (s, 1H), 6.44 (s, 1H), 6.66 ppm (s, 1H); 13C NMR
(CDCl3): d=21.15, 25.20, 28.34, 33.11, 113.33, 117.73, 126.17, 137.89,
146.75, 151.62 ppm; HRMS (FAB): m/z calcd for C10H12O: 148.0888 [M+
]; found: 148.0886.
7-Chloromethylnaphtho
ried out in toluene at 808C by following the general procedure J and the
product was purified by silica-gel column chromatography (hexane/
EtOAc 3:1) (80% yield). M.p. 127–1298C; H NMR (CDCl3): d=4.64 (s,
2H), 6.19 (s, 2H), 6.72 (s, 1H), 6.88 (d, J=1.5 Hz, 1H), 7.16 (d, J=
8.6 Hz, 1H), 7.32 (br s, 1H), 7.36 ppm (d, J=8.6 Hz, 1H); 13C NMR
(CDCl3): d=46.76, 102.04, 109.59, 111.32, 111.54, 119.70, 122.39, 131.17,
134.45, 139.33, 143.25, 150.58 ppm; HRMS (FAB): m/z calcd for
C12H9ClO3: 236.0240 [M+]; found: 236.0237.
A
G
1
5,7-Dimethyl-4-indanol (6e): The reaction was carried out by following
general procedure J and the product was purified by preparative TLC
(hexane/EtOAc 5:1) (88% yield). M.p. 117–1188C; 1H NMR (CDCl3):
d=2.12 (quint, J=7.4 Hz, 4H), 2.16 (s, 3H), 2.21 (s, 3H), 2.82 (q, J=
7.7 Hz, 2H), 4.31 (s, 1H), 6.75 ppm (s, 1H); 13C NMR (CDCl3): d=15.28,
18.35, 25.03, 29.06, 31.75, 121.00, 125.47, 128.57, 129.97, 142.39,
148.12 ppm; HRMS (FAB): m/z calcd for C11H14O: 162.1045 [M+];
found: 162.1049.
7-Hydroxy-benzo[b]thiophene-5-carboxylic acid methyl ester (6p): The
reaction was carried out in toluene at 808C by following the general pro-
cedure J and the product was purified by preparative TLC (hexane/
EtOAc 3:1) (70% yield). M.p. 188–1918C; 1H NMR (D6-acetone): d=
3.89 (s, 3H), 7.45 (s, 1H), 7.53 (d, J=5.4 Hz, 1H), 7.75 (d, J=5.4 Hz,
1H), 8.11 (d, J=1.2 Hz, 1H), 9.57 ppm (s, 1H); 13C NMR (D6-acetone):
d=52.27, 108.76, 117.97, 125.84, 129.03, 132.93, 142.46, 152.86,
167.49 ppm; HRMS (FAB): m/z calcd for C10H8O3S: 208.0194 [M+];
found: 208.0191.
6,7-Dimethyl-4-indanol (6 f): The reaction was carried out in toluene at
808C by following general procedure J and the product was purified by
preparative TLC (hexane/EtOAc 5:1) (92% yield). M.p. 106–1078C;
1H NMR (CDCl3): d=2.10 (q, J=7.6 Hz, 2H), 2.10 (s, 3H), 2.21 (s, 3H),
2.84 (q, J=7.3 Hz, 4H), 4.34 (s, 1H), 6.48 ppm (s, 1H); 13C NMR
(CDCl3): d=15.25, 19.55, 24.83, 28.89, 32.33, 114.37, 124.42, 126.14,
135.91, 145.29, 149.29 ppm; HRMS (FAB): m/z calcd for C11H14O:
162.1045 [M+]; found: 162.1041.
Acknowledgement
We appreciate the financial support from the Sumitomo Foundation and
the Mitsubishi Chemical Corporation Fund, and a Grant-in-Aid for Sci-
entific Research from the Ministry of Education, Culture, Sports, Science
and Technology, Japan.
6-Methoxycarbonyl-4-indanol (6g): The reaction was carried out in tolu-
ene at 808C by following general procedure J and the product was puri-
fied by preparative TLC (hexane/EtOAc 3:1) (95% yield). M.p. 153–
1558C; 1H NMR (CDCl3): d=2.13 (quint, J=7.4 Hz, 2H), 2.90 (t, J=
7.4 Hz, 2H), 2.94 (t, J=7.7 Hz, 2H), 3.90 (s, 3H), 5.84 (s, 1H), 7.42 (s,
1H), 7.49 ppm (s, 1H); 13C NMR (CDCl3): d=25.02, 29.11, 32.96, 52.14,
114.19, 118.07, 129.61, 135.60, 146.93, 151.99, 167.72 ppm; HRMS (FAB):
m/z calcd for C11H13O3: 193.0856 [M++H]; found: 193.0856.
[1] For a comprehensive review, see: Modern Arene Chemistry, (Ed.: D.
Astruc), Wiley-VCH, Weinheim, 2002.
[2] For example, see: a) R. L. Danheiser, S. K. Gee, J. Org. Chem. 1984,
49, 1672–1674; b) P. Turnbull, H. W. Moore, J. Org. Chem. 1995, 60,
644–649; c) T. Takahashi, Z. Xi, A. Yamazaki, Y. Liu, K. Nakajima,
M. Kotora, J. Am. Chem. Soc. 1998, 120, 1672–1680; d) K. H. Dçtz,
P. Tomuschat, Chem. Soc. Rev. 1999, 28, 187–198; e) A. R. Katritz-
ky, J. Li, L. Xie, Tetrahedron 1999, 55, 8263–8293; f) S. Saito, Y. Ya-
mamoto, Chem. Rev. 2000, 100, 2901–2915; g) D. Suzuki, H. Urabe,
F. Sato, J. Am. Chem. Soc. 2001, 123, 7925–7926; h) C. B. de Koning,
A. L. Rousseau, W. A. L. van Otterlo, Tetrahedron 2003, 59, 7–36;
i) Y. Yamamoto, T. Arakawa, R. Ogawa, K. Itoh, J. Am. Chem. Soc.
2003, 125, 12143–12160; j) T. Shibata, T. Fujimoto, K. Yokota, K.
Takagi, J. Am. Chem. Soc. 2004, 126, 8382–8383; k) X. Bi, D. Dong,
Q. Liu, W. Pan, L. Zhao, B. Li, J. Am. Chem. Soc. 2005, 127, 4578–
4579; l) N. Asao, Synlett 2006, 1645–1656; m) K. Tanaka, T. Osaka,
K. Noguchi, M. Hirano, Org. Lett. 2007, 9, 1307–1310; n) S. Serra,
C. Fuganti, E. Brenna, Chem. Eur. J. 2007, 13, 6782–6791; o) M.
Gayral, J. M. Brown, Synlett 2007, 2823–2826.
7-Methoxymethyl-5-methyl-4-indanol (6h): The reaction was carried out
in toluene at 808C by following the general procedure J and the product
was purified by preparative TLC (hexane/EtOAc 5:1) (85% yield).
1H NMR (CDCl3): d=2.12 (quint, J=7.3 Hz, 2H), 2.22 (s, 3H), 2.82 (t,
J=7.3 Hz, 2H), 2.91 (t, J=7.4 Hz, 2H), 3.35 (s, 3H), 4.34 (s, 2H), 4.62
(br s, 1H), 6.92 ppm (s, 1H); 13C NMR (CDCl3): d=15.24, 25.08, 28.76,
31.12, 57.79, 72.76, 121.09, 125.34, 129.13, 129.70, 142.85, 149.921 ppm;
HRMS (FAB): m/z calcd for C12H16O2: 192.1150 [M+]; found: 192.1157.
4-Methoxymethyl-2-methyl-5,6,7,8,9,10-hexahydro-1-benzocyclooctenol
(6k): The reaction was carried out in toluene at 808C by following the
general procedure J, and the product was purified by preparative TLC
(hexane/EtOAc 5:1) (98% yield). M.p. 82–838C; 1H NMR (CDCl3): d=
1.31–1.39 (m, 4H), 1.62–1.68 (m, 4H), 2.19 (s, 3H), 2.77–2.81 (m, 4H),
3.33 (s, 3H), 4.33 (s, 2H), 4.59 (s, 1H), 6.88 ppm (s, 1H); 13C NMR
(CDCl3): d=15.74, 24.46, 26.30, 26.42, 27.24, 29.45, 31.15, 57.72, 73.32,
119.83, 126.99, 130.03, 139.33, 151.14 ppm; HRMS (FAB): m/z calcd for
C15H22O2: 234.1620 [M+]; found: 234.1621.
[3] For a review, see: T. J. Donohoe, A. J. Orr, M. Bingham, Angew.
Chem. 2006, 118, 2730–2736; Angew. Chem. Int. Ed. 2006, 45, 2664–
2670.
6,7-Dimethoxy-2,4-dimethyl-1-naphthalenol (6l): The reaction was car-
ried out by following general procedure J and the product was purified
by silica-gel column chromatography (hexane/EtOAc 3:1) (84% yield).
[4] For reports on the direct synthesis of carbocyclic aromatic com-
pounds by using RCM, see: a) A. Iuliano, P. Piccioli, D. Fabbri, Org.
Lett. 2004, 6, 3711–3714; b) E. R. Walker, S. Y. Leung, A. G. M.
Barrett, Tetrahedron Lett. 2005, 46, 6537–6540; c) M. C. Bonifacio,
C. R. Robertson, J.-Y. Jung, B. T. King, J. Org. Chem. 2005, 70,
8522–8526; d) S. C. Pelly, C. J. Parkinson, W. A. L. Van Otterlo,
C. B. De Koning, J. Org. Chem. 2005, 70, 10474–10481; e) S. K. Col-
lins, A. Grandbois, M. P. Vachon, J. Cꢁtꢂ, Angew. Chem. 2006, 118,
2989–2992; Angew. Chem. Int. Ed. 2006, 45, 2923–2926; For reports
of the RCM/elimination protocol, see: f) P. Evans, R. Grigg, M. I.
Ramzan, V. Sridharan, M. York, Tetrahedron Lett. 1999, 40, 3021–
3024; g) K. S. Huang, E. C. Wang, Tetrahedron Lett. 2001, 42, 6155–
6157; h) Y. Chen, H. V. R. Dias, C. J. Lovely, Tetrahedron Lett. 2003,
44, 1379–1382; i) P.-Y. Chen, H.-M. Chen, L.-Y. Chen, J.-Y. Tzeng,
J.-C. Tsai, P.-C. Chi, S.-R. Li, E.-C. Wang, Tetrahedron 2007, 63,
2824–2828; For reports of RCM/oxidation protocols, see: j) S.
Kotha, K. Mandal, Tetrahedron Lett. 2004, 45, 2585–2588; k) S. Ma,
F. Yu, J. Zhao, Synlett 2007, 583–586; l) S. Kotha, V. R. Shah, K.
1
M.p. 129–1318C; H NMR (CDCl3): d=2.35 (s, 3H), 2.53 (s, 3H), 4.02 (s,
3H), 4.03 (s, 3H), 4.83 (br s, 1H), 6.95 (s, 1H), 7.12 (s, 1H), 7.44 ppm (s,
1H); 13C NMR (CDCl3): d=15.43, 18.88, 55.70, 55.80, 100.88, 103.13,
114.23, 119.81, 124.63, 127.80, 146.23, 148.68, 148.81 ppm; HRMS (FAB):
m/z calcd for C14H16O3: 232.1099 [M+]; found: 232.1092.
9-Hydroxynaphthol
N
N
(6m): the reaction was carried out in toluene at 808C by following gener-
al procedure J and the product was purified by silica-gel column chroma-
tography (hexane/EtOAc 4:1 to 2:1) (81% yield). M.p. 199–2018C;
1H NMR (CDCl3): d=3.94 (s, 3H), 6.23 (s, 2H), 6.69 (s, 1H), 7.22 (d, J=
8.6 Hz, 1H), 7.41 (d, J=1.2 Hz, 1H), 7.53 (d, J=8.6 Hz, 1H), 8.12 ppm
(d, J=1.2 Hz, 1H); 13C NMR (D6-DMSO (DMSO=dimethyl sulfoxide)):
d=52.00, 101.45, 106.30, 111.46, 114.27, 122.12, 123.59, 125.28, 130.52,
140.77, 145.23, 151.85, 166.32 ppm; HRMS (FAB): m/z calcd for
C13H10O5: 246.0528 [M+]; found: 246.0531.
8260
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Chem. Eur. J. 2008, 14, 8246 – 8261

Synthesis of Arenes by Ring-Closing Metathesis
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Received: March 15, 2008
Published online: July 28, 2008
Chem. Eur. J. 2008, 14, 8246 – 8261
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
8261