Synthesis of naphthalenophane-type macrocyclic compounds using Mn(III)-based dihydrofuran-clipping reaction

Article abstract of DOI:10.1016/j.tet.2016.09.025

The Mn(III)-based oxidation of 2,7-, 1,8-, and 1,5-disubstituted naphthalenes bearing both the 1,4-dioxa-7,7-diphenylhep-6-enyl and 1,4-dioxa-5,7-dioxooctyl groups gave new [12]naphthalenophanes along with the corresponding diploids via assembly of the dihydrofuran ring. A similar reaction of the 2,6-disubstituted naphthalene having the same substituents did not produce the naphthalenophane, but the diploid, [12,12](2,6)naphthalenophane, was obtained in a small amount. The 2,6-disubstituted naphthalene tethered to the 1,4,7-trioxa-10,10-diphenyldec-9-enyl and 1,4,7-trioxa-8,10-dioxoundecyl groups also underwent the dihydrofuran-clipping reaction to afford a trace amount of the desired [18](2,6)naphthalenophane. The reaction details and the structure determination of the products are described.

Full text of DOI:10.1016/j.tet.2016.09.025

Tetrahedron 72 (2016) 6963e6971
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of naphthalenophane-type macrocyclic compounds using
Mn(III)-based dihydrofuran-clipping reaction
a
a
b,
*
Chiaki Matsumoto , Ken-ji Yasutake , Hiroshi Nishino
a
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Ch u^ ou-Ku, Kumamoto 860-8555,
Japan
b
Department of Chemistry, Kumamoto University, Kurokami 2-39-1, Ch u^ ou-Ku, Kumamoto 860-8555, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 June 2016
Received in revised form 12 September 2016
Accepted 13 September 2016
Available online 15 September 2016
The Mn(III)-based oxidation of 2,7-, 1,8-, and 1,5-disubstituted naphthalenes bearing both the 1,4-dioxa-
7,7-diphenylhep-6-enyl and 1,4-dioxa-5,7-dioxooctyl groups gave new [12]naphthalenophanes along
with the corresponding diploids via assembly of the dihydrofuran ring. A similar reaction of the 2,6-
disubstituted naphthalene having the same substituents did not produce the naphthalenophane, but
the diploid, [12,12](2,6)naphthalenophane, was obtained in a small amount. The 2,6-disubstituted
naphthalene tethered to the 1,4,7-trioxa-10,10-diphenyldec-9-enyl and 1,4,7-trioxa-8,10-dioxoundecyl
groups also underwent the dihydrofuran-clipping reaction to afford a trace amount of the desired
[18](2,6)naphthalenophane. The reaction details and the structure determination of the products are
described.
Dedicated to Dr. Kazu Kurosawa, Professor
Emeritus of Kumamoto University, who was
awarded the 2015 Order of the Sacred
Treasure, Gold Rays with Neck Ribbon.
Ó 2016 Elsevier Ltd. All rights reserved.
Keywords:
Naphthalenophanes
Macrocyclic compounds
Oxidation
4,5-Dihydrofurans
Manganese(III) acetate
4
,5
1
. Introduction
depending on the ring size.
Although macrolides have been
6
7
prepared by Yamaguchi,
Corey-Nicolaou,
Shiina macro-
8
9
The synthesis of cyclic compounds from acyclic linear com-
pounds as the starting materials is one of the goals of organic
synthesis. There are many cyclic products in nature from small to
large rings including heterocycles. In 1926, Ruzicka found that the
structure of the most famous perfume, muscone, was a fifteen-
lactonization, and ring-closing metathesis (RCM), the synthesis of
cyclophanes containing a flat and rigid aromatic ring is more
challenging in organic chemistry. We recently reported the syn-
thesis of cyclophane-type macrocycles consisting of benzene and
biphenyl from a 21 to 100 ring size using Mn(III)-mediated oxida-
10
1
3,11
membered cyclic ketone. Ever since then, macrocyclic com-
tive radical cyclization.
The characteristic of the reaction is as-
pounds are attractive for investigation from the standpoint of not
only flavor chemistry, but also pharmaceutical and supramolecular
chemistries such as antibiotics, molecular recognition, anion
binding, metal ion transport, enzymatic catalysis, chemical
switching, etc.2 Macrocyclic cyclophanes consisting of an aromatic
unit and aliphatic chain are also interesting compounds because
sembly of the dihydrofuran by intramolecular addition resulting in
forming macrocycles, the so-called ‘dihydrofuran-clipping re-
action.’ In this case, we could achieve the macrocyclization using
the relatively flexible chain binding with a disubstituted benzene
and biphenyl. In connection with our study, we were very in-
terested in the synthesis of cyclophanes consisting of a more flat
and rigid aromatic unit such as naphthalene from the standpoint of
the potential of the reaction and the distorted structure. In this
paper, we describe the synthesis of naphthalenophanes using the
Mn(III)-mediated dihydrofuran-clipping reaction and the charac-
teristics of the products.
,3
the aromatic
p-electrons of the cyclophanes undergo many in-
teractions with metal cations and guest polycyclic aromatics
*
Corresponding author. Fax: þ81 96 342 3374; e-mail address: nishino@sci.
kumamoto-u.ac.jp (H. Nishino).
http://dx.doi.org/10.1016/j.tet.2016.09.025
0
040-4020/Ó 2016 Elsevier Ltd. All rights reserved.

6964
C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
2
. Results and discussion
6) or under concentrated conditions (entries 7e9, 11), a more polar
mixture was produced, and after separation, the corresponding
diploid 3a was barely isolated together with 2a. The factor, which
complicated the reaction, would be the following reasons: the
benzylic and allylic oxidation of 1a with manganese(III) acetate to
break the side-chain of 1a, and the intermolecular addition of 1a to
produce the oligomer. In order to overcome this difficulty, we
considered the conditions whose contact of the oxidant and the
substrate 1a as well as each 1a should decrease as much as possible.
Therefore, we chose more diluted conditions and successively
added two or three portions of the oxidant to the reaction mixture
Initially, we prepared disubstituted naphthalenes 1aed bearing
the 1,4-dioxa-7,7-diphenylhep-6-enyl and 1,4-dioxa-5,7-dioxooctyl
groups (Scheme 1). Naphthalenediols were allowed to react with
ethyl bromoacetate to give the corresponding bis(ethoxycarbonyl-
methyloxy)-substituted naphthalenes. The carboxylates were re-
duced by lithium aluminum hydride (LAH) to give the diols, one of
which was protected by a tetrahydropyranyl group (THP). The THP-
protected alcohols were then allowed to react with 3-bromo-1,1-
diphenyl-1-prorene, followed by deprotection and esterification
with diketene to finally give the desired disubstituted naphthalenes
13
(entries 3,10,12). A solution of 1a in acetic acid (5 mL) was poured
1
aed.
into a boiling mixture of three equivalents of manganese(III) ace-
Scheme 1. Preparation of disubstituted naphthalenes 1a-d.
With the substrate naphthalenes 1aed in hand, the macro-
tate and acetic acid (50 mL) using a syringe (0.2 mL/min) and the
rest of the oxidant (3 equiv) was added after 10 min since the
brown color of the reaction mixture turned transparent, which
meant the consumption of the brownish Mn(III) oxidant, and
continued to heat under reflux. As a result, the reaction finished
after 31 min and the maximum yield of the product 2a was realized
(35% as shown in entry 10).
cyclization using manganese(III) acetate was investigated. First of
all, we chose the 2,7-disubstituted naphthalene 1a, and the pre-
liminary reaction was carried out at the molar ratio of
1
a:Mn(OAc)
3
¼1:3 in boiling acetic acid (10 mL) (Scheme 2 and
12
Table 1, entry 1). Although the reaction gave an intractable mix-
ture, we were please to isolate the desired naphthalenophane 2a in
7
% yield. We were then sure of the usefulness of the dihydrofuran-
With this technique in mind, we examined the dihydrofuran-
clipping reaction of other substituted naphthalenes 1bed under
various conditions (Scheme 3 and Table 2). Although the reaction
clipping reaction and scrutinized the reaction under various con-
ditions (Table 1). When the reaction was carried out at 100 C (entry
ꢀ
3
Scheme 2. Oxidation of 1a with Mn(OAc) .

C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
6965
3
Scheme 3. Oxidation of 1bed with Mn(OAc) .
Table 1
a
Table 2
Oxidation of 2,7-disubstituted naphthalene 1a with Mn(OAc)
3
a
Oxidation of disubstituted naphthalenes 1bed with Mn(OAc)
3
Entry 1a:Mn(OAc) b
AcOH/mL Temp/ C Time/min Product Yield/%c
ꢀ
3
AcOH/mL Temp/ C Time/ Product (Yield/%)c 1/rec/%
ꢀ
Entry 1
1:Mn
(OAc)
b
2
a
3a
3
min
1
2
3
4
5
6
7
8
9
1
1
1
1:3
1:3
1:3
1:3
1:3
1:3
1:4
1:6
1:6
1:6
1:8
1:8
10
50
50
100
100
200
50
50
100
50
Reflux
Reflux
Reflux
100
Reflux
100
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
5
7
1
2
3
4
5
6
7
8
1b: 1,8- 1:3
1b: 1,8- 1:4
1b: 1,8- 1:4
1b: 1,8- 1:4
1b: 1,8- 1:4d
100
100
50
100
100
50
50
50
50
50
100
100
150
100
100
50
Reflux
100
5
6
5
4
26
21
29
2b (8)
2b (8)
d
11
17
5
10
30
8
14
18
41
11
40
20
26
12
8
14
16
17
13
35
13
32
e,f
Reflux
Reflux
Reflux
Reflux
Reflux
70
2b (15)
2b (20)
2b (30)
2b (28)
2b (15)
10
16
d,e
22
16
21
10
1b: 1,8- 1:4
1b: 1,8- 1:6
1c: 1,5- 1:4
1c: 1,5- 1:4
1c: 1,5- 1:4
1c: 1,5- 1:3
1c: 1,5- 1:4
1c: 1,5- 1:4
1c: 1,5- 1:4
d,e
100 Complex mixture
9
4
8
12
5
5
11
32
5
9
100
2c (4)
2c (7)
2c (7)
2c (8)
2c (5)
2c (2)
2c (15) 3c (2)
2c (12) 3c (2)
3d (4)
3c (6)
3c (7)
3c (12)
3c (8)
3c (8)
e,f
e,f
0
1
2
10
11
12
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
50
50
17
3
8
13
14
15
16
17
18
a
The reaction of 1a (0.2 mmol) was carried out in acetic acid under an argon
f
atmosphere.
1c: 1,5- 1:4d
1c: 1,5- 1:8
1d: 2,6- 1:4
1d: 2,6- 1:4
b
Molar ratio.
Isolated yield based on the amount of 1a used.
The naphthalene 1a (15%) was recovered.
Two- or three-portions of Mn(OAc)
The naphthalene 1a was dropwise added during the reaction.
d,e
c
d
e
f
100
50
11
3d (2)
3
were successively added.
a
The reaction of 1 (0.2 mmol) was carried out in acetic acid under an argon
atmosphere.
b
was plagued by low yields, the modified technique mentioned
above was effective for the 1,8-disubstituted naphthalene 1b (entry
Molar ratio.
Isolated yield based on the amount of 1 used.
The naphthalene 1 was dropwise added during the reaction.
Three-portions of Mn(OAc)
c
d
e
f
6
). In addition, the distance between the a-carbonyl carbon and
3
were successively added.
alkenic double bond in 1b would be close to each other, so that the
NaOAc (2 equiv) was added.
intramolecular addition would be superior to the intermolecular
3
reaction, such as the diploid and oligomer formation (entries 1e7),
and thus the synthesis of naphthalenophane 2b was realized in
a yield similar to that of 2a (entry 5). The reaction of the 1,5-
disubstituted naphthalene 1c of which the reaction site was far-
ther than that of 1a and 1b was more difficult and we were again
afflicted by the indecent side reactions (entries 8e16). However,
the naphthalenophane 2c could be barely isolated in 15% yield to-
gether with a small amount of the diploid 3c (entry 15). Isolation of
a monoploid naphthalenophane, except for the diploid 3d, failed
for the reaction of the 2,6-disubstituted naphthalene 1d of which
the distance between the reaction sites was the farthest (entries 17
and 18).1
In order to further explore the possibility of the dihydrofuran-
clipping reaction for the 2,6-disubstituted naphthalene, we pre-
pared a naphthalene 4 bearing longer tethers, i.e., the 1,4,7-trioxa-
10,10-diphenyldec-9-enyl
and
1,4,7-trioxa-8,10-dioxoundecyl
groups, which underwent the reaction under modified condi-
3
tions. As a result, although each reaction site in 4 might be still
apart and the benzylic and allylic oxidation and oligomerization
predominantly proceeded, the corresponding naphthalenophane 5
could be isolated in a very low yield (3%) (see Scheme 4).
The structure of the product 2a was deduced by a spectroscopic
4e19
analysis. A triplet at
d
6.27 ppm (1H, J¼7.0 Hz) assigned to the
3
Scheme 4. Oxidation of 4 with Mn(OAc) .

6966
C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
Scheme 5. Result of 2D NMR spectrum of [12](2,7)naphthalenophane 2a.
olefinic sp2 proton and a singlet at
methylene proton adjacent to the carbonyl group of 1a in the
d
3.49 ppm (2H) due to the
1
H
3
NMR spectrum disappeared and a broad singlet assigned to an sp
methine proton newly appeared at 3.92 ppm (1H, H-13) in that of
a. In the 13C NMR spectrum of 2a, the carbonyl group of 1a
d
2
appeared at
d
200.2 and 167.0 ppm then converted into the enol
167.2 (C-16) and 163.9 ppm (C-2). The sp2
125.2 and 124.5 ppm in 1a transformed into an
alkoxyl sp quaternary carbon (C-14) at 93.2 ppm and a methine
49.4 ppm in 2a. These data showed the
presence of the 4,5-dihydrofuran ring in the product 2a. In addition,
several methylene protons corresponding to the allylic ( 4.18 (2H,
4.54, 4.26, 4.20, and
ester group shown at
vinyl carbons at
d
d
3
d
3
sp carbon (C-13) at
d
d
d, J¼6.8 Hz)) and O-methylene protons (
d
3
.82 ppm (t, J¼4.5 Hz)) of 1a shifted from downfield to upfield in
1
the range from
d 4.78 to 2.50 ppm in the H NMR spectrum of 2a
(
d
see Experimental section). Furthermore, a singlet appeared at
Fig. 2. ORTEP drawing of 2c.
2.24 ppm due to the methyl protons of 1a that also shifted upfield
20
(d 2.09 ppm) in 2a. These results clearly supported the fact that
both the paramagnetic and diamagnetic shift must be caused by the
construction of the naphthalenophane. In order to clarify the cor-
relation of the protons and carbons of 2a, the 2D NMR spectrum,
disubstituted naphthalene 1c was also obtained as a single crystal
from CH
2 2
Cl and the exact [12](1,5)naphthalenophane structure
such as HH COSY, HMQC, and HMBC, was taken in CDCl
3
. The results
was proved by the X-ray analysis (see Experimental section,
2
2
are shown in Scheme 5. All of the data supported the structure of
Fig. 2).
21
the naphthalenophane 2a. Finally, a single crystal of 2a was
successfully grown from CHCl /hexane and subjected to an X-ray
3
3. Conclusion
crystallographic measurement. As a result, we obtained the exact
structure of the product 2a as a [12](2,7)naphthalenophane and
illustrated in Fig. 1.15 In addition, the product 2c from the 1,5-
We have accomplished the unique synthesis of naph-
thalenophane macrocycles using the Mn(III)-mediated dihy-
drofuran-clipping reaction and the characterization of the
dihydrofuran-fused naphthalenophanes obtained from the re-
action. It was surprising that the strained [12]naphthalenophanes
2aec could be obtained from the reaction of the 2,7-, 1,8-, and 1,5-
disubstituted naphthalenes bearing both the 1,4-dioxa-7,7-
3
diphenylhept-6-enyl and 1,4-dioxa-5,7-dioxooctyl groups. In this
study, it was proved that the reaction could be used for the syn-
thesis of macrocyclic compounds including aromatics as a single
technique. However, it was difficult to optimize the reaction
depending on the position of the substituent and probably tethered
chain length.
4
4
. Experimental section
.1. Measurements
Meltingpoints were taken usinga Yanagimoto micromelting point
apparatus and are uncorrected. The NMR spectrawere recorded using
a JNM ECX 500 or AL300 FT-NMR spectrometer at 500 or 300 MHz for
1
13
the H and at 125 or 75 MHz for C, with tetramethylsilane as the
internal standard. The chemical shifts are reported as values (ppm)
and the coupling constants in Hz. The following abbreviations are
d
Fig. 1. ORTEP drawing of 2a.

C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
6967
used for the multiplicities; s, singlet; d, doublet; t, triplet; q, quartet;
m, multiplet; brs, broad singlet for the H NMR spectrum. The IR
(CH
2
C]O), 30.0 (CH
3
). FAB HRMS (acetone/NBA/NaI): calcd for
1
33
C H
32
O
6
547.2097 (MþNa); found 547.2105.
3
spectra were measured in CHCl or KBr using a Shimadzu 8400 FTIR
ꢁ1
spectrometer and expressed in cm . The EIMS spectra were obtained
by a Shimadzu QP-5050A gas chromatograph-mass spectrometer at
the ionizing voltage of 70 eV. The high-resolution mass spectra and
the elemental analyses were performed at the Instrumental Analysis
Center, Kumamoto University, Kumamoto, Japan. The X-ray analysis
was performed by a SuperNova A diffractometer with a Cu micro-
focus source and the final structures obtained were very high qual-
ity and automatically solved by the AutoChem module.
4
.2.2. 2-((8-(2-((3,3-Diphenylallyl)oxy)ethoxy)naphthalen-1-yl)oxy)
ethyl 3-oxobutanoate (1b). Yellow liquid. R O-hexane, 5:5
¼0.31 (Et
1744, 1717 (C]O). H NMR (500 MHz, CDCl
7.30e7.06 (14H, m, arom H), 6.68 (2H, d, J¼7.7 Hz, arom H), 6.17
1H, t, J¼6.7 Hz, C]CH), 4.42 (2H, t, J¼4.7 Hz, CH ), 4.11 (2H, t,
), 4.05 (2H, t, J¼4.7 Hz,
), 3.28 (2H, s, CH C]O), 2.03 (3H, s,
200.6 (CH C]O), 167.3 (>C]O),
f
2
4
.2. Materials
1
v/v). IR (CHCl
d
3
)
n
3
)
2 2
Manganese(II) acetate tetrahydrate, Mn(OAc) $4H O, was pur-
(
2
chased from Wako Pure Chemical Ind., Ltd. Manganese(III) acetate
dihydrate, Mn(OAc) $2H O, was prepared according to our modi-
J¼4.7 Hz, CH
2
), 4.06 (2H, d, J¼6.7 Hz, CH
2
3
2
CH
CH
), 3.74 (2H, t, J¼4.7 Hz, CH
2
2
2
fied method.23 3-Bromo-1,1-diphenylprop-1-ene was prepared by
the Grignard reaction of propiophenone with phenylmagnesium
bromide followed by dehydration and bromination. 1,8-
Naphthosultone, 1,5-naphthalenediol, ethyl bromoacetate, lithium
aluminum hydride, diketene, propiophenone, and 2-(2-
chloroethoxy)ethanol were purchased from Tokyo Kasei Co., Ltd.,
and 2,7-naphthalenediol, 2,6-naphthalenediol, N-bromosuccini-
mide (NBS), sodium hydride, bromobenzene, and dihydropyran
13
3
). C NMR (125 MHz, CDCl
3
)
d
3
1
56.0, 155.9, 144.9, 141.9, 139.3, 137.6, 118.6 (arom C), 129.9 (2C),
28.37 (2C), 128.34 (2C), 127.8 (2C), 127.74, 127.70, 126.6, 126.4,
25.6, 122.0, 121.3 (C]CH), 109.6, 108.2 (arom CH), 69.0, 68.9, 68.7,
8.1, 64.2 (CH ), 50.0 (CH C]O), 30.2 (CH ). FAB HRMS (acetone/
NBA): calcd for C33 524.2199 (M); found 524.2224.
1
1
6
2
2
3
32 6
H O
(
DHP) were from Wako Pure Chemical Ind., Ltd., and p-toluene-
sulfonic acid (p-TsOH), imidazole, and magnesium were from
Kishida Chemical Co., Inc., and used as received. Flash column
chromatography was performed on silica gel 60N (40e50
which was purchased from Kanto Chemical Co., Inc., and pre-
parative thin layer chromatography (TLC) on Wakogel B-10 (45 m)
mm),
m
from Wako Pure Chemical Ind., Ltd. The solvents were commer-
cially available first grade and used as received.
The disubstituted naphthalene 1a was prepared by the reaction
of 2,7-dihydroxynaphthalene with ethyl bromoacetate, reduction
with lithium aluminum hydride (LAH), protection of one of the
hydroxyl groups with dihydropyran (DHP), reaction with 3-bromo-
4.2.3. 2-((5-(2-((3,3-Diphenylallyl)oxy)ethoxy)naphthalen-1-yl)oxy)
ethyl 3-oxobutanoate (1c). Yellow microcrystals (from CHCl
3
), mp
ꢀ
87e90 C. R
O). H NMR (500 MHz, CDCl ) d
3
f
¼0.44 (Et
2
O-hexane, 7:3 v/v). IR (KBr)
n
1751, 1717 (C]
1
7.77 (1H, d, J¼8.5 Hz, arom H), 7.71
(1H, d, J¼8.5 Hz, arom H), 7.24e7.17 (5H, m, arom H), 7.15e7.10 (5H,
m, arom H), 7.08 (2H, dd, J¼8.0, 1.7 Hz, arom H), 6.68 (1H, d,
J¼7.6 Hz, arom H), 6.66 (1H, d, J¼7.7 Hz, arom H), 6.16 (1H, t,
1,1-diphenylpropene, deprotection, and then esterification with
diketene. The other disubstituted naphthalenes 1bed and 4 were
also prepared by a similar procedure (see Supplementary data).
J¼6.7 Hz, C]CH), 4.48 (2H, t, J¼4.5 Hz, CH
2
), 4.12 (2H, t, J¼4.5 Hz,
), 3.76
CH
2H, t, J¼4.5 Hz, CH
NMR (125 MHz, CDCl
54.0, 145.3, 141.9, 139.3, 126.9, 126.7 (arom C), 129.9 (2C), 128.34
2C), 128.30 (2C), 127.8 (2C), 127.7, 127.6, 125.5,125.4,125.2 (C]CH),
15.3,114.5,105.9,105.8 (arom CH), 69.2, 68.8, 67.9, 66.2, 63.7 (CH ),
). FAB HRMS (acetone/NBA): calcd for
524.2199 (M); found 524.2213.
2
), 4.11 (2H, t, J¼4.7 Hz, CH
), 3.35 (2H, s, CH
200.5 (CH
2
), 4.08 (2H, d, J¼6.7 Hz, CH
C]O), 2.03 (3H, s, CH
C]O), 167.3 (>C]O), 154.5,
2
13
(
2
2
3
).
C
3
)
d
3
1
(
1
2
2 3
50.0 (CH C]O), 30.3 (CH
33 32 6
C H O
4
.2.1. 2-((7-(2-((3,3-Diphenylallyl)oxy)ethoxy)naphthalen-2-yl)oxy)
ethyl 3-oxobutanoate (1a). Yellow liquid. R O-hexane, 5:5
¼0.35 (Et
1746,1719 (C]O). H NMR (500 MHz, CDCl 7.65
1H, d, J¼8.7 Hz, arom H), 7.64 (1H, d, J¼9.6 Hz, arom H), 7.37e7.34
3H, m, arom H), 7.26e7.23 (5H, m, arom H), 7.18 (2H, d, J¼1.6,
.1 Hz, arom H), 7.03e6.98 (4H, m, arom H), 6.27 (1H, t, J¼6.8 Hz,
C]CH), 4.54 (2H, t, J¼4.5 Hz, CH ), 4.26 (2H, t, J¼4.5 Hz, CH ), 4.20
2H, t, J¼4.5 Hz, CH ), 4.18 (2H, d, J¼6.8 Hz, CH ), 3.82 (2H, t, J¼4.5,
CH ), 3.49 (2H, s, CH
CDCl 200.2 (CH C]O), 167.0 (OC]O), 157.4, 156.8, 144.9, 141.7,
39.1, 135.6 (arom C), 125.2 (C]CH), 124.5 (>C]CH), 129.7 (2C),
29.2 (2C), 129.0 (2C), 128.1 (2C), 127.5 (2C), 127.4 (2C), 116.6, 116.0,
06.3, 106.2 (arom CH), 68.9, 68.5, 67.3, 65.5, 63.5 (CH ), 49.8
f
2
1
v/v). IR (CHCl
(
(
3
)
n
3
) d
8
2
2
4.2.4. 2-((6-(2-((3,3-Diphenylallyl)oxy)ethoxy)naphthalen-2-yl)oxy)
(
2
2
ethyl 3-oxobutanoate (1d). Yellow liquid. R ¼0.31 (Et O-hexane, 5:5
f
2
1
3
1
2
2
C]O), 2.24 (3H, s, CH
3
). C NMR (125 MHz,
3 3
v/v). IR (CHCl ) n 1745, 1717 (C]O). H NMR (500 MHz, CDCl ) d 7.61
3
)
d
3
(1H, d, J¼8.9 Hz, arom H), 7.60 (1H, d, J¼8.9 Hz, arom H), 7.36e7.31
(3H, m, arom H), 7.26e7.24 (5H, m, arom H), 7.18 (2H, dd, J¼1.7,
8.1 Hz, arom H), 7.16e7.11 (2H, m, arom H), 7.07 (2H, d, J¼1.7 Hz,
1
1
1
2
arom H), 6.27 (1H, t, J¼6.7 Hz, C]CH), 4.52 (2H, t, J¼4.7 Hz, CH ),
2

6968
C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
4
.24 (2H, t, J¼4.7 Hz, CH
J¼4.7 Hz, CH ), 3.80 (2H, t, J¼4.7 Hz, CH
.23 (3H, s, CH
67.0 (>C]O), 155.5, 155.0, 145.1, 139.0130.1, 129.8 (arom C), 141.9
C]CH), 129.8 (2C), 128.5, 128.33 (2C), 128.3, 128.2 (2C), 127.7 (2C),
27.7, 127.6, 119.6, 119.0, 107.4, 107.2 (arom CH), 69.1, 68.7, 67.5, 65.9,
3.4 (CH ), 50.0 (CH C]O), 30.2 (CH ). FAB HRMS (acetone/NBA):
calcd for C33 524.2199 (MH); found 524.2223.
2
), 4.17 (2H, d, J¼6.7 Hz, CH
), 3.49 (2H, s, CH
). C NMR (125 MHz, CDCl 200.5 (CH
2
), 4.16 (2H,
C]O),
C]O),
2
2
2
13
2
1
(
1
3
3
)
d
3
6
2
2
3
H
32
O
6
5
2 2
4
1
.3.1. [12](2,7)Naphthalenophane (2a): 1 -Methyl-1 ,1 -diphenyl-
2
3
,1 -dihydro-3,6,8,11-tetraoxa-1(3,4)-furana-7(2,7)-naph-
thalenacyclododecaphan-2-one. Pale pink prisms (from CHCl
3
/
ꢀ
hexane), mp 260e261 C. R
f
¼0.49 (EtOAc-hexane, 2:8 v/v). IR
1
(
(
5
3
KBr) n 1676 (C]O), 1636 (C]C). H NMR (500 MHz, CDCl ) d 7.55
0
0
1H, d, J¼9.0 Hz, naph CH-4 or 5 ), 7.52 (1H, d, J¼9.0 Hz, naph CH-
0
0
0
0
or 4 ), 7.53 (1H, d, J¼2.5 Hz, naph CH-1 or 8 ), 7.52 (1H, d,
0
0
J¼2.5 Hz, naph CH-8 or 1 ), 7.30e7.14 (10H, m, phꢂ2), 6.88 (1H, dd,
0
0
0
0
J¼2.5, 9.0 Hz, CH-3 or 6 ), 6.83 (1H, dd, J¼2.5, 9.0 Hz, CH-6 or 3 ),
4
.2.5. 2-(2-((6-(2-(2-((3,3-Diphenylallyl)oxy)ethoxy)ethoxy)naph-
4
.78 (1H, ddd, J¼14.0, 3.5, 2.0 Hz, HeCHe at C-4), 4.67 (1H, ddd,
thalen-2-yl)oxy)ethoxy)ethyl 3-oxobutanoate (4). Yellow liquid.
1
J¼14.0, 8.0, 2.0 Hz, HeCHe at C-5), 4.35 (1H, dt, J¼14.0, 3.5 Hz,
R
f
¼0.63 (Et
CDCl
7.58 (2H, d, J¼8.8 Hz, arom H), 7.32e7.12 (12H, m, arom H),
.06 (2H, m, arom H), 6.24 (1H, t, J¼6.6 Hz, C]CH), 4.29 (2H, t,
), 4.14 (4H, m, CH ),
.85e3.81 (4H, m, CH ), 3.68 (2H, t,
J¼4.5 Hz, CH ), 3.57 (2H, t, J¼4.5 Hz, CH
.16 (3H, s, CH
66.7 (OC]O), 155.0, 154.8, 144.1, 138.8, 127.16, 127.14, (arom C),
41.4 (>C]CH), 129.3 (2C), 127.84 (2C), 127.82 (3C), 127.79 (3C),
27.19 (3C), 119.0, 118.8, 106.7 (arom CH), 125.3 (C]CH), 70.4, 69.3,
9.23, 69.19, 68.6, 68.5, 67.1, 67.0, 63.4 (CH ), 49.5 (CH C]O), 29.7
CH ). FAB HRMS (acetone/NBA): calcd for C37 612.2723 (M);
found 612.2726.
2 3
O). IR (CHCl ) n 1745, 1717 (C]O). H NMR (500 MHz,
HeCHe at C-5), 4.13 (1H, ddd, J¼13.8, 7.3, 1.5 Hz, HeCHe at C-9),
3
) d
4
.05 (1H, ddd, J¼14.0, 8.0, 2.0 Hz, HeCHe at C-4), 3.97 (1H, dq,
7
J¼13.8, 2.0 Hz, HeCHe at C-9), 3.92 (1H, br s, HeC< at C-13), 3.62
J¼4.5 Hz, CH
2
2
), 4.08 (2H, d, J¼6.6 Hz, C]CHCH
2
(
1H, dd, J¼10.0, 3.0 Hz, HeCHe at C-12), 2.98 (1H, d, J¼10.0 Hz,
3
2
), 3.73 (2H, t, J¼4.5 Hz, CH
2
HeCHe at C-12), 2.76 (1H, dd, J¼11.5, 2.0 Hz, HeCHe at C-10), 2.50
2
2
), 3.39 (2H, s, CH
2
C]O),
13
(1H, ddd, J¼11.5, 7.3, 2.0 Hz, HeCHe at C-10), 2.09 (3H, s, CH at C-
3
2
1
1
1
6
(
3 3 3
). C NMR (125 MHz, CDCl ) d 200.1 (CH C]O),
13
1
6). C NMR (125 MHz, CDCl
3
)
d
167.2 (C]CCH
3
at C-16), 163.9
0
0
(
>C]O at C-2), 155.1, 154.9 (naph-C-O at C-2 and C-7 ), 1434.9,
0
0
1
39.5 (Ph-C), 134.7, 123.2 (naph-C at 4 a and C-8 a), 127.9, 127.4
0
0
(naph-CH at C-4 and C-5 ), 127.2 (2C), 126.9, 126.3 (2C), 1256.9,
2
2
0
1
6
1
25.7 (2C), 125.0 (2C, Ph-CH), 116.3, 116.0 (naph-CH at C-3 and C-
3
40 8
H O
0
0
0
), 1078.8, 107.0 (naph-CH at C-1 and C-8 ), 102.3 (C]CCH
), 93.2 (CeO at C-14), 69.6 (CH at C-10), 67.4 (CH at C-9), 66.9
at C-12), 66.3 (CH at C-5), 63.2 (CH at C-4), 49.4 (C]CCH at
C-13), 14.1 (CH ). FAB HRMS (acetone/NBA/NaI): calcd for
Na 545.1940 (MþNa); found 545.1899. X-ray crystallo-
graphic data: empirical formula C33 ; formula weight 522.57;
colorless prisms; space group P2
/n; cell lengths a¼10.3788(7),
3
at C-
2
2
(CH
2
2
2
4
.3. Oxidation of 2-((7-(2-((3,3-diphenylallyl)oxy)ethoxy)
3
naphthalen-2-yl)oxy)ethyl 3-oxobutanoate (1a) with man-
ganese(III) acetate
33 30 6
C H O
30 6
H O
1
To a 100 mL three-necked flask, manganese(III) acetate dihy-
ꢀ
b¼13.70209(8), c¼18.70260(12) A; cell angles
a
¼90.00,
drate, Mn(OAc)
3
$2H
2
O (161 mg, 0.6 mmol) and glacial acetic acid
ꢀ
ꢀ
3
b
¼104.8307(7),
g
¼90.00 ; cell volume 2571.14 A ; formula units
(
50 mL) were added and degassed under reduced pressure for
0
3
per cell Z¼4, Z ¼0; density
r
¼1.350 g/cm ; absorption coefficient
¼1.54184; total data collected 5352;
¼0.1264; GOF¼1.039.
3
0 min using an ultrasonicator for exchange with an argon atmo-
m
¼0.748; radiation (CuK
a
) l
sphere. The mixture was heated under an argon atmosphere using
R¼0.0479; R
w
ꢀ
an oil bath at 140 C, and after boiling, a solution of the allylox-
ynaphthalenyl oxobutanoate 1a (105 mg, 0.2 mmol) in glacial acetic
acid (5 mL) was dropwise added (0.1 mL/min) using a syringe.
When the solution of 1a (0.2 mL) was poured into the reaction
mixture, the dark-brown color of the reaction mixture turned
transparent, so that additional Mn(OAc)
was added to the mixture. Normally, three portions of
Mn(OAc) $2H O (107 mg, 0.2 mmol) were successively added after
3 2
$2H O (161 mg, 0.6 mmol)
3
2
decoloration of the dark-brownish reaction mixture. Dropwise
adding of the rest of the solution of 1a resumed and the reaction
mixture was continued to be heated under reflux until the dark-
brown color of the solution turned transparent again (total for
41 min). The solvent was removed under reduced pressure and the
residue was triturated with 2 M hydrochloric acid (30 mL). The
aqueous solution was extracted three times with chloroform
(
25 mL) and the combined extracts were washed with a saturated
aqueous solution of sodium hydrogencarbonate, brine, dried over
anhydrous sodium sulfate, and then concentrated to dryness. The
residue was separated on silica gel TLC developed with chloroform,
giving the desired naphthalenophane 2a (37 mg, 35%) (Table 1,
entry 10). The TLC separation of the more polar products afforded
the diploid 3a (45 mg) in 22% maximum yield (Table 1, entry 6). The
physical data of 2a and 3a are given below.
5
5
4
1
3
.3.2. [12,12](2,7)Naphthalenophane
(3a):
1 ,13 -Dimethyl-
2
2
2
2
2
3
2
3
,1 ,13 ,13 - t e t r a p h e n y l - 1 ,1 ,13 ,13 - t e t r a h y d r o -
,6,8,11,15,18,20,23-octaoxa-1(3,4),13(4,3)-difurana-7,19(2,7)-di-
liquid. IR
8.07e6.90 (32H,
and CH), 2.39e2.02 (12H, m,
naphthalenacyclotetracosaphane-2,14-dione. Brown
1
(CHCl
3 3
) n 1728 (C]O). H NMR (500 MHz, CDCl ) d
m, arom H), 4.72e3.47 (16H, m, CH
2

C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
6969
CH
2
and CH
3
). FAB HRMS (acetone/NBA/NaI): calcd for C66
60
H O
12Na
naphthalenophane 2c (16 mg) was obtained in 15% yield (Table 2,
entry 15). The physical data of 2c are given below.
1067.3982 (MþNa); found 1067.4015.
4
.4. Oxidation of 2-((8-(2-((3,3-diphenylallyl)oxy)ethoxy)
naphthalen-1-yl)oxy)ethyl 3-oxobutanoate (1b) with man-
ganese(III) acetate
To a 200 mL three-necked flask, manganese(III) acetate dihy-
drate, Mn(OAc) $2H O (210 mg, 0.8 mmol) and glacial acetic acid
50 mL) were added and degassed under reduced pressure for
3
2
(
3
0 min using an ultrasonicator for exchange with an argon atmo-
5
2 2
sphere. The mixture was heated under an argon atmosphere using
an oil bath at 140 C, and after boiling, a solution of the allylox-
4.5.1. [12](1,5)Naphthalenophane (2c): 1 -Methyl-1 ,1 -diphenyl-
ꢀ
2
3
1 ,1 -dihydro-3,6,8,11-tetraoxa-1(3,4)-furana-7(1,5)-naph-
ynaphthalenyl oxobutanoate 1b (105 mg, 0.2 mmol) in glacial acetic
acid (50 mL) was dropwise added using a 100 mL dropping funnel.
The reaction mixture was continued to be heated under reflux until
the dark-brown color of the solution turned transparent (total for
thalenacyclododecaphan-2-one. Colorless prisms (from CH Cl ), mp
2
2
ꢀ
226e227 C. R ¼0.43 (EtOAc-hexane, 2:8 v/v). IR (KBr)
f
n 1690 (C]
8.03 (1H, d, J¼8.5 Hz, arom H), 7.88
1
O). H NMR (500 MHz, CDCl )
3
d
(1H, d, J¼8.5 Hz, arom H), 7.44 (1H, t, J¼7.5 Hz, arom H), 7.35 (1H, t,
J¼7.5 Hz, arom H), 7.31e7.14 (10H, m, arom H), 7.11 (1H, d, J¼7.5 Hz,
arom H), 7.07 (1H, d, J¼7.5 Hz, arom H), 4.88e4.84 (1H, m),
4.67e4.57 (2H, m), 4.12e4.06 (3H, m), 3.16 (1H, m), 2.93e2.88 (1H,
m), 2.37 (1H, dd, J¼9.6 and 6.7 Hz), 2.06e2.03 (1H, m), 1.87 (1H, dd,
2
6 min). The solvent was removed under reduced pressure and the
residue was triturated with 2 M hydrochloric acid (30 mL). The
aqueous solution was extracted three times with chloroform
(
25 mL) and the combined extracts were washed with a saturated
13
aqueous solution of sodium hydrogencarbonate, brine, dried over
anhydrous sodium sulfate, and then concentrated to dryness. The
residue was separated on silica gel TLC developed with EtOAc/
hexane (3:7 v/v), giving the desired naphthalenophane 2b (31 mg,
J¼9.6 and 2.1 Hz), 1.94 (3H, s, CH ). C NMR (125 MHz, CDCl )
3
3
d
3
167.1 (C]CCH at C-16), 164.1 (>C]O at C-2), 156.4, 155.7, 144.7,
140.5, 130.3, 129.3 (arom C), 128.2 (2C), 128.1, 128.0, 127.6, 127.1
(2C), 126.9, 126.7, 126.0, 125.4, 124.8, 117.5, 117.1, 114.9, 113.8 (arom
CH), 102.9 (C]CCH3 at C-1), 93.9 (CeO at C-14), 73.6, 72.2, 70.8,
3
0%) (Table 2, entry 5). The physical data of 2b are given below.
6
7.2, 64.2 (CH
etone/NBA): calcd for C33
X-ray crystallographic data: empirical formula C33
weight 522.57; colorless prisms; space group P2 /n; cell lengths
2
), 49.7 (C]CCH at C-13), 14.7 (CH
523.2121 (MþH); found 523.2119.
; formula
3
). FAB HRMS (ac-
31 6
H O
30 6
H O
1
ꢀ
a¼12.49783(14), b¼9.48078(11), c¼22.6036(2) A; cell angles
ꢀ
ꢀ
3
a
¼90.00,
formula units per cell Z¼4; density
coefficient
¼0.741; radiation (CuK
lected 5352; R¼0.0500; R ¼0.1355; GOF¼1.041.
b
¼104.2923(11),
g
¼90.00 ; cell volume 2595.39(5) A ;
3
r
¼1.337 g/cm ; absorption
¼1.54184; total data col-
m
a
) l
w
4
8
.4.1. [12](1,8)Naphthalenophane (2b): 12-Methyl-14,14-diphenyl-
,9,14a,15,17,18-hexahydro-11H,14H-furo[3,4-m]naphtho[1,8-ef]
[
R
(
1,4,8,11]tetraoxacyclopentadecin-11-one. Yellow
amorphous.
1
f
¼0.56 (EtOAc-hexane, 3:7 v/v). IR (CHCl
3
)
n
1697 (C]O). H NMR
500MHz,CDCl
3
)
d
7.56(2H, d,J¼7.0Hz, H-3andH-4), 7.36e7.17(12H,
m, arom H), 6.75 (1H, d, J¼7.0 Hz, H-1 or H-6), 6.67 (1H, d, J¼7.5 Hz, H-
6
4
or H-1), 4.81e4.77 (1H, m, H-9), 4.39e4.37 (2H, m, H-8 and H-9),
.29e4.27 (1H, m, H-8), 4.22e4.21 (2H, m, H-18), 4.10 (1H, br s, H-
1
4a), 3.80e3.77 (1H, m, H-17), 3.75e3.72 (1H, m, H-15), 3.59e3.56
13
(
1H, m, H-17), 3.52e3.49 (1H, m, H-15), 2.36 (3H, s, CH
125 MHz, CDCl 168.4 (C-12),165.6 (C-11),156.1,155.7 (C-6a and C-
9a), 145.1, 140.5, 137.5, 117.4 (arom C), 128.1 (2C), 127.7, 127.5 (2C),
27.1 (2C), 126.8 (2C), 126.2 (2C), 120.7 (2C), 120.4, 105.9, 105.7 (arom
CH), 103.8 (C-11a), 94.8 (C-14), 70.1 (C-15), 69.4 (C-18), 67.5 (C-17),
6.3 (C-8), 62.0 (C-9), 51.3 (C-14a), 14.3 (CH ). FAB HRMS (acetone/
NBA/NaI): calcd for C33
Na 545.1940 (MþNa); found 545.1919.
3
). C NMR
(
1
1
3
) d
5
5
4
1
3
.5.2. [12,12](1,5)Naphthalenophane
(3c):
1 ,13 -dimethyl-
2
2
2
2
2
3
2
3
,1 ,13 ,13 - t e t r a p h e n y l - 1 ,1 ,13 ,13 - t e t r a h y d r o -
,6,8,11,15,18,20,23-octaoxa-1(3,4),13(4,3)-difurana-7,19(1,5)-di-
amorphous.
naphthalenacyclotetracosaphane-2,14-dione. Yellow
¼0.44 (EtOAc-hexane, 3:7 v/v). IR (CHCl 1697 (C]O). H NMR
500 MHz, CDCl
6
3
1
R
(
f
3
) n
30 6
H O
3
)
d
7.78 (2H, t, J¼8.5 Hz, arom H), 7.63e7.59 (4H, m,
arom H), 7.53 (2H, t, J¼8.6 Hz, arom H), 7.39e7.14 (20H, m, arom H),
6.74 (2H, d, J¼7.6 Hz, arom H), 6.08 (1H, d, J¼7.5 Hz, arom H), 6.04
(1H, d, J¼7.5 Hz, arom H), 4.79e4.75 (2H, m), 4.44e4.27 (6H, m),
4.09 (2H, dd, J¼17.1 and 7.8 Hz), 3.58 (2H, ddd, J¼18.2, 9.8, 2.3 Hz),
4
.5. Oxidation of 2-((5-(2-((3,3-diphenylallyl)oxy)ethoxy)
naphthalen-1-yl)oxy)ethyl 3-oxobutanoate (1c) with man-
ganese(III) acetate
3
.19e3.04 (6H, m), 2.88e2.77 (2H, m), 2.71e2.64 (2H, m), 2.39 (6H,
Manganese(III) acetate dihydrate, Mn(OAc)
3
$2H
2
O (210 mg,
s, CH ). FAB HRMS (acetone/NBA): calcd for C66H60O12 1044.4085
3
0
.8 mmol) in glacial acetic acid (90 mL) was degassed under re-
(M); found 1044.4095.
duced pressure for 30 min using an ultrasonicator for exchange
with an argon atmosphere and heated using an oil bath at 140 C.
After boiling, a solution of the allyloxynaphthalenyl oxobutanoate
ꢀ
4.6. Oxidation of 2-((6-(2-((3,3-diphenylallyl)oxy)ethoxy)
naphthalen-2-yl)oxy)ethyl 3-oxobutanoate (1d) with Man-
ganese(III) acetate
1
c (105 mg, 0.2 mmol) in glacial acetic acid (10 mL) was dropwise
added and the mixture was continued to be heated under reflux
until the dark-brown color of the solution turned transparent (total
for 11 min). After the same work-up described above, the desired
To glacial acetic acid (100 mL), manganese(III) acetate dihydrate,
Mn(OAc) $2H O (220 mg, 0.8 mmol) and the allyloxynaphthalenyl
3 2

6970
C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
oxobutanoate 1d (104.5 mg, 0.2 mmol) were added and degassed
7.02 (2H, d, J¼7.1 Hz, arom H), 4.41e4.31 (6H, m), 4.04e3.99 (1H,
m), 3.82 (2H, t, J¼4.3 Hz), 3.66 (2H, t, J¼4.3 Hz), 3.54e3.51 (4H, m),
3.12 (1H, dd, J¼9.6, 2.3 Hz), 3.05 (1H, ddd, J¼2.8, 5.8, 12.0 Hz),
according to the same procedure described above and then heated
ꢀ
at 140 C. It was confirmed by the color change from dark brown to
transparent of the reaction mixture that the Mn(III) was completely
consumed after 5 min. After the same work-up described above, the
corresponding diploid 3d (8.1 mg) was obtained in 4% yield along
with an intractable mixture (Table 2, entry 17). The physical data of
2.84e2.79 (1H, m), 2.71e2.67 (1H, m), 1.92 (3H, s, CH
3
). FAB HRMS
(acetone/NBA): calcd for C37H O 610.2567 (M); found 610.2652.
38 8
Acknowledgements
3
d are given below.
This research was supported by a Grant-in-Aid for Scientific
Research (C), No. 25410049, from the Japan Society for the Pro-
motion of Science. We also acknowledge Nissan Chemical In-
dustries, Ltd., for their financial support.
Supplementary data
Supplementary data (Preparation details of the disubstituted
1
13
naphthalenes 1aed and 4, copies of H NMR, C NMR, DEPT, IR, and
MS spectral charts of disubstituted naphthalenes 1aed and 4,
naphthalenophanes 2aec, 3a, 3c, 3d, 5, and 2D NMR spectral charts
of 2a, 2c are available in Supplementary data.) related to this article
can be found at http://dx.doi.org/10.1016/j.tet.2016.09.025.
5
5
4
1
3
.6.1. [12,12](2,6)Naphthalenophane
(3d):
1 ,13 -dimethyl-
2
2
2
2
2
3
2
3
,1 ,13 ,13 - t e t r a p h e n y l - 1 ,1 ,13 ,13 - t e t ra h y d r o -
,6,8,11,15,18,20,23-octaoxa-1(3,4),13(4,3)-difurana-7,19(2,6)-di-
¼0.35
1701 (C]O). H NMR
7.61e7.00 (28H, m, arom H), 6.85 (2H, dt, J¼8.5,
References and notes
naphthalenacyclotetracosaphane-2,14-dione. Brown liquid. R
f
1. Ruzicka, L. Helv. Chim. Acta 1926, 9, 715e729.
2. Ito, Y.; Yoshinaga, T.; Nishino, H. Tetrahedron 2010, 66, 2683e2694 and the
references cited therein.
1
(
EtOAc-hexane, 3:7 v/v). IR (CHCl
3
) n
(
500 MHz, CDCl
3
) d
3. Ito, Y.; Tomiyasu, Y.; Kawanabe, T.; Uemura, K.; Ushimizu, Y.; Nishino, H. Org.
2
.4 Hz, arom H), 6.52 (2H, dd, J¼10.0, 2.4 Hz, arom H), 4.6e3.2 (22H,
Biomol. Chem. 2011, 9, 1491e1507 and the references cited therein.
4
. For review, see: (a) Cram, D. J.; Cram, J. M. Acc. Chem. Res. 1971, 4, 204e213; (b)
Misumi, S.; Otsubo, T. Acc. Chem. Res. 1978, 11, 251e256; (c) Cyclophanes; Keehn,
P. M., Rosenfeld, S. M., Eds.; Academic: New York, NY, 1983; (d) V o€ gtle, F. Cy-
m, CH
2
, CH), 2.36 (6H, s, CH
3
ꢂ2). FAB HRMS (acetone/NBA): calcd
for C66H O12 1044.4085 (M); found 1044.4106.
60
clophan Chemie; Teubner, B. G.: Stuttgart, Germany, 1990; (e) Pascal, R. A., Jr. Eur.
J. Org. Chem. 2004, 3763e3771; (f) Gleiter, R.; Hopf, H. In Modern Cyclophane
Chemistry; WILEY-VCH: Weinheim, Germany, 2004.
4
.7. Oxidation of 2-(2-((6-(2-(2-((3,3-Diphenylallyl)oxy)eth-
5. (a) Tobe, Y.; Ueda, K.; Kaneda, T.; Kakiuchi, K.; Odaira, Y.; Kai, Y.; Kasai, N. J. Am.
Chem. Soc. 1987, 109, 1136e1144; (b) Cory, R. M.; McPhail, C. L. Tetrahedron Lett.
oxy)ethoxy)naphthalen-2-yl)oxy)ethoxy)ethyl 3-
oxobutanoate (4) with Manganese(III) acetate
1996, 37, 1987e1990; (c) Rajakumar, P.; Srisailas, M. Tetrahedron Lett. 2003, 44,
2
2
885e2887; (d) Wei, C.; Mo, K.-F.; Chan, T.-L. J. Org. Chem. 2003, 68,
948e2951; (e) Kato, S.; Matsumoto, T.; Ideta, K.; Shimosaki, T.; Goto, K.;
Shinmyozu, T. J. Org. Chem. 2006, 71, 4723e4733; (f) Shibahara, M.; Watanabe,
M.; Iwanaga, T.; Ideta, K.; Shinmyozu, T. J. Org. Chem. 2007, 72, 2865e2877; (g)
Kato, S.; Nonaka, Y.; Shimasaki, T.; Goto, K.; Shinmyozu, T. J. Org. Chem. 2008, 73,
4063e4075; (h) Shibahara, M.; Watanabe, M.; Iwanaga, T.; Matsumoto, T.;
Ideta, K.; Shinmyozu, T. J. Org. Chem. 2008, 73, 4433e4442; (i) Miyazaki, T.;
Shibahara, M.; Fujishige, J.; Watanabe, M.; Goto, K.; Shinmyozu, T. J. Org. Chem.
To glacial acetic acid (45 mL), manganese(III) acetate dihydrate,
Mn(OAc) $2H O (110 mg, 0.4 mmol) was added and degassed
3 2
according to the same procedure described above. The solution was
heated under reflux and the allyloxynaphthalenyl oxobutanoate 4
(
122.3 mg, 0.2 mmol) dissolved in acetic acid (5 mL) was slowly
2014, 79, 11440e11453; (j) Fujitsuka, M.; Miyazaki, T.; Lu, C.; Shinmyozu, T.;
added (0.5 mL/min) using a syringe. When the solution of 4 in
acetic acid (1.6 mL) was added, the color of the solution changed
Majima, T. J. Phys. Chem. A 2016, 120, 1184e1189.
. (a) Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc.
Jpn. 1979, 52, 1989e1993; (b) Hu, T.; Takenaka, N.; Panek, J. S. J. Am. Chem. Soc.
6
from dark brown to transparent. Additional Mn(OAc)
3 2
$2H O
2002, 124, 12806e12815.
(
107.8 mg, 0.4 mmol) was then put into the boiling solution and the
7. Corey, E. J.; Nicolaou, K. C. J. Am. Chem. Soc. 1974, 96, 5614e5616.
8. (a) Shiina, I.; Kubota, M.; Osumi, H.; Hashizume, M. J. Org. Chem. 2004, 69,
rest of 4 in acetic acid was slowly added. The Mn(III) was com-
pletely consumed within 17 min. After the same work-up men-
tioned above, the residue was separated by silica gel TLC developed
with EtOAc/hexane (5:5 v/v), isolating the desired [18](2,6)naph-
thalenophane 5 (3.5 mg, 3%). The physical data of 5 are given below.
1822e1830; (b) Shiina, I.; Hashizume, M.; Yamai, Y.; Oshiumi, H.; Shimazaki, T.;
Takasuna, Y.; Ibuka, R. Chem.dEur. J. 2005, 11, 6601e6608.
9
. Schinzer, D.; Limberg, A.; Bauer, A.; Bohm, O. M.; Cordes, M. Angew. Chem., Int.
€
Ed. Engl. 1997, 36, 523e524.
0. (a) Yanagidate, M.; Takayama, K.; Takeuchi, M.; Nishimura, J.; Shizuka, H. J. Phys.
Chem. 1993, 97, 8881e8888; (b) Morita, M.; Kishi, T.; Tanaka, M.; Tanaka, J.;
Ferguson, J.; Sakata, Y.; Misumi, S.; Hayashi, T.; Mataga, N. Bull. Chem. Soc. Jpn.
1
1978, 51, 3449e3457; (c) Nakamura, Y.; Tsuihiji, T.; Mita, T.; Minowa, T.; Tobita,
S.; Shizuka, H.; Nishimura, J. J. Am. Chem. Soc. 1996, 118, 1006e1012; (d) Na-
kamura, Y.; Kaneko, M.; Tani, K.; Shinmyozu, T.; Nishimura, J. J. Org. Chem. 2002,
67, 8706e8709; (e) Ohkita, H.; Ito, S.; Yamamoto, M.; Tohda, Y.; Tani, K. J. Phys.
Chem. A 2002, 106, 2140e2145; (f) Benten, H.; Ohkita, H.; Ito, S.; Yamamoto, M.;
Sakumoto, N.; Hori, K.; Tohda, Y.; Tani, K.; Nakamura, Y.; Nishimura, J. J. Phys.
Chem. B 2005, 109, 19681e19687; (g) Benten, H.; Guo, J.; Ohkita, H.; Ito, S.;
Yamamoto, M.; Sakumoto, N.; Hori, K.; Tohda, Y.; Tani, K. J. Phys. Chem. B 2007,
111, 10905e10914; (h) Tani, K.; Sakumoto, N.; Kubono, K.; Hori, K.; Tohda, Y.;
Benten, H.; Ohkita, H.; Ito, S.; Yamamoto, M. Chem. Lett. 2009, 38, 140e141; (i)
Tamai, Y.; Ohkita, H.; Shimada, J.; Benten, H.; Ito, S.; Yamanaka, S.; Hisada, K.;
Tani, K.; Kubono, K.; Shinmyozu, T. J. Phys. Chem. A 2013, 117, 7776e7785.
11. Recent reviews for the Mn(III)-based oxidation: (a) Demir, A. S.; Emrullahoglu,
M. Curr. Org. Synth. 2007, 4, 321e351; (b) Pan, X.-Q.; Zou, J.-P.; Zhang, W. Mol.
Divers 2009, 13, 421e438; (c) Burton, J. W. Manganese(III) Acetate, CAN, and
Fe(III) Salts in Oxidative Radical Chemistry In Encyclopedia of Radicals in
Chemistry, Biology and Materials; Chatgilialoglu, C., Studer, A., Eds.; Wiley: New
York, NY, 2012; pp 901e941; (d) Jahn, U. Top. Curr. Chem. 2012, 320, 121e190; (e)
Mondal, M.; Bora, U. RSC Adv. 2013, 3, 18716e18754; (f) Wang, G.-W.; Li, F.-B. J.
5
2 2
4
1
.7.1. [18](2,6)Naphthalenophane (5): 1 -methyl-1 ,1 -diphenyl-
2
3
,1 -dihydro-3,6,9,11,14,17-hexaoxa-1(3,4)-furana-10(2,6)-naph-
¼0.66 (EtOAc-
1728 (C]O). H NMR (500 MHz,
7.59 (2H, t, J¼9.0 Hz, arom H), 7.42e7.18 (12H, m, arom H),
thalenacyclooctadecaphan-2-one. Yellow liquid. R
f
1
hexane, 5:5 v/v). IR (CHCl
CDCl
3
) n
3
) d

C. Matsumoto et al. / Tetrahedron 72 (2016) 6963e6971
6971
Nanosci. Nanotech 2007, 7, 1162e1175; (g) Nishino, H. Manganese(III)-Based
Peroxidation of Alkenes to Heterocycles In Topics in Heterocyclic Chemistry,
Bioactive Heterocycles I; Eguchi, S., Ed.; Springer: Berlin, Germany, 2006;
pp 39e76.
Actually, the oxidation of a mixture of 1,1-diphenylethene and ethyl 1,1,1-
trifluoroacetoacetate with Mn(OAc)
(molar ratio¼1:1:2) afforded ethyl 5,5-
diphenyl-2-(trifluoromethyl)-4,5-dihydrofuran-3-carboxylate
3
19
in 41% yield,
while the same reaction using the acetoacetate gave the corresponding dihy-
drofuran in 77% yield.1
6b
1
2. When the reaction was conducted using the stoichiometric amount of the
oxidant (1a:Mn(OAc)
recovered.
3. Ito, Y.; Jogo, S.; Fukuda, N.; Okumura, R.; Nishino, H. Synthesis 2011, 1365e1374.
4. One of the reviewers suggested that the yield of naphthalenophanes which
3
¼1:2),
a
small amount of the naphthalene 1a was
16. (a) Yilmaz, M.; Yakut, M.; Pekel, T. Synth. Commun. 2008, 38, 914e927; (b)
Matsumoto, R.; Nishino, H. Synth. Commun. 2015, 45, 1807e1816.
17. Nishino, H.; Kajikawa, S.; Hamada, Y.; Kurosawa, K. Tetrahedron Lett. 1995, 36,
5753e5756.
1
1
would be obtained using 1,1-bis(4-halophenyl)ethenyl substrate might increase
compared to that using the 1,1-diphenylethenyl-naphthalenes 1aed. However,
the effect of the substituent group such as a halo group has already been
proved, that is, the yield of dihydrofurans produced by the Mn(III)-based oxi-
18. Ouyang, J.; Nishino, H.; Kurosawa, K. J. Heterocycl. Chem. 1995, 32, 1783e1792.
19. Wang, Y.; Han, J.; Chen, J.; Cao, W. Chem. Commun. 2016, 6817e6820.
20. The methyl protons of 3-acetyl-2-methyl-5,5-diphenyl-4,5-dihydrofuran nor-
mally appeared at
d 2.32 ppm. See Nishino, H. Bull. Chem. Soc. Jpn. 1985, 58,
16
dation of 1,1-bis(4-halophenyl)ethenes in the presence of acetoacetate esters
1922e1927.
and acetylacetone17 was quite similar or low compared to that using 1,1-
diphenylethene. Furthermore, it was reported that the Mn(III)-based macro-
cyclization using 4-chlorophenyl-substituted diene led to decrease the yield of
the corresponding macrodiolide compared to that using the diene bearing
phenyl group.18
21. One of the reviewers suggested that conformational ring flipping of 2a would
not be permitted at room temperature because the peaks of H-12 methylene
and H-13 methine protons distinguishably appeared. However, when the
naphthalene ring of 2a would rotate, dihedral one of the H-12 methylene
proton and H-13 methine proton angle was almost similar both in the most
stable rotamers based on our molecular modeling study.
22. X-ray coordinates were deposited with the Cambridge Crystallographic Data
Centre:(a) 2a: CCDC 1483190 and (b) 2c: CCDC 1483191.
23. Kikue, N.; Takahashi, T.; Nishino, H. Heterocycles 2015, 90, 540e562.
1
5. One of the reviewers also suggested that the reaction of naphthyl 1,1,1-
trifluoroacetoacetate ester instead of acetoacetate esters such as 1aed should
be carried out. However, it could be considered that the use of the tri-
fluoroacetoacetate ester might be unsuitable in the dihydrofuranation due to
the strong electron-withdrawing character of the trifluoromethyl group.