Alkenylation of 1- and 2-naphthols by using magnesium alkylidene carbenoids as electrophilic alkenylating agents

Article abstract of DOI:10.1055/s-0032-1318132

1- and 2-Naphthols were successfully alkenylated in a regioselective manner by treating the corresponding lithium 1- and 2-naphtholates with magnesium alkylidene carbenoids. The magnesium alkylidene carbenoids were generated in situ by a sulfoxide-magnesium exchange reaction of 1-chlorovinyl 4-tolyl sulfoxides with isopropylmagnesium chloride. The reaction of magnesium alkylidene carbenoids with lithium 2-naphtholates took place at the 1-position of the naphthyl ring to give 1-(alk-1-enyl)-2-naphthols in respectable yields. The alkenylation of 1-naphthols proceeded at the 2-position of the naphthol ring to give 2-(alk-1-enyl)-1-naphthols in yields of 56-67%. In contrast to the reaction of lithium naphtholates with magnesium alkylidene carbenoids, the reaction of lithium phenolates gave low yields of the corresponding alk-1-enyl aryl ethers. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0032-1318132

PAPER
▌659
paper
Alkenylation of 1- and 2-Naphthols by Using Magnesium Alkylidene Carbeno-
ids as Electrophilic Alkenylating Agents
Alkenylation of Naphthols by Magnesium Alkylidene Carbenoids
Tsutomu Kimura,a Masaya Watanabe,b Gaku Kashiwamura,b Jo Sakurada,b Tsuyoshi Satoh*a,b
a
Department of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826,
Japan
b
Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo
162-0826, Japan
Fax +81(3)52614631; E-mail: tsatoh@rs.kagu.tus.ac.jp
Received: 04.12.2012; Accepted after revision: 07.01.2013
sium alkylidene carbenoids as reactive intermediates
Abstract: 1- and 2-Naphthols were successfully alkenylated in a re-
(Scheme 1).6 These magnesium alkylidene carbenoids,
gioselective manner by treating the corresponding lithium 1- and 2-
generated in situ, function as electrophilic alkenylating
agents for various nucleophiles, including Grignard re-
naphtholates with magnesium alkylidene carbenoids. The magne-
sium alkylidene carbenoids were generated in situ by a sulfoxide–
magnesium exchange reaction of 1-chlorovinyl 4-tolyl sulfoxides agents, aryllithiums, lithium acetylides, lithium amides,
lithium thiolates, or lithium enolates,7 although the nu-
cleophilic substitution reaction does not generally occur at
with isopropylmagnesium chloride. The reaction of magnesium al-
kylidene carbenoids with lithium 2-naphtholates took place at the 1-
position of the naphthyl ring to give 1-(alk-1-enyl)-2-naphthols in
the vinylic carbon atom of the haloalkene. Meanwhile,
respectable yields. The alkenylation of 1-naphthols proceeded at the
2-position of the naphthol ring to give 2-(alk-1-enyl)-1-naphthols in
phenolic compounds are known to act as carbon nucleo-
philes toward dichlorocarbene in the Reimer–Tiemann re-
action.8 In addition, we recently found that the reaction of
lithium phenolates or naphtholates with cyclopropyl- or
cyclobutylmagnesium carbenoids gives spirocyclic die-
nones through a Buchner ring expansion.9 If phenolic
compounds could be alkenylated by magnesium alkyli-
dene carbenoids, then a variety of ortho-alkenylphenolic
compounds might be directly obtained. Here, we report
the synthesis of alkenylated 1- and 2-naphthols through
the substitution reaction of lithium 1- and 2-naphtholates
with magnesium alkylidene carbenoids. The reaction of
lithium phenolates with magnesium alkylidene carben-
oids is also reported.
yields of 56–67%. In contrast to the reaction of lithium naphtholates
with magnesium alkylidene carbenoids, the reaction of lithium phe-
nolates gave low yields of the corresponding alk-1-enyl aryl ethers.
Key words: alkenation, phenols, carbenoids, sulfoxides, alkenes,
arenes, organometallic reagents
ortho-Alkenylphenolic compounds, such as 2-(alk-1-
enyl)-1-naphthols and 1-(alk-1-enyl)-2-naphthols, are im-
portant synthetic intermediates, especially as precursors
of derivatives of benzofurans or naphthofurans.1 The clas-
sical route for the synthesis of such compounds involves
allylation of the hydroxy group in a phenolic compound,
Claisen rearrangement of the resultant allyl aryl ether, and
subsequent transition metal-catalyzed isomerization of
the allylarene.2 The Heck reaction has become the most
R2
R2
R3MgCl
Nu–
Cl
Ar
Cl
R1
R1
popular method for the construction of styrene units.1c,3
A
S
MgCl
regioselective ortho-monohalogenation of electron-rich
phenolic compounds is required for the synthesis of ortho-
alkenylphenolic compounds by means of the Heck reac-
tion.4 Direct alkenylation with alkynes is a simple and
straightforward method for the introduction of alkenyl
groups into phenolic compounds.5 However, because the
reaction has to be carried out in the presence of a Lewis
acid under harsh reaction conditions, its synthetic scope is
limited. Accordingly, the development of an alternative
route for the preparation of ortho-alkenylphenolic com-
pounds is required.
O
1
R2
R2
H3O+
H
MgCl
R1
R1
Nu
Nu
Scheme 1 Reaction of magnesium alkylidene carbenoids with nu-
cleophiles
We examined the alkenylation of 2-naphthol (2a) by using
the spirocyclic 1-chlorovinyl 4-tolyl sulfoxide 1a as the
source of the corresponding magnesium alkylidene car-
benoid (Scheme 2). A solution of isopropylmagnesium
chloride in tetrahydrofuran was added to a mixture of lith-
ium 2-naphtholate (1.5 equiv) [prepared from 2-naphthol
(2a) and butyllithium] and sulfoxide 1a in tetrahydrofuran
at –78 °C, and the reaction mixture was allowed to warm
Previously, we found that treatment of 1-chlorovinyl 4-
tolyl sulfoxides 1 with Grignard reagents provides magne-
SYNTHESIS 2013, 45, 0659–0667
Advanced online publication: 24.01.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0032-1318132; Art ID: SS-2012-F0936-OP
© Georg Thieme Verlag Stuttgart · New York

660
T. Kimura et al.
PAPER
O
O
Cl
O
S
O
O
O
O
Tol
1a
i-PrMgCl
O
O
+
+
+
Cl
HO
THF
–78 °C to –10 °C
•
HO
2
H
/BuLi
3a 7% yield
4 22% yield
5 36% yield
2a
Scheme 2 Alkenylation of 2-naphthol (2a) with a magnesium alkylidene carbenoid generated from sulfoxide 1a
to –10 °C. Acidic workup of the reaction mixture gave the I by water, and the latter appeared to originate from the di-
alkenylated 2-naphthol 3a in 7% yield, together with the merization of magnesium alkylidene carbenoid I as a re-
chloroalkene 4 (22%) and cumulene 5 (36%).
sult of the low nucleophilicity of lithium 2-naphtholate.
To eliminate trace amounts of the proton source from the
reaction medium, we added tert-butylmagnesium chlo-
ride, which is not reactive toward sulfoxide 1a, to the re-
action mixture before conducting the sulfoxide–
magnesium exchange reaction. We also reduced the con-
centration of the magnesium alkylidene carbenoid I from
0.5 mol/L to 0.1 mol/L in an attempt to limit the self-cou-
pling reaction of magnesium alkylidene carbenoid I. Fur-
thermore, we used five equivalents of lithium 2-
naphtholate to compensate for its low nucleophilicity. As
a result, we obtained the desired 1-(alk-1-enyl)-2-naph-
thol 3a in 66% yield, and we reduced the yields of byprod-
ucts 4 and 5 to 6% and 7%, respectively (Table 1, entry 1).
1
A comparison of the H NMR spectrum of 2-naphthol
(2a) with that of the product 3a showed that the signal for
the aromatic proton at the 1-position (δ = 7.13 ppm) dis-
appeared and a signal at δ = 6.30 ppm, corresponding to
an alkenyl proton, appeared, demonstrating that the alke-
nyl group had been introduced at the 1-position of the
naphthol ring. The presence of a phenolic hydroxy group
in product 3a was confirmed by a H–D exchange experi-
ment with methanol-d4 and by the iron(III) chloride test.
The alkenylation of 2-naphthol might occur by the follow-
ing mechanism (Scheme 3). Initially, the magnesium al-
kylidene carbenoid I is generated from sulfoxide 1a and
isopropylmagnesium chloride by a sulfoxide–magnesium
exchange reaction.6 Subsequent nucleophilic substitution
of lithium 2-naphtholate by the magnesium alkylidene
carbenoid I takes place predominantly at the 1-position of
the naphthol ring to give cyclohexadienone II.9b,10 The
nonaromatic intermediate II tautomerizes to the more-sta-
ble aromatic 2-naphtholate III. Finally, protonation of 2-
naphtholate III leads to the formation of the 1-(alk-1-
enyl)-2-naphthol 3a.
We then examined the alkenylation of the substituted 2-
naphthols 2b and 2c and the related compounds 2d and 2e
with the magnesium alkylidene carbenoid generated from
sulfoxide 1a under the optimized reaction conditions de-
scribed above (Table 1, entries 2–5). Alkenylation of 7-
methoxy-2-naphthols (2b) with the magnesium alkyli-
dene carbenoid gave the corresponding 1-(alk-1-enyl)-2-
naphthol 3b in 78% yield (entry 2). 6-Bromo-2-naphthol
(2c) similarly gave the 1-(alk-1-enyl)-2-naphthol 3c in
62% yield (entry 3). 2-Methoxynaphthalene (2d) did not
react with the magnesium alkylidene carbenoid (entry 4),
indicating that a phenolic hydroxy group is essential for
the alkenylation reaction to occur. The lithium thiolate
prepared from naphthalene-2-thiol (2e) exhibited a differ-
ent reactivity toward the magnesium alkylidene carbenoid
(entry 5). In this reaction, the sulfur atom was alkenylated
to give alk-1-enyl aryl sulfide 3e′ (Figure 1) in 87% yield,
and 1-(alk-1-enyl)naphthalene-2-thiol 3e was not formed.
The trend for the reactivity observed for the reaction of
lithium naphthalene-2-thiolate is analogous to that ob-
served for the reaction of lithium benzenethiolates.7e
Li+ –
O
sulfoxide–magnesium
exchange reaction
i-PrMgCl
R
Cl
R
1a
MgCl
I
R
R
MgCl
H
R
O
R
proton
transfer
H
H3O+
ClMgO
3a
II
III
Scheme 3 A plausible mechanism for the alkenylation of 2-naphthol
with magnesium alkylidene carbenoid I
To explore the scope of the alkenylation reaction further,
we examined a range of magnesium alkylidene carben-
oids as alkenylating agents for lithium 2-naphtholate (Ta-
ble 2). The reaction of lithium 2-naphtholate with
magnesium alkylidene carbenoids generated from sulfox-
ides 1b–e containing rings of various sizes gave moderate
yields of the corresponding 1-(alk-1-enyl)-2-naphthols
3f–i (Table 2, entries 1–4). The acyclic 2,2-dialkyl-substi-
We then examined various reaction conditions in an at-
tempt to improve the efficiency of the alkenylation reac-
tion. Chloroalkene 4 and cumulene 5 were the major
byproducts in this reaction.7a The former seemed to arise
from the protonation of magnesium alkylidene carbenoid
Synthesis 2013, 45, 659–667
© Georg Thieme Verlag Stuttgart · New York

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Alkenylation of Naphthols by Magnesium Alkylidene Carbenoids
661
Table 1 Alkenylation of 2-Naphthols and Related Compounds 2a–e
with the Magnesium Alkylidene Carbenoid Generated from Sulfox-
ide 1a
Table 2 Alkenylation of 2-Naphthol (2a) with Magnesium Alkyli-
dene Carbenoids Generated from Sulfoxides 1b–i
R
O
Cl
R
R
O
Cl
O
S
O
Tol
R
1
+
i-PrMgCl
HO
S
O
O
Tol
THF
–78 to –10 °C
HO
1a
i-PrMgCl
/BuLi
+
R1E
R2
R3
3
THF
–78 to –10 °C
R1E
R2
/BuLi
R3
2a
3
Entry
1
Reactant CR2
Product
Yield (%)
38
2
Entry Reactant ER1
R2
R3
3
Yield (%)
1b
3f
1
2
3
4
5
2a
2b
2c
2d
2e
OH
OH
OH
OMe
SH
H
H
H
Br
H
H
3a
3b
3c
3d
3e
66
78
62
0a
OMe
H
2
3
1c
3g
3h
50
51
H
1d
H
0b
a Chloroalkene 4 and cumulene 5 were obtained in 26% and 40%
yields, respectively.
b Sulfide 3e′ (Figure 1) was obtained in an 87% yield.
4
1e
3i
48
O
O
H
5
1f
CMe2
CEt2
3j
61
44
53
0
6
1g
1h
1i
3k
3l
S
7
C[(CH2)2Ph]2
CPh2
3e'
8a
3m
Figure 1 Sulfide byproduct from an alkenylation of naphthalene-2-
thiol (2e) (Table 1, entry 5)
a 2-Chloro-1,1-diphenylethene and diphenylacetylene were obtained
in 22% and 77% yields, respectively.
tuted sulfoxides 1f–h could also be used in the alkenyl-
ation reaction and gave the desired products 3j–l in 44–
53% yield (entries 5–7, respectively), whereas alkenyl-
ation using sulfoxide 1i, which contains two phenyl
groups in the β-position, failed due to the ease with which
diphenylacetylene is formed through the Fritsch–Butten-
berg–Wiechell rearrangement of the resultant magnesium
alkylidene carbenoid (entry 8).
of 89:11. These geometrical outcomes suggest that the re-
action might proceed by an SN2-type mechanism at the
carbenoid carbon atom.7f,10 The geometry-selective syn-
thesis of 1-(alk-1-enyl)-2-naphthols is difficult to achieve
at this stage because the magnesium alkylidene carben-
oids gradually isomerize.7a For instance, when the reac-
tions shown in entries 1 and 2 were conducted without
lithium 2-naphtholate, the chloroalkene was obtained as a
mixture of the (E)- and (Z)-isomers with E/Z ratios of
72:28 and 59:41, respectively.
In an attempt to synthesize (E)- and (Z)-1-(alk-1-enyl)-2-
naphthols selectively, we examined the reaction of 2-
naphthol (2a) with the two geometrical isomers of each of
the 1-chlorovinyl 4-tolyl sulfoxides 1j–l bearing two dif-
ferent substituents in the β-position (Table 3).7f In all cas-
es, the reaction proceeded with partial geometric
isomerization to give the 1-(alk-1-enyl)-2-naphthols 3n–p
as mixtures of (E)- and (Z)-isomers (entries 1–6). In the
case of the reaction with the sulfoxide (E)-1l, the (Z)-1-
(alk-1-enyl)-2-naphthol (Z)-3p was obtained as the major
isomer with an E/Z ratio of 14:86 (entry 5). Similarly, the
reaction with the other isomer, (Z)-1l, preferentially gave
the (E)-1-(alk-1-enyl)-2-naphthol (E)-3p with an E/Z ratio
We also examined the alkenylation of 1-naphthols 6 (Ta-
ble 4). 1-Naphthol (6a) underwent alkenylation with the
magnesium alkylidene carbenoid generated from sulfox-
ide 1a to give a 67% yield of the 2-(alk-1-enyl)-1-naph-
thol 7a (entry 1). The presence of an electron-donating or
electron-withdrawing group at the 4-position had hardly
any effect on the efficiency of the reaction (entries 2 and
3). The alkenylation of phenanthren-1-ol (6d) took place
at the 2-position to provide the 2-(alk-1-enyl)phenan-
thren-1-ol 7d in 56% yield (entry 4).
© Georg Thieme Verlag Stuttgart · New York
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662
T. Kimura et al.
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Table 3 Alkenylation of 2-Naphthol (2a) with Magnesium Alkylidene Carbenoids Generated from (E)- and (Z)-1-Chlorovinyl 4-Tolyl Sulf-
oxides (E)- and (Z)-1j–l
R2
R2
O
R1
HO
i-PrMgCl
Cl
HO
R1
+
/BuLi
THF
–78 to –10 °C
S
Tol
2a
3
1
Entry
1
Reactant
R1
R2
Product
Yield (%)
E/Z ratio
(E)-1j
3n
3n
72
67
31:69
2
(Z)-1j
68:32
3
4
5
6
(E)-1k
(Z)-1k
(E)-1l
(Z)-1l
CH=CH2
Me
Me
3o
3o
3p
3p
48
45
43
63
40:60
71:29
14:86
89:11
CH=CH2
Me
(CH2)4Me
Me
(CH2)4Me
of the phenol also proceeded at the oxygen atom to give
low yields of the corresponding ethers 10b–d (entries 2–
4). Although the factor primarily responsible for the dif-
ference in the reactivity of lithium phenolates and lithium
naphtholates toward magnesium alkylidene carbenoids
remains to be clarified,11 it is noteworthy that a new bond
between a vinylic carbon and an oxygen atom was formed
directly. However, a significant amount of cumulene 5
was also produced, and this reaction does not, at this
stage, appear to have much promise for the synthesis of
vinyl ethers.
Table 4 Alkenylation of 1-Naphthols 6 with the Magnesium Alkyl-
idene Carbenoid Generated from Sulfoxide 1a
Cl
Tol
S
O
O
OH
R1
O
1a
+
i-PrMgCl
O
THF
–78 to –10 °C
R3
OH
O
R2
7
/BuLi
R3
In summary, we have succeeded in directly alkenylating
1- and 2-naphthols by using magnesium alkylidene car-
benoids as alkenylating agents. The present method al-
lowed us to introduce a variety of alkenyl groups onto the
naphthol ring in a regiospecific manner. Studies on further
applications of the direct alkenylation of nucleophiles
with magnesium alkylidene carbenoids are currently on-
going and will be reported in due course.
R1
R2
6
Entry
6
R1
R2
R3
7
Yield (%)
1
2
3
6a
6b
6c
H
H
H
H
H
H
H
7a
7b
7c
67
62
63
OMe
Cl
OH
Melting points were measured on a Yanaco MP-S3 apparatus and
are uncorrected. NMR spectra were recorded in CDCl3 soln by us-
ing JEOL JNM-LA 300, JEOL JNM-LA 500, and Bruker AV 600
spectrometers. The geometries of (E)-3p and (Z)-3p were assigned
on the basis of their NOESY spectra. Mass spectra were obtained at
70 eV by direct insertion with a HITACHI M-80B mass spectrom-
eter. IR spectra were recorded on a PerkinElmer Spectrum One
FTIR instrument. Silica gel 60 N (Kanto Chemical) containing
0.5% fluorescence reagent 254 and a quartz column were used for
column chromatography, and the products that absorbed UV light
were detected by UV irradiation. The geometric isomers (E)-3p and
(Z)-3p were separated by means of recycling gel-permeation chro-
matography using an LC-9201 system (Japan Analytical Industry
4
6d
7d
56
Finally, we subjected phenols 8 to the alkenylation reac-
tion (Table 5). In contrast to the reaction with 1- and 2-
naphthols, the reaction with phenol (8a) gave the alk-1-
enyl phenyl ether 10a and not the corresponding ortho-
(alk-1-enyl)phenol 9a (entry 1). Analysis of the product
10a by using the iron(III) chloride test showed the ab- Co., Ltd.). Anhyd THF was purchased from Kanto Chemical Co.,
Inc. and used as supplied. All reactions involving air- or water-sen-
sitive compounds were routinely conducted under a positive pres-
sence of a phenolic hydroxy group. The reaction of phe-
nols 8b–d bearing various substituents on the 4-position
Synthesis 2013, 45, 659–667
© Georg Thieme Verlag Stuttgart · New York

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Alkenylation of Naphthols by Magnesium Alkylidene Carbenoids
663
Table 5 Reaction of Phenols 8 with the Magnesium Alkylidene Carbenoid Generated from Sulfoxide 1a
R
OH
OH
R
Cl
Tol
i-PrMgCl
O
S
+
+
+
5
/BuLi
O
O
O
THF
–78 to –10 °C
O
O
O
O
R
8
1a
9
10
Entry
Reactant
R
Phenol Product Yield (%)
Ether Product
Yield (%) of 10
Yield (%) of 5
1
2
3
4
8a
8b
8c
8d
H
9a
9b
9c
9d
0
0
0
0
10a
10b
10c
10d
20
25
27
25
22
19
16
20
OMe
F
Ph
sure of argon in glassware that had been flame-dried. Sulfoxides 1
were prepared according to the procedure described in the litera-
ture.12 Sulfoxides 17a,f,12,13 and 1-(alk-1-enyl)-2-naphthols 3g14a and
3j14b are known compounds.
IR (neat): 3385 (OH), 2951, 2887, 1623, 1513, 1267, 1222, 1139,
1121, 1085, 1032, 909, 831, 756 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.59–1.68 (m, 2 H), 1.90 (t,
J = 6.5 Hz, 2 H), 2.18 (t, J = 6.5 Hz, 2 H), 2.62–2.70 (m, 2 H), 3.88
(s, 3 H), 3.95–4.02 (m, 4 H), 5.39 (s, 1 H), 6.24 (s, 1 H), 6.96–7.08
(m, 3 H), 7.60–7.70 (m, 2 H).
13C NMR (126 MHz, CDCl3): δ = 26.8, 33.3, 35.2, 36.5, 55.2, 64.4
(2 × C), 103.2, 108.4, 114.4, 115.0, 115.1, 115.2, 124.1, 128.6,
129.8, 134.4, 147.8, 150.8, 158.2.
MS (EI): m/z (%) = 326 (100) [M+], 281 (14), 264 (15), 225 (14),
211 (23), 187 (71), 153 (24), 140 (41), 96 (20).
HRMS (EI): m/z [M+] calcd for C20H22O4: 326.1518; found:
326.1517.
1-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-2-naphthol (3a);
Typical Procedure
A 1.65 M soln of BuLi in hexane (0.606 mL, 1.00 mmol) was added
dropwise to a soln of 2-naphthol (2a; 144 mg, 1.00 mmol) in THF
(1.0 mL) at –78 °C, and the mixture was stirred at –78 °C for 10
min. A soln of sulfoxide 1a (65.4 mg, 0.200 mmol) in THF (1.0 mL)
and a 1.03 M soln of t-BuMgCl in THF (0.194 mL, 0.200 mmol)
were then added to the soln at –78 °C. A 2.0 M soln of i-PrMgCl in
THF (0.280 mL, 0.56 mmol) was then added dropwise at –78 °C.
The mixture was allowed to warm to –10 °C over 1 h then the reac-
tion was quenched with sat. aq NH4Cl (1.5 mL) and the mixture was
extracted with CHCl3 (3 × 7 mL). The organic layers were com-
bined, dried (MgSO4), and concentrated under reduced pressure.
The residue was purified by column chromatography (silica gel,
hexane–EtOAc) to give 3a as a yellow oil [yield: 39.1 mg (0.132
mmol, 66%); Rf = 0.12 (hexane–EtOAc, 5:1)], together with 4 as a
colorless oil [yield: 2.2 mg (0.012 mmol, 6%); Rf = 0.39 (hexane–
EtOAc, 5:1)], and 5 as a colorless solid [yield: 2.0 mg (0.0066
mmol, 7%); Rf = 0.21 (hexane–EtOAc, 5:1)].
1-(1,4-Dioxaspiro[4.5]decan-8-ylidenemethyl)-6-bromonaph-
thalen-2-ol (3c)
Yield: 46.4 mg (62%); yellow oil.
IR (neat): 3334 (OH), 2951, 2885, 1614, 1589, 1498, 1268, 1204,
1140, 1121, 1090, 1074, 1033, 909, 886, 823, 757, 734 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.62 (t, J = 6.5 Hz, 2 H), 1.90 (t,
J = 6.5 Hz, 2 H), 2.14 (t, J = 6.5 Hz, 2 H), 2.61–2.69 (m, 2 H), 3.95–
4.02 (m, 4 H), 5.43 (s, 1 H), 6.25 (s, 1 H), 7.20 (d, J = 8.9 Hz, 1 H),
7.48 (dd, J = 2.0, 8.9 Hz, 1 H), 7.56–7.64 (m, 2 H), 7.92 (d, J = 2.0
Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 26.8, 33.3, 35.0, 36.3, 64.4
(2 × C), 108.3, 114.2, 116.2, 117.0, 118.1, 125.9, 127.9, 129.5,
129.9, 130.1, 131.6, 148.4, 150.5.
MS (EI): m/z (%) = 374 (100) [M+], 236 (22), 165 (19), 153 (22),
140 (62), 121 (19), 96 (30).
HRMS (EI): m/z [M+] calcd for C19H19BrO3: 374.0518; found:
3a
IR (neat): 3411 (OH), 2951, 2885, 1620, 1595, 1269, 1203, 1140,
1121, 1087, 1033, 908, 817, 750 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.62 (t, J = 6.5 Hz, 2 H), 1.91 (t,
J = 6.5 Hz, 2 H), 2.12–2.22 (m, 2 H), 2.66 (dt, J = 1.1, 6.5 Hz, 2 H),
3.95–4.01 (m, 4 H), 5.42 (s, 1 H), 6.30 (s, 1 H), 7.19 (d, J = 8.8 Hz,
1 H), 7.33 (ddd, J = 1.3, 6.9, 8.2 Hz, 1 H), 7.43 (ddd, J = 1.3, 6.9,
8.2 Hz, 1 H), 7.67–7.82 (m, 3 H).
H/D exchange experiment: a soln of 3a (10 mg, 0.034 mmol) in
CD3OD (2 mL) was stirred at r.t. for 24 h. The intensity of the signal
at 5.42 ppm decreased to 54%.
13C NMR (126 MHz, CDCl3): δ = 26.8, 33.3, 35.1, 36.3, 64.4
(2 × C), 108.4, 114.9, 115.9, 117.0, 123.2, 124.1, 126.3, 128.2,
128.7, 128.9, 133.1, 147.7, 150.2.
MS (EI): m/z (%) = 296 (100) [M+], 234 (18), 195 (17), 181 (38),
165 (20), 158 (38), 153 (22), 140 (39), 96 (22).
HRMS (EI): m/z [M+] calcd for C19H20O3: 296.1412; found:
296.1412.
374.0512.
8-[(2-Naphthylsulfanyl)methylene]-1,4-dioxaspiro[4.5]decane
(3e′)
Yield: 54.3 mg (87%); colorless crystals; mp 72.2–73.3 °C (hex-
ane).
IR (KBr): 2950, 1623, 1588, 1136, 1113, 1083, 1036, 942, 910, 853,
825, 810, 741, 682 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.75 (t, J = 6.5 Hz, 2 H), 1.79 (t,
J = 6.5 Hz, 2 H), 2.48 (t, J = 6.5 Hz, 2 H), 2.59 (t, J = 6.5 Hz, 2 H),
4.00 (s, 4 H), 6.06 (s, 1 H), 7.40 (dd, J = 2.3, 8.6 Hz, 1 H), 7.42 (t,
J = 7.6 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 1 H), 7.71 (br s, 1 H), 7.74 (d,
J = 7.6 Hz, 1 H), 7.75 (d, J = 8.6 Hz, 1 H), 7.78 (d, J = 7.6 Hz, 1 H).
1-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-7-methoxy-2-naph-
thol (3b)
Yield: 50.9 mg (78%); yellow oil.
© Georg Thieme Verlag Stuttgart · New York
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T. Kimura et al.
PAPER
13C NMR (126 MHz, CDCl3): δ = 27.0, 33.2, 34.9, 35.9, 64.4
(2 × C), 108.5, 113.7, 125.5, 125.6, 126.4, 126.5, 127.0, 127.7,
128.4, 131.6, 133.8, 134.6, 145.1.
MS (EI): m/z (%) = 312 (100) [M+], 212 (10), 153 (49), 128 (13),
115 (21), 109 (18), 99 (15).
HRMS (EI): m/z [M+] calcd for C19H20O2S: 312.1184; found:
312.1185.
1H NMR (500 MHz, CDCl3): δ = 1.02–1.50 (m, 22 H), 1.65–1.74
(m, 2 H), 1.88–2.04 (m, 2 H), 2.33–2.44 (m, 2 H), 5.46 (s, 1 H), 6.25
(s, 1 H), 7.19 (d, J = 8.7 Hz, 1 H), 7.32 (t, J = 7.6 Hz, 1 H), 7.42 (t,
J = 7.6 Hz, 1 H), 7.70 (d, J = 8.7 Hz, 1 H), 7.72 (d, J = 7.6 Hz, 1 H),
7.76 (d, J = 7.6 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 26.1, 26.4, 26.50, 26.53, 26.7,
27.5, 27.6, 27.7, 31.2, 36.3, 116.4, 116.8, 123.1, 124.2, 126.1,
128.1, 128.6, 128.8, 133.1, 149.7, 152.1.
MS (EI): m/z (%) = 364 (100) [M+], 181 (37), 157 (25), 144 (20).
HRMS (EI): m/z [M+] calcd for C26H36O: 364.2766; found:
1-(Cyclopentylidenemethyl)-2-naphthol (3f)
Yield: 17.0 mg (38%); yellow oil.
IR (neat): 3507 (OH), 2955, 2868, 1622, 1595, 1516, 1465, 1388,
1265, 1204, 1140, 814, 747 cm–1.
364.2769.
1-(2-Methylprop-1-en-1-yl)-2-naphthol (3j)14b
Yield: 24.2 mg (61%); colorless oil.
1H NMR (500 MHz, CDCl3): δ = 1.69 (quint, J = 7.1 Hz, 2 H), 1.79
(quint, J = 7.1 Hz, 2 H), 2.07 (br t, J = 7.1 Hz, 2 H), 2.63 (br t,
J = 7.1 Hz, 2 H), 5.52 (s, 1 H), 6.41–6.46 (m, 1 H), 7.19 (d, J = 8.9
Hz, 1 H), 7.32 (t, J = 7.4 Hz, 1 H), 7.43 (t, J = 7.4 Hz, 1 H), 7.69 (d,
J = 8.9 Hz, 1 H), 7.75 (d, J = 7.4 Hz, 1 H), 7.76 (d, J = 7.4 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 26.2, 30.6, 34.0, 112.1, 117.0,
117.3, 123.1, 124.1, 126.2, 128.2, 128.6, 128.8, 132.6, 149.8, 154.5.
IR (neat): 3511 (OH), 2972, 2934, 2912, 1620, 1595, 1516, 1465,
1388, 1267, 1206, 1141, 959, 812, 749 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.61 (s, 3 H), 2.09 (s, 3 H), 5.43
(s, 1 H), 6.28 (s, 1 H), 7.20 (d, J = 8.5 Hz, 1 H), 7.32 (t, J = 7.6 Hz,
1 H), 7.43 (t, J = 7.6 Hz, 1 H), 7.71 (d, J = 8.5 Hz, 1 H), 7.72 (d,
J = 7.6 Hz, 1 H), 7.77 (d, J = 7.6 Hz, 1 H).
MS (EI): m/z (%) = 224 (100) [M+], 195 (17), 181 (62), 165 (18),
157 (20), 152 (15), 144 (16).
13C NMR (126 MHz, CDCl3): δ = 19.6, 25.5, 116.7, 116.8, 116.9,
123.1, 124.2, 126.2, 128.2, 128.8, 133.0, 142.9, 150.1.
MS (EI): m/z (%) = 198 (100) [M+], 183 (69), 181 (19), 165 (39),
HRMS (EI): m/z [M+] calcd for C16H16O: 224.1201; found:
224.1205.
155 (18), 152 (16), 128 (15).
HRMS (EI): m/z [M+] calcd for C14H14O: 198.1045; found:
198.1049.
1-(Cyclohexylidenemethyl)-2-naphthol (3g)14a
Yield: 23.8 mg (50%); yellow oil.
IR (neat): 3510 (OH), 2929, 2854, 1621, 1596, 1516, 1465, 1390,
1203, 1141, 814, 747 cm–1.
1-(2-Ethylbut-1-en-1-yl)-2-naphthol (3k)
Yield: 19.9 mg (44%); yellow oil.
1H NMR (500 MHz, CDCl3): δ = 1.37–1.54 (m, 2 H), 1.57–1.66 (m,
2 H), 1.76 (br quint, J = 6.0 Hz, 2 H), 2.00 (t, J = 6.0 Hz, 2 H), 2.48
(br s, 2 H), 5.47 (s, 1 H), 6.20 (s, 1 H), 7.19 (d, J = 9.0 Hz, 1 H), 7.32
(t, J = 7.7 Hz, 1 H), 7.43 (t, J = 7.7, Hz, 1 H), 7.70 (d, J = 9.0 Hz, 1
H), 7.76 (d, J = 7.7 Hz, 2 H).
13C NMR (126 MHz, CDCl3): δ = 26.4, 27.8, 29.0, 30.3, 36.8,
113.1, 116.2, 116.8, 123.1, 124.2, 126.2, 128.2, 128.6, 128.7, 133.2,
150.0, 150.7.
IR (neat): 3512 (OH), 2966, 2934, 1621, 1595, 1516, 1464, 1387,
1267, 1205, 1141, 816, 747 cm–1.
1H NMR (300 MHz, CDCl3): δ = 0.88 (t, J = 7.6 Hz, 3 H), 1.27 (t,
J = 7.4 Hz, 3 H), 1.97 (q, J = 7.6 Hz, 2 H), 2.41 (dq, J = 1.3, 7.4 Hz,
2 H), 5.45 (s, 1 H), 6.19 (s, 1 H), 7.20 (d, J = 8.8 Hz, 1 H), 7.32 (ddd,
J = 1.3, 6.8, 8.1 Hz, 1 H), 7.42 (ddd, J = 1.3, 6.8, 8.1 Hz, 1 H), 7.66–
7.80 (m, 3 H).
MS (EI): m/z (%) = 238 (100) [M+], 195 (16), 181 (49), 165 (13),
157 (53), 152 (14), 144 (17), 128 (13).
HRMS (EI): m/z [M+] calcd for C17H18O: 238.1358; found:
238.1363.
13C NMR (126 MHz, CDCl3): δ = 12.5, 13.1, 24.6, 28.5, 114.3,
116.7, 116.8, 123.1, 124.1, 126.1, 128.1, 128.6, 128.8, 133.1, 149.8,
154.5.
MS (EI): m/z (%) = 226 (85) [M+], 197 (100), 181 (30), 179 (22),
169 (20), 165 (17), 157 (19), 152 (20), 144 (24), 141 (19), 128 (19),
115 (15).
1-(Cyclooctylidenemethyl)-2-naphthol (3h)
Yield: 27.1 mg (51%); yellow oil.
HRMS (EI): m/z [M+] calcd for C16H18O: 226.1358; found:
226.1355.
IR (neat): 3511 (OH), 2923, 2854, 1621, 1595, 1516, 1466, 1447,
1388, 1267, 1208, 1141, 814, 747 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.21–1.75 (m, 8 H), 1.88 (br s, 2
H), 2.13 (br s, 2 H), 2.55 (br s, 2 H), 5.46 (s, 1 H), 6.35 (s, 1 H), 7.19
(d, J = 8.8 Hz, 1 H), 7.32 (t, J = 7.8 Hz, 1 H), 7.43 (t, J = 7.8 Hz, 1
H), 7.70 (d, J = 8.8 Hz, 1 H), 7.74 (d, J = 7.8 Hz, 1 H), 7.77 (d,
J = 7.8 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 25.2, 26.0, 26.7, 27.2, 28.8, 30.8,
36.0, 116.7, 116.9, 117.0, 123.1, 124.1, 126.2, 128.2, 128.7, 128.8,
133.0, 149.8, 153.5.
MS (EI): m/z (%) = 266 (100) [M+], 207 (21), 195 (19), 181 (65),
164 (21), 157 (69), 152 (18), 144 (28), 128 (13).
HRMS (EI): m/z [M+] calcd for C19H22O: 266.1671; found:
266.1670.
1-[4-Phenyl-2-(2-phenylethyl)but-1-en-1-yl]-2-naphthol (3l)
Yield: 40.1 mg (53%); yellow oil.
IR (neat): 3494 (OH), 3061, 3026, 2926, 2857, 1621, 1595, 1516,
1496, 1464, 1455, 1388, 1207, 1140, 816, 749, 699 cm–1.
1H NMR (500 MHz, CDCl3): δ = 2.26 (br s, 2 H), 2.53–2.68 (m, 2
H), 2.79 (br s, 2 H), 3.01 (br s, 2 H), 4.83 (s, 1 H), 6.11 (s, 1 H), 6.87
(d, J = 7.4 Hz, 2 H), 7.05–7.14 (m, 4 H), 7.26–7.31 (m, 4 H), 7.31–
7.40 (m, 3 H), 7.43 (d, J = 8.4 Hz, 1 H), 7.66 (d, J = 8.7 Hz, 1 H),
7.72 (d, J = 7.8 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 32.6, 33.8, 34.0, 37.6, 116.2,
116.9, 119.0, 123.1, 124.2, 125.9, 126.2, 126.3, 128.0, 128.1, 128.2,
128.5, 128.7, 128.8, 132.9, 141.1, 141.2, 148.3, 149.8.
MS (EI): m/z (%) = 378 (100) [M+], 195 (25), 181 (22), 157 (74),
143 (23), 129 (17), 105 (33), 91 (41).
HRMS (EI): m/z [M+] calcd for C28H26O: 378.1984; found:
378.1982.
1-(Cyclopentadecylidenemethyl)-2-naphthol (3i)
Yield: 35.0 mg (48%); yellow oil.
IR (neat): 3514 (OH), 2928, 2857, 1621, 1596, 1516, 1463, 1388,
1348, 1267, 1207, 1141, 815, 758 cm–1.
Synthesis 2013, 45, 659–667
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Alkenylation of Naphthols by Magnesium Alkylidene Carbenoids
665
1-(Cyclohex-2-en-1-ylidenemethyl)-2-naphthol (3n)
Obtained as a 31:69 mixture of geometric isomers (Table 3, entry
1); yield: 34.0 mg (72%); yellow oil.
1H NMR (500 MHz, CDCl3): δ = 0.97 (br t, J = 6.7 Hz, 3 H), 1.36–
1.46 (m, 4 H), 1.58 (s, 3 H), 1.65 (quint, J = 7.4 Hz, 2 H), 2.37 (t,
J = 7.4 Hz, 2 H), 5.41 (s, 1 H), 6.28 (s, 1 H), 7.20 (d, J = 8.7 Hz, 1
H), 7.32 (t, J = 8.0 Hz, 1 H), 7.43 (t, J = 8.0 Hz, 1 H), 7.70 (d,
J = 8.0 Hz, 1 H), 7.71 (d, J = 8.7 Hz, 1 H), 7.77 (d, J = 8.0 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 14.1, 17.7, 22.6, 27.8, 31.7, 39.3,
116.3, 116.7, 116.9, 123.1, 124.1, 126.2, 128.2, 128.7, 128.8, 132.9,
147.1, 149.9.
MS (EI): m/z (%) = 254 (100) [M+], 197 (30), 183 (90), 181 (33),
179 (21), 165 (20), 157 (41), 152 (18), 144 (44).
HRMS (EI): m/z [M+] calcd for C18H22O: 254.1671; found:
254.1675.
IR (neat): 3514 (OH), 2935, 1621, 1594, 1516, 1465, 1388, 1267,
1204, 1141, 958, 816, 750 cm–1.
1H NMR (500 MHz, CDCl3) (M: major isomer, m: minor isomer):
δ = 1.67 (quint, J = 6.2 Hz, 2 Hm), 1.90 (quint, J = 6.0 Hz, 2 HM),
2.15–2.27 (m, 2 HM, 4 Hm), 2.68 (t, J = 6.0 Hz, 2 HM), 5.34 (s, 1 Hm),
5.53 (s, 1 HM), 5.93–6.07 (m, 2 HM, 1 Hm), 6.24 (s, 1 HM), 6.34 (s, 1
Hm), 6.43–6.47 (m, 1 Hm), 7.194 (d, J = 8.4 Hz, 1 HM), 7.195 (d,
J = 9.4 Hz, 1 Hm), 7.32 (t, J = 7.7 Hz, 1 HM), 7.33 (t, J = 7.7 Hz, 1
Hm), 7.41–7.46 (m, 1 HM, 1 Hm), 7.712 (d, J = 8.4 Hz, 1 HM), 7.715
(d, J = 9.4 Hz, 1 Hm), 7.72 (d, J = 7.7 Hz, 1 Hm), 7.74 (d, J = 7.7 Hz,
1 HM), 7.766 (d, J = 7.7 Hz, 1 HM), 7.773 (d, J = 7.7 Hz, 1 Hm).
13C NMR (126 MHz, CDCl3): δ = 22.4, 23.3, 25.7, 26.1, 26.7, 31.9,
115.4, 115.9, 116.9, 117.0, 123.2, 123.3, 124.2, 124.3, 124.9,
126.27, 126.31, 128.1, 128.2, 128.8, 129.0, 129.8, 131.9, 132.9,
134.2, 141.4, 143.6, 150.1, 150.2.
2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-1-naphthol (7a)
Yield: 39.7 mg (67%); yellow oil.
IR (neat): 3416 (OH), 2926, 2850, 1718, 1572, 1385, 1271, 1245,
1120, 1085, 1033, 759 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.67 (t, J = 6.5 Hz, 2 H), 1.85 (t,
J = 6.5 Hz, 2 H), 2.31 (t, J = 6.5 Hz, 2 H), 2.55 (t, J = 6.5 Hz, 2 H),
3.95–4.02 (m, 4 H), 5.52 (s, 1 H), 6.29 (s, 1 H), 7.15 (d, J = 8.4 Hz,
1 H), 7.38 (d, J = 8.4 Hz, 1 H), 7.43–7.50 (m, 2 H), 7.74–7.80 (m, 1
H), 8.19–8.25 (m, 1 H).
MS (EI): m/z (%) = 236 (100) [M+], 219 (12), 207 (39), 194 (14),
181 (29), 165 (13), 157 (25), 152 (12), 129 (12).
HRMS (EI): m/z [M+] calcd for C17H16O: 236.1201; found:
236.1199.
13C NMR (126 MHz, CDCl3): δ = 26.6, 33.5, 35.2, 36.1, 64.4
(2 × C), 108.4, 117.1, 117.3, 119.5, 122.2, 123.9, 125.2, 126.1,
127.40, 127.44, 133.8, 145.7, 148.0.
MS (EI): m/z (%) = 296 (100) [M+], 234 (14), 195 (18), 181 (23),
158 (22), 140 (51), 96 (22).
HRMS (EI): m/z [M+] calcd for C19H20O3: 296.1412; found:
296.1414.
1-(2-Methylbuta-1,3-dien-1-yl)-2-naphthol (3o)
Obtained as a 40:60 mixture of geometric isomers (Table 3, entry
3); yield: 20.2 mg (48%); yellow oil.
IR (neat): 3520 (OH), 3060, 2924, 1621, 1595, 1515, 1465, 1388,
1267, 1206, 1141, 818, 748 cm–1.
1H NMR (500 MHz, CDCl3) (M: major isomer, m: minor isomer):
δ = 1.75 (s, 3 Hm), 2.20 (s, 3 HM), 5.20 (d, J = 11.0 Hz, 1 HM), 5.26
(s, 1 Hm), 5.28 (d, J = 10.6 Hz, 1 Hm), 5.40 (s, 1 HM), 5.42 (d,
J = 17.6 Hz, 1 Hm), 5.47 (d, J = 17.4 Hz, 1 HM), 6.35 (dd, J = 11.0,
17.4 Hz, 1 HM), 6.52 (s, 1 HM), 6.60 (s, 1 Hm), 6.77 (dd, J = 10.6,
17.6 Hz, 1 Hm), 7.195 (d, J = 9.3 Hz, 1 HM), 7.204 (d, J = 8.7 Hz, 1
Hm), 7.34 (t, J = 8.0 Hz, 1 HM), 7.40 (t, J = 8.0 Hz, 1 Hm), 7.44 (t,
J = 8.0 Hz, 1 HM, 1 Hm), 7.68 (d, J = 8.0 Hz, 1 Hm), 7.71 (d, J = 8.0
Hz, 1 HM), 7.73 (d, J = 9.3 Hz, 1 HM), 7.74 (d, J = 8.7 Hz, 1 Hm),
7.776 (d, J = 8.0 Hz, 1 HM), 7.783 (d, J = 8.0 Hz, 1 Hm).
MS (EI): m/z (%) = 210 (38) [M+], 195 (100), 181 (10), 165 (20),
152 (15).
HRMS (EI): m/z [M+] calcd for C15H14O: 210.1045; found:
210.1046.
2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)-4-methoxy-1-naph-
thol (7b)
Yield: 40.4 mg (62%); yellow oil.
IR (neat): 3391 (OH), 2952, 2886, 1621, 1596, 1459, 1390, 1288,
1225, 1122, 1097, 1081, 1033, 759 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.68 (t, J = 6.5 Hz, 2 H), 1.85 (t,
J = 6.5 Hz, 2 H), 2.34 (t, J = 6.5 Hz, 2 H), 2.55 (t, J = 6.5 Hz, 2 H),
3.94 (s, 3 H), 3.97–4.01 (m, 4 H), 5.17 (s, 1 H), 6.27 (s, 1 H), 6.49
(s, 1 H), 7.43–7.54 (m, 2 H), 8.14–8.20 (m, 2 H).
13C NMR (126 MHz, CDCl3): δ = 26.7, 33.4, 35.2, 36.1, 55.7, 64.4
(2 × C), 105.2, 108.4, 116.0, 117.8, 121.7, 122.0, 124.8, 125.4,
125.6, 125.9, 141.8, 145.2, 148.7.
MS (EI): m/z (%) = 326 (100) [M+], 280 (14), 225 (11), 211 (11),
202 (14), 187 (23), 140 (62), 99 (29), 96 (20), 86 (11).
1-[(1Z)-2-Methylhept-1-en-1-yl]-2-naphthol [(Z)-3p]
Yield: 21.9 mg (43%); yellow oil.
HRMS (EI): m/z [M+] calcd for C20H22O4: 326.1518; found:
326.1518.
IR (neat): 3512 (OH), 2955, 2929, 2858, 1622, 1595, 1516, 1465,
1388, 1267, 1205, 1141, 815, 747 cm–1.
1H NMR (500 MHz, CDCl3): δ = 0.70 (t, J = 6.9 Hz, 3 H), 1.00–
1.13 (m, 4 H), 1.34 (quint, J = 7.4 Hz, 2 H), 1.88–1.99 (m, 2 H),
2.07 (s, 3 H), 5.46 (s, 1 H), 6.23 (s, 1 H), 7.19 (d, J = 8.8 Hz, 1 H),
7.31 (t, J = 8.0 Hz, 1 H), 7.42 (t, J = 8.0 Hz, 1 H), 7.70 (d, J = 8.0
Hz, 1 H), 7.72 (d, J = 8.8 Hz, 1 H), 7.76 (d, J = 8.0 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 13.7, 22.2, 22.9, 27.1, 31.4, 33.0,
116.77, 116.80, 123.1, 124.3, 126.1, 128.1, 128.7, 128.75, 128.81,
133.1, 147.3, 149.9.
MS (EI): m/z (%) = 254 (100) [M+], 197 (20), 183 (60), 181 (19),
157 (28), 144 (27).
HRMS (EI): m/z [M+] calcd for C18H22O: 254.1671; found:
254.1675.
4-Chloro-2-(1,4-dioxaspiro[4.5]dec-8-ylidenemethyl)-1-naph-
thol (7c)
Yield: 41.6 mg (63%); yellow oil.
IR (neat): 3410 (OH), 2952, 2886, 1595, 1380, 1270, 1215, 1121,
1081, 1033, 760 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.67 (t, J = 6.5 Hz, 2 H), 1.85 (t,
J = 6.5 Hz, 2 H), 2.30 (dt, J = 1.1, 6.5 Hz, 2 H), 2.55 (dt, J = 1.1, 6.5
Hz, 2 H), 3.96–4.01 (m, 4 H), 5.53 (s, 1 H), 6.21 (s, 1 H), 7.26 (s, 1
H), 7.49–7.63 (m, 2 H), 8.13–8.28 (m, 2 H).
13C NMR (126 MHz, CDCl3): δ = 26.7, 33.4, 35.1, 36.1, 64.4
(2 × C), 108.3, 116.2, 117.3, 122.4, 122.7, 124.2, 124.9, 126.0,
127.08, 127.11, 130.6, 146.7, 147.2.
1-[(1E)-2-Methylhept-1-en-1-yl]-2-naphthol [(E)-3p]
Yield: 32.0 mg (63%); yellow oil.
MS (EI): m/z (%) = 330 (100) [M+], 268 (16), 215 (18), 206 (29),
193 (18), 165 (18), 140 (79), 99 (34), 96 (30).
HRMS (EI): m/z [M+] calcd for C19H19ClO3: 330.1023; found:
330.1020.
IR (neat): 3513 (OH), 2956, 2929, 2857, 1621, 1595, 1517, 1465,
1387, 1266, 1207, 1141, 815, 747 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 659–667

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T. Kimura et al.
PAPER
2-(1,4-Dioxaspiro[4.5]dec-8-ylidenemethyl)phenanthren-1-ol
IR (neat): 2956, 2880, 1688, 1606, 1518, 1485, 1375, 1248, 1202,
1101, 1074, 1031, 905, 763 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.67–1.79 (m, 4 H), 2.29 (dt,
J = 1.0, 6.4 Hz, 2 H), 2.48 (dt, J = 1.0, 6.4 Hz, 2 H), 3.99 (s, 4 H),
6.27–6.31 (m, 1 H), 7.01–7.09 (m, 2 H), 7.27–7.35 (m, 1 H), 7.38–
7.46 (m, 2 H), 7.49–7.58 (m, 4 H).
MS (EI): m/z (%) = 322 (100) [M+], 261 (12), 238 (12), 170 (31),
153 (98), 109 (20).
HRMS (EI): m/z [M+] calcd for C21H22O3: 322.1569; found:
322.1569.
(7d)
Yield: 38.8 mg (56%); colorless oil.
IR (neat): 3419 (OH), 2951, 2886, 1598, 1574, 1462, 1239, 1215,
1137, 1120, 1083, 1033, 753 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.69 (t, J = 6.5 Hz, 2 H), 1.87 (t,
J = 6.5 Hz, 2 H), 2.35 (t, J = 6.5 Hz, 2 H), 2.58 (t, J = 6.5 Hz, 2 H),
3.97–4.02 (m, 4 H), 5.56 (s, 1 H), 6.34 (s, 1 H), 7.34 (d, J = 8.5 Hz,
1 H), 7.58 (t, J = 7.7 Hz, 1 H), 7.63 (t, J = 7.7 Hz, 1 H), 7.74 (d,
J = 9.3 Hz, 1 H), 7.89 (d, J = 7.7 Hz, 1 H), 8.19 (d, J = 9.3 Hz, 1 H),
8.22 (d, J = 8.5 Hz, 1 H), 8.64 (d, J = 7.7 Hz, 1 H).
13C NMR (126 MHz, CDCl3): δ = 26.6, 33.5, 35.2, 36.1, 64.4
(2 × C), 108.4, 114.4, 117.0, 119.2, 120.6, 121.4, 122.9, 126.1,
126.4, 126.5, 127.8, 128.5, 130.0, 130.7, 132.0, 146.2, 148.8.
MS (EI): m/z (%) = 346 (100) [M+], 284 (15), 245 (19), 231 (21),
215 (13), 208 (42), 202 (17), 140 (35), 96 (27).
Iron(III) Chloride Test
0.1 M aq FeCl3 (1 mL, 0.1 mmol) was added to a soln of 3a (10.0
mg, 0.034 mmol) in 1:1 H2O–EtOH (2 mL) at r.t. The color of the
soln immediately changed from yellow to green. When a soln of
FeCl3 was added to a soln of 10a, the color of the soln did not
change.
HRMS (EI): m/z [M+] calcd for C23H22O3: 346.1569; found:
346.1564.
Acknowledgment
8-(Phenoxymethylene)-1,4-dioxaspiro[4.5]decane (10a)
Yield: 9.8 mg (20%); colorless oil.
This work was supported by Grant-in-Aid for Scientific Research
No. 22590021 from the Ministry of Education, Culture, Sports, Sci-
ence and Technology, Japan, and by a TUS Grant for Research Pro-
motion from Tokyo University of Science, which we gratefully
acknowledge. We thank Prof. Takao Saito (Tokyo University of
Science) for the use of his recycling gel-permeation chromatogra-
phy system.
IR (neat): 2950, 2882, 1686, 1597, 1492, 1236, 1102, 1078, 1034,
907, 754, 692 cm–1.
1H NMR (500 MHz, CDCl3): δ = 1.69 (t, J = 6.5 Hz, 2 H), 1.74 (t,
J = 6.5 Hz, 2 H), 2.27 (t, J = 6.5 Hz, 2 H), 2.46 (t, J = 6.5 Hz, 2 H),
3.99 (s, 4 H), 6.25 (s, 1 H), 6.98 (d, J = 7.9 Hz, 2 H), 7.02 (t, J = 7.9
Hz, 1 H), 7.30 (t, J = 7.9 Hz, 2 H).
13C NMR (126 MHz, CDCl3): δ = 22.4, 27.3, 34.8, 36.0, 64.3
(2 × C), 108.9, 115.8, 122.0, 122.5, 129.5, 133.3, 157.7.
MS (EI): m/z (%) = 246 (55) [M+], 153 (100), 109 (81), 94 (12), 91
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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(15), 81 (14), 77 (15).
HRMS (EI): m/z [M+] calcd for C15H18O3: 246.1256; found:
246.1251.
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8-[(4-Methoxyphenoxy)methylene]-1,4-dioxaspiro[4.5]decane
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Yield: 13.8 mg (25%); yellow oil.
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8-[(4-Fluorophenoxy)methylene]-1,4-dioxaspiro[4.5]decane
(10c)
Yield: 14.3 mg (27%); colorless oil.
IR (neat): 2951, 2883, 1687, 1504, 1444, 1375, 1246, 1204, 1124,
1102, 1034, 907, 831, 756, 681 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.65–1.76 (m, 4 H), 2.25 (dt,
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264.1164.
8-[(Biphenyl-4-yloxy)methylene]-1,4-dioxaspiro[4.5]decane
(10d)
Yield: 16.1 mg (25%); colorless oil.
Synthesis 2013, 45, 659–667
© Georg Thieme Verlag Stuttgart · New York

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Synthesis 2013, 45, 659–667