Rhenium-catalyzed synthesis of naphthalene derivatives via insertion of aldehydes into a C-H bond

Article abstract of DOI:10.1016/j.tet.2007.05.083

A rhenium complex, [ReBr(CO)₃(THF)]₂, catalyzed reactions of aromatic ketimines and aldehydes with dienophiles, followed by dehydration, to give naphthalene derivatives in good to excellent yields. This reaction proceeds via C-H bond activation, insertion of an aldehyde, intramolecular nucleophilic cyclization, reductive elimination, elimination of aniline and Diels-Alder reaction. After dehydration, naphthalene derivatives were formed.

Full text of DOI:10.1016/j.tet.2007.05.083

Tetrahedron 63 (2007) 8463–8468
Rhenium-catalyzed synthesis of naphthalene
derivatives via insertion of aldehydes into a C–H bond
*
Yoichiro Kuninobu, Yuta Nishina and Kazuhiko Takai
*
Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University,
Tsushima, Okayama 700-8530, Japan
Received 20 March 2007; revised 11 May 2007; accepted 22 May 2007
Available online 26 May 2007
Dedicated to Professor Hisashi Yamamoto in recognition of his significant contribution to modern synthetic organic chemistry
Abstract—A rhenium complex, [ReBr(CO)3(THF)]2, catalyzed reactions of aromatic ketimines and aldehydes with dienophiles, followed by
dehydration, to give naphthalene derivatives in good to excellent yields. This reaction proceeds via C–H bond activation, insertion of an
aldehyde, intramolecular nucleophilic cyclization, reductive elimination, elimination of aniline and Diels–Alder reaction. After dehydration,
naphthalene derivatives were formed.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
We report herein the rhenium-catalyzed synthesis of naph-
thalene derivatives by the reactions of aromatic ketimines
and aldehydes with olefins via C–H bond activation.
Naphthalene derivatives are useful compounds because, for
example, they are partial structures of bioactive molecules1
and liquid crystals.2 Various methods have been reported for
the transition metal-catalyzed or -mediated synthesis of
naphthalene derivatives including gold-catalyzed [4+2]
cycloaddition of o-alkynylbenzaldehydes with alkynes,3
palladium-catalyzed [2+2+2] cocycloaddition of arynes
and diynes,4 ruthenium-catalyzed aromatization of aromatic
enynes,5 ruthenium-catalyzed cyclization of iodoalkyne-
epoxide functionalities,6 and Diels–Alder reaction of
pentacarbonylbenzopyranylidenetungsten(0) complexes with
electron-rich alkenes.7 One way to improve the previous
syntheses is to construct the naphthalene skeleton using
a method based on C–H bond activation.8,9 If this can be
achieved, it would offer an efficient and useful way to syn-
thesize naphthalene derivatives. In 2006, we reported on
the synthesis of isobenzofuran derivatives via C–H bond
activation (Eq. 1), and these compounds can be trapped easily
by dienophiles via a Diels–Alder reaction.9e The Diels–
Alder adducts can be converted easily to naphthalene deriv-
atives via dehydration under acidic conditions.10
2. Results and discussion
Treatment of aromatic ketimine 1a (0.50 mmol), benzalde-
hyde 2a (1.00 mmol), and cyclooctene 3a with a catalytic
amount of [ReBr(CO)3(THF)]2 (2.5 mol %) in toluene at
115 ꢀC for 24 h, followed by treatment with acetic acid and
sulfuric acid at 25 ꢀC for 1.5 h gave naphthalene derivative
4a in 53% yield (Eq. 2). When this reaction was carried out
˚
in the presence of molecular sieves (4 A), the yield of the
naphthalene 4a increased to 73% (Eq. 2). However, this
reaction did not proceed in the presence of transition-metal
complexes, which are usually employed as catalysts for C–H
bond activation and successive insertion of unsaturated mol-
ecules: Ru3(CO)12, RuH2(CO)(PPh3)3, and RhCl(PPh3)3.
Ph
[ReBr(CO)3(THF)]2 (2.5 mol%)
O
Ph
additive
N
+
+
Ph
H
toluene, 115 °C, 24 h
1a
2a
3a
Ph
Ph
O
Ph
[ReBr(CO)3(THF)]2 (2.5 mol%)
MS4Å
O
H2SO4
AcOH
Ph
N
+
Ph
H
toluene, 115 °C, 24 h
Ph
additive
Ph
1a
(1.0 equiv)
2a
6
(2.0 equiv)
93%
ð1Þ
4a 53%
MS4 Å 4a 73%
* Corresponding authors. E-mail addresses: kuninobu@cc.okayama-u.ac.
jp; ktakai@cc.okayama-u.ac.jp
ð2Þ
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.05.083

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Y. Kuninobu et al. / Tetrahedron 63 (2007) 8463–8468
Table 1. Reactions between ketimines, aldehydes and cyclooctenea
R1
R3
R1
[ReBr(CO)3(THF)]2 (2.5 mol%)
MS4Å
O
R2
H2SO4
AcOH
N
+
+
R3
H
toluene, 115 °C, 24 h
1
2
3a
4
Entry
1
R1
Ph
R2
R3
Product
Yieldb (%)
75
PhCH2 1b
Ph 1c
Ph 2a
4a
Ph
2
Ph 2a
Ph 2a
4b
67
Ph
3
1d
4c
79
N
Ph
4
5
6
7
Ph
Ph
Ph
Ph
Ph 1a
Ph 1a
Ph 1a
Ph 1a
p-(MeO)C6H4 2b
p-MeC6H4 2c
p-CF3C6H4 2d
o-MeC6H4 2e
4d
4e
4f
66
72
88
74
4g
8
Ph
Ph 1a
2f
4b
76
Ph
9c
Ph
Me
Ph 1a
Ph 1e
nC8H17 2g
Ph 2a
4h
4i
35
11
10c
a
1 (1.0 equiv), 2 (2.0 equiv), 3a (2.0 equiv).
Isolated yield.
3a (10 equiv).
b
c
The phenyl group on a nitrogen atom of ketimine 1a could be
replaced by a benzyl group without decreasing the yield of
naphthalene 4a (Table 1, entry 1). By using a ketimine 1c,
which was derived from trans-chalcone (benzylidene-
acetophenone) and aniline, the corresponding naphthalene
derivative 4b was obtained in 67% yield (Table 1, entry 2).
Ketimine having an alkyl group at R1 position, 1d, also
afforded tetracyclic compound 4c in 79% yield (Table 1,
entry 3).
obtained in 76% yield (Table 1, entry 8); however, a reac-
tion of 1a with an aliphatic aldehyde, nonanal 2g, pro-
duced naphthalene 4h in 35% yield (Table 1, entry 9).
Another approach to obtain a naphthalene having 1-alkyl-
3-phenyl substituents is a reaction between an imine
derived from an alkyl phenyl ketone and benzaldehyde.
Treatment of a ketimine of acetophenone (R1¼Me) and
benzaldehyde with a catalytic amount of [ReBr(CO)3-
(THF)]2 gave the desired naphthalene 4i in 11% yield
(Table 1, entry 10).
Next, we examined the substituents on the aromatic ring of
aldehydes. The treatment of ketimine 1a with aldehydes
having electron-donating groups, such as a para-methoxy
and para-methyl groups, provided the corresponding
naphthalenes 4d and 4e in 66 and 72% yields, respectively
(Table 1, entries 4 and 5). The yield increased and the
naphthalene derivative 4f was obtained in 88% yield
with an aldehyde bearing an electron-withdrawing group
(Table 1, entry 6). In spite of the bulkiness, o-tolualdehyde
2e afforded the corresponding naphthalene 4g in 74%
yield (Table 1, entry 7). A reaction of 1a with cinnamalde-
hyde 2f also proceeded, and naphthalene derivative 4b was
Several dienophiles could be used in the synthesis of
naphthalene derivatives (Eqs. 3 and 4). By the treatment
of aromatic ketimine 1a with benzaldehyde 2a and male-
imide 3b in the presence of a catalytic amount of [Re-
Br(CO)3(THF)]2 and molecular sieves, Diels–Alder adduct
5a was formed in 79% yield. After isolation, the Diels–Alder
adduct 5a was exposed to acidic conditions, causing dehy-
drative aromatization. As a result, naphthalene derivative
4j was obtained in 86% yield (Eq. 3). Dimethyl maleate 3c
also gave the corresponding naphthalene derivative 4k in
good yield (Eq. 4).
Ph
O
O
Ph
[ReBr(CO)3(THF)]2 (2.5 mol%)
MS4Å
O
Ph
N
+
+
N Me
O
N Me
Ph
H
toluene, 115 °C, 24 h
1a
2a
O
3b
O
Ph
5a 79%
ð3Þ
Ph
O
H2SO4, AcOH
N Me
CH2Cl2, 25 °C, 1.5 h
O
Ph
4j 86%

Y. Kuninobu et al. / Tetrahedron 63 (2007) 8463–8468
8465
Ph
Ph
[ReBr(CO)3(THF)]2 (2.5 mol%)
CO2Me
CO2Me
O
Ph
MS4Å
N
+
+
O
Ph
H
toluene, 115 °C, 24 h
CO2Me
CO2Me
1a
2a
Ph
5b 80%
3c
ð4Þ
Ph
CO2Me
H2SO4, AcOH
CH2Cl2, 25 °C, 1.5 h
CO2Me
Ph
4k 96%
Ph
O
route A
Ph
N
+
N
Ph
H
1a
2g
[ReBr(CO)3(THF)]2 (2.5 mol%)
MS4Å
H2SO4
AcOH
(2.0 equiv)
O
ð5Þ
toluene, 115 °C, 24 h
+
Ph
route B
Ph
H
4l: 50% (route A)
1e
2a
4l: 75% (route B)
(2.0 equiv)
n
C8H17
[ReBr(CO)3(THF)]2 (2.5 mol%)
MS4Å
O
H2SO4
AcOH
N
+
n
Ph
C8H17
H
ð6Þ
ð8Þ
toluene, 115 °C, 24 h
1e
2h
(1.0 equiv)
4m:
38%
An aliphatic aldehyde 2g could be used as the aldehyde com-
ponent of the naphthalene formation (Eq. 5, route A). In ad-
dition, ketimine 1e, which can isomerize to an enamine,
could be employed (Eq. 5, route B). After acidic treatment,
routes A and B produced naphthalene derivative 4l in 50 and
75% yields, respectively (Eq. 5). By the reaction of ketimine
1e with aliphatic aldehyde 2h, the corresponding naphtha-
lene derivative 4m was produced in 38% yield (Eq. 6).
Ph
O
Ph
H2SO4
AcOH, 25 °C, 1.5 h
Ph
5c
Ph
4a >99%
The proposed reaction mechanism is as follows (Scheme 1):
(1) coordination of a nitrogen atom of an imine to a rhenium
center; (2) C–H bond activation;9 (3) insertion of an aldehyde
to the rhenium–carbon bond of the aryl-rhenium intermedi-
ate; (4) intramolecular nucleophilic attack of the alkoxy-
rhenium moiety to a carbon atom of the imine; (5) reductive
elimination and elimination of aniline; (6) Diels–Alder reac-
tion with a dienophile; (7) dehydration under acidic condi-
tions. Since the formed aniline reacts with the aldehyde,
2 equiv of the aldehyde is necessary to complete the reaction.
To confirm the reaction mechanism, the following reactions
were carried out (Eqs. 7 and 8). The reaction of aromatic ke-
timine 1a with benzaldehyde 2a in the presence of a rhenium
catalyst, [ReBr(CO)3(THF)]2, and molecular sieves gave
isobenzofuran 6 in 93% yield (Eq. 1).11,12 The reactive diene
moiety of isobenzofuran can be used for the Diels–Alder re-
action.13 In fact, when a reaction of isobenzofuran 6 was
conducted in the presence of cyclooctene 3a, the Diels–
Alder adduct 5c was produced in 87% yield (endo/exo¼
88/12) (Eq. 7). The formed Diels–Alder adduct 5c was
aromatized without isolation via the ring opening reaction
of cyclic ether and the elimination of water by treatment
with acetic acid and sulfuric acid at 25 ꢀC for 1.5 h.14 The
reaction produced the corresponding naphthalene derivative
4a in quantitative yield (Eq. 8).
3. Conclusion
In conclusion, we have succeeded in the synthesis of naph-
thalene derivatives by the reactions of aromatic ketimines
and aldehydes with dienophiles, in the presence of a [Re-
Br(CO)3(THF)]2 catalyst, followed by dehydration. This re-
action proceeds via C–H bond activation, insertion of an
aldehyde, intramolecular nucleophilic cyclization, reductive
elimination, elimination of aniline, a Diels–Alder reaction,
and successive dehydration. By using this reaction, such sub-
stituents as aryl, alkenyl, alkyl, ester, and imide groups can
be introduced to the naphthalene frameworks. We hope
that this method will become a useful tool to synthesize
substituted naphthalene derivatives.
Ph
O
Ph
O
+
toluene, 115 °C, 24 h
Ph
Ph
5c
6
3a
87% (endo / exo = 88 / 12)
ð7Þ

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Y. Kuninobu et al. / Tetrahedron 63 (2007) 8463–8468
R1
R1
O
(THF)]2 (10.6 mg, 0.0125 mmol), and toluene (1.0 mL)
was stirred at 115 ꢀC for 24 h. Then, acetic acid (3.0 mL)
and sulfuric acid (1.0 mL) were added, and the mixture
was stirred at room temperature for 1.5 h. The crude product
was extracted with hexane and purified by column chroma-
tography on silica gel to give naphthalene derivative 4.
acidic conditions
H2O
R3
R1
R3
R1
O
R2
4.1.1.1. 5,12-Diphenyl-6,7,8,9,10,11-hexahydro-cyclo-
octa[b]naphthalene (4a). 1H NMR (400 MHz, CDCl3)
d 1.40 (m, 4H), 1.51 (m, 4H), 2.82 (t, J¼6.0 Hz, 4H), 7.21–
7.24 (m, 4H), 7.32–7.35 (m, 4H), 7.43–7.47 (m, 2H), 7.49–
7.53 (m, 4H); 13C NMR (100 MHz, CDCl3) d 26.3, 29.3,
31.4, 124.5, 126.3, 126.8, 128.1, 128.2, 130.4, 131.8; IR
(Nujol, n/cmꢁ1) 1599 (w), 1558 (w), 1505 (w), 1457 (s),
1377 (s), 1351 (m), 1072 (m), 1029 (m), 1005 (m), 941
(m), 764 (s), 742 (s), 703 (s), 685 (m), 665 (m). Anal. Calcd
for C28H26: C, 92.77; H, 7.23. Found: C, 92.56; H, 7.30.
N
R3
R2NH2
Re(I)
R3CHO
H2O
R1
R1
R3
R2
N
R2
N
N
Re
H
R2
Re
H
O
H
R3
H
R1
R2
N
R3CHO
4.1.1.2. 5-Phenyl-12-styryl-6,7,8,9,10,11-hexahydro-
cycloocta[b]naphthalene (4b). 1H NMR (400 MHz,
CDCl3) d 1.38–1.47 (m, 6H), 1.74 (m, 2H), 2.75 (m, 2H),
3.08 (m, 2H), 6.76 (d, J¼16.8 Hz, 1H), 7.17–7.32 (m,
6H), 7.35–7.40 (m, 3H), 7.42–7.46 (m, 2H), 7.51 (d,
J¼16.5 Hz, 1H), 7.56–7.58 (m, 2H), 8.18 (d, J¼8.4 Hz,
1H); 13C NMR (100 MHz, CDCl3) d 26.3, 26.5, 29.1, 29.2,
30.5, 31.5, 124.7, 124.7, 125.7, 126.4, 126.6, 126.8, 126.8,
127.6, 128.1, 128.7, 130.3, 130.9, 132.2, 133.5, 135.6,
137.4, 137.6, 137.8, 137.8, 140.6; IR (Nujol, n/cmꢁ1) 3060
(w), 3024 (w), 1599 (w), 1487 (m), 1449 (s), 1376 (m),
1072 (w), 1033 (w), 967 (m), 909 (w), 767 (s), 754 (m),
704 (m), 692 (s), 666 (w). Anal. Calcd for C30H28: C,
92.74; H, 7.26. Found: C, 92.85; H, 7.38.
Re H
O
R3
Scheme 1. Proposed mechanism of the formation of naphthalene
derivatives.
4. Experimental
4.1. General
All reactions were carried out in dry solvent under an argon
atmosphere. Toluene was purchased from Wako Pure Chem-
ical Industries and was dried and degassed before use. [Re-
Br(CO)3(THF)]2 was prepared by heating a THF solution of
ReBr(CO)5 at reflux temperature for 16 h and recrystallized.
Ketimines were prepared by condensation of the corre-
sponding ketones with the corresponding aminesꢀin the pres-
4.1.1.3. 2,3,8,9,10,11,12,13-Octahydro-7-phenyl-1H-
cycloocta[a]phenalene (4c). H NMR (400 MHz, CDCl3)
1
d 1.39–1.47 (m, 6H), 1.74–1.77 (m, 2H), 2.09–2.16 (m,
2H), 2.73–2.76 (m, 2H), 3.03–3.06 (m, 2H), 3.08–3.11 (m,
2H), 3.15–3.19 (m, 2H), 7.00–7.03 (m, 1H), 7.11–7.13 (m,
2H), 7.24–7.26 (m, 1H), 7.38–7.47 (m, 3H); 13C NMR
(100 MHz, CDCl3) d 23.3, 26.3, 26.6, 27.6, 28.2, 29.5,
29.9, 31.5, 31.6, 123.1, 124.1, 124.8, 126.6, 128.1, 128.8,
130.4, 132.0, 132.2, 135.7, 136.4, 137.5, 141.2; IR (Nujol,
n/cmꢁ1) 1653 (m), 1558 (m), 1540 (w), 1506 (w), 1487
(w), 1457 (s), 1376 (s), 1339 (m), 1325 (m), 1204 (m),
1056 (m), 762 (m), 702 (s). Anal. Calcd for C29H30O: C,
91.97; H, 8.03. Found: C, 92.17; H, 8.12.
˚
ence of molecular sieves (4 A) in toluene at 100 C for 10 h,
and were used after distillation or recrystallization. Alde-
hydes and cyclooctene were purchased from Wako Pure
Chemical Industries, Tokyo Kasei Kogyo Co. and Aldrich
˚
Co., and used after distillation. Molecular sieves (4 A,
powder) were used after vacuum drying at 150 ꢀC for 5 h.
N-Methyl maleimide and dimethyl maleate were purchased
from Tokyo Kasei Kogyo Co. and Nacalai Tesque Co., and
used as received.
1H (400 MHz) and 13C (100 MHz) NMR spectra were
recorded using a JEOL JNM-LA400 spectrometer. Proton
chemical shifts are reported relative to Me4Si (CDCl3) at
d 0.00 ppm or residual solvent peak (CDCl3 at d 7.26 ppm).
Carbon chemical shifts are reported relative to CDCl3 at d
4.1.1.4. 5-(4-Methoxy-phenyl)-12-phenyl-6,7,8,9,10,11-
hexahydro-cycloocta[b]naphthalene (4d). 1H NMR
(400 MHz, CDCl3) d 1.33–1.57 (m, 8H), 2.75–2.85 (m,
4H), 3.92 (s, 3H), 7.02–7.07 (m, 2H), 7.18–7.35 (m, 8H),
7.41–7.53 (m, 3H); 13C NMR (100 MHz, CDCl3) d 26.4,
29.3, 29.3, 31.4, 31.5, 55.3, 113.5, 124.5, 126.3, 126.4,
126.8, 128.1, 130.4, 131.8, 132.2, 137.7, 137.9, 138.2,
140.7, 158.4; IR (Nujol, n/cmꢁ1) 1608 (m), 1512 (s), 1457
(s), 1376 (m), 1285 (w), 1244 (s), 1173 (m), 1033 (m), 765
(m), 731 (w), 704 (w). Anal. Calcd for C29H28O: C, 88.73;
H, 7.19. Found: C, 88.96; H, 7.28.
ꢀ ꢀ
77.00 ppm.IRspectrawererecordedonaNicoletProtege 460.
1,3-Diphenylisobenzofuran 6 is already known and commer-
cially available. The structure of the reaction product was
determined by comparing the spectrum data of the product
with that of 6.
4.1.1. Synthesis of naphthalene derivatives by one-pot
reaction. A mixture of aromatic ketimine 1 (0.500 mmol),
4.1.1.5. 5-Phenyl-12-p-tolyl-6,7,8,9,10,11-hexahydro-
cycloocta[b]naphthalene (4e). 1H NMR (400 MHz, CDCl3)
d 1.31–1.61 (m, 8H), 2.48 (s, 3H), 2.77–2.81 (m, 4H), 7.16–
7.28 (m, 6H), 7.28–7.36 (m, 4H), 7.41–7.54 (m, 3H);
aldehyde
1.00 mmol), molecular sieves (4 A, 200 mg), [ReBr(CO)3-
2
(1.00 mmol), cyclooctene 3a (110 mg,
˚

Y. Kuninobu et al. / Tetrahedron 63 (2007) 8463–8468
8467
13C NMR (100 MHz, CDCl3) d 21.4, 26.3, 29.3, 31.4, 31.5,
124.5, 126.3, 126.4, 126.8, 128.1, 128.8, 130.2, 130.4,
131.7, 131.9, 136.3, 137.5, 137.6, 137.8, 138.0, 140.7; IR
(Nujol, n/cmꢁ1) 1513 (w), 1502 (w), 1463 (s), 1376 (s),
1035 (w), 1005 (w), 809 (m), 777 (w), 763 (s), 748 (m),
702 (s), 685 (w). Anal. Calcd for C29H28: C, 92.50; H, 7.50.
Found: C, 92.60; H, 7.45.
J¼5.3, 3.0 Hz, 2H), 7.21 (dd, J¼5.3, 3.0 Hz, 2H), 7.36–
7.45 (m, 6H), 7.66 (d, J¼6.9 Hz, 4H); 13C NMR
(100 MHz, CDCl3) d 25.4, 26.2, 30.4, 46.8, 91.4, 121.3,
126.1, 128.3, 128.4, 128.6, 137.3, 146.8; IR (Nujol,
n/cmꢁ1) 3055 (w), 1734 (w), 1700 (w), 1684 (w), 1635 (w),
1601 (w), 1521 (w), 1506 (w), 1445 (s), 1364 (m), 1315
(m), 1015 (m), 979 (m), 972 (m), 771 (m), 753 (s), 798 (s),
666 (m), 642 (m). Anal. Calcd for C28H28O: C, 88.38; H,
7.42. Found: C, 88.18; H, 7.33.
4.1.1.6. 5-Phenyl-12-(4-trifluoromethyl-phenyl)-6,7,
8,9,10,11-hexahydro-cycloocta[b]naphthalene (4f). 1H
NMR (400 MHz, CDCl3) d 1.33–1.59 (m, 8H), 2.74–2.81
(m, 4H), 7.11–7.14 (m, 1H), 7.21–7.25 (m, 3H), 7.31–7.33
(m, 2H), 7.43–7.53 (m, 5H), 7.86 (d, J¼8.1 Hz, 2H); 13C
NMR (100 MHz, CDCl3) d 26.3, 26.3, 29.3, 31.3, 31.4,
31.4, 124.8, 124.9, 125.2, 125.7, 126.6, 127.0, 127.4,
128.2, 130.3, 130.8, 131.3, 131.8, 136.5, 137.6, 137.7,
138.7, 140.4, 144.7; IR (Nujol, n/cmꢁ1) 1616 (w), 1456
(m), 1376 (w), 1324 (s), 1165 (m), 1121 (s), 1105 (w),
1066 (m). Anal. Calcd for C29H25F3: C, 80.91; H, 5.85.
Found: C, 80.97; H, 5.83.
4.1.2. Synthesis of naphthalene derivatives via isolation
of Diels–Alder adduct. A mixture of benzhydrylidene-
phenyl-amine 1a (129 mg, 0.500 mmol), benzaldehyde 2a
(106 mg, 1.00 mmol), olefin 3 (0.600 mmol), molecular
˚
sieves (4 A, 200 mg), [ReBr(CO)3(THF)]2 (10.6 mg,
0.0125 mmol), and toluene (2.0 mL) was stirred at 115 ꢀC
for 24 h. The Diels–Alder adduct 5 was isolated by column
chromatography on silica gel. Then, dichloromethane
(3.0 mL), acetic acid (3.0 mL), and sulfuric acid (1.0 mL)
were added to the Diels–Alder adduct 5, and the mix-
ture was stirred at room temperature for 1.5 h. The crude
product was extracted with dichloromethane and purified
by column chromatography on silica gel to give naphthalene
derivative 4.
4.1.1.7. 5-Phenyl-12-o-tolyl-6,7,8,9,10,11-hexahydro-
cycloocta[b]naphthalene (4g). 1H NMR (400 MHz, CDCl3)
d 1.21–1.50 (m, 8H), 1.96 (s, 3H), 2.59–2.70 (m, 1H), 2.78–
2.89 (m, 3H), 7.12–7.15 (m, 1H), 7.19–7.26 (m, 4H), 7.31–
7.37 (m, 5H), 7.45–7.53 (m, 3H); 13C NMR (100 MHz,
CDCl3) d 20.0, 26.4, 29.2, 29.3, 30.5, 31.4, 124.5, 124.7,
125.6, 125.7, 126.5, 126.8, 127.2, 128.0, 128.2, 129.9,
130.3, 130.6, 130.7, 131.0, 131.9, 137.0, 137.1, 137.3,
137.8, 137.9, 139.8, 140.7; IR (Nujol, n/cmꢁ1) 2360 (w),
2341 (w), 1652 (w), 1558 (w), 1506 (w), 1457 (s), 1377 (s),
762 (w), 742 (w), 703 (m). Anal. Calcd for C29H28: C,
92.50; H, 7.50. Found: C, 92.56; H, 7.52.
4.1.2.1. 2-Methyl-4,9-diphenyl-benzo[f]isoindole-1,3-
dione (4j). H NMR (400 MHz, CDCl3) d 3.05–3.08 (m,
1
3H), 7.42–7.49 (m, 4H), 7.55–7.63 (m, 8H), 7.81–7.87 (m,
2H); 13C NMR (100 MHz, CDCl3) d 23.9, 123.8, 128.2,
128.4, 128.5, 128.7, 129.7, 134.7, 135.4, 139.4, 167.4; IR
(Nujol, n/cmꢁ1) 1761 (m), 1734 (m), 1714 (s), 1608 (w),
1518 (w), 1462 (s), 1442 (s), 1375 (s), 1255 (w), 1235 (m),
1048 (w), 1008 (m), 779 (m), 762 (m), 739 (m), 727 (w),
670 (w), 661 (w). Anal. Calcd for C25H17NO2: C, 82.63;
H, 4.72; N, 3.85. Found: C, 82.37; H, 4.92; N, 3.75.
4.1.1.8. 5-Octyl-12-phenyl-6,7,8,9,10,11-hexahydro-
cycloocta[b]naphthalene (4h). 1H NMR (400 MHz, CDCl3)
d 1.01–1.15 (m, 3H), 1.40–1.70 (m, 14H), 1.70–1.84 (m,
2H), 1.84–2.09 (m, 2H), 7.37–7.47 (m, 4H), 7.56–7.65 (m,
4H), 8.21 (d, J¼8.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 14.2, 22.7, 26.4, 26.5, 28.0, 29.1, 29.4, 29.5, 29.7, 30.6,
31.0, 31.3, 31.6, 32.0, 123.7, 124.2, 126.6, 127.2, 128.0,
130.4, 130.6, 132.3, 135.2, 136.7, 137.0, 137.8, 141.0; IR
(Nujol, n/cmꢁ1) 1600 (w), 1506 (w), 1493 (m), 1467 (s),
1377 (m), 1077 (m), 1033 (m), 887 (w), 761 (s), 703 (s),
688 (w). Anal. Calcd for C30H38: C, 90.39; H, 9.61. Found:
C, 90.35; H, 9.88.
4.1.2.2. 1,4-Diphenyl-naphthalene-2,3-dicarboxylic
acid dimethyl ester (4k). 1H NMR (400 MHz, CDCl3)
d 3.51 (s, 6H), 7.35–7.42 (m, 4H), 7.42–7.53 (m, 8H),
7.62–7.67 (m, 2H); 13C NMR (100 MHz, CDCl3) d 52.2,
127.4, 127.6, 127.8, 128.0, 128.7, 129.9, 132.7, 137.5,
139.1, 168.8; IR (Nujol, n/cmꢁ1) 1736 (s), 1703 (w), 1459
(m), 1436 (m), 1405 (w), 1377 (m), 1357 (w), 1235 (s),
1171 (w), 1133 (m), 983 (w), 858 (w), 777 (m), 727 (m),
703 (m). Anal. Calcd for C26H20O4: C, 78.77; H, 5.09.
Found: C, 78.84; H, 5.19.
4.1.1.9. 5-Methyl-12-phenyl-6,7,8,9,10,11-hexahydro-
cycloocta[b]naphthalene (4i). 1H NMR (400 MHz,
CDCl3) d 1.22–1.47 (m, 6H), 1.62–1.80 (m, 2H), 2.65 (s,
3H), 2.66–2.77 (m, 2H), 3.00–3.10 (m, 2H), 7.11–7.23 (m,
4H), 7.30–7.47 (m, 4H), 7.99 (d, J¼8.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3) d 15.0, 26.3, 26.4, 28.3, 29.8,
30.2, 31.7, 123.7, 124.3, 124.7, 126.7, 127.1, 128.1, 130.0,
130.4, 131.4, 131.9, 136.5, 137.5, 137.9, 140.9; IR (Nujol,
n/cmꢁ1) 1575 (w), 1493 (w), 1463 (s), 1378 (m), 1147 (w),
1071 (w), 1027 (w), 752 (s), 703 (s), 644 (w); HRMS calcd
for C23H24: 300.1878. Found: 300.1883.
4.1.2.3. 3a,4,9,9a-tetrahydro-2-methyl-4,9-diphenyl-
4,9-epoxybenzo[f]isoindole-1,3-dione (5a). 1H NMR
(400 MHz, CDCl3) d 2.41 (s, 6H), 4.08 (s, 2H), 6.93–6.99
(m, 2H), 7.13–7.18 (m, 2H), 7.42–7.48 (m, 2H), 7.48–7.56
(m, 4H), 8.00–8.06 (m, 4H); 13C NMR (100 MHz, CDCl3)
d 24.2, 54.3, 90.3, 120.5, 127.1, 128.0, 128.6, 128.6; IR (Nu-
jol, n/cmꢁ1) 1769 (m), 1700 (s), 1500 (w), 1457 (m), 1437
(m), 1378 (w), 1354 (w), 1312 (m), 1295 (m), 1280 (w),
1127 (m), 1006 (s), 968 (w), 940 (w), 911 (m), 810 (w),
774 (s), 759 (s), 732 (m), 702 (s), 658 (m).
4.1.2.4.
1,8-Diphenyl-11-oxa-tricyclo[6.2.1.02,7]un-
deca-2,4,6-triene-9,10-dicarboxylic acid dimethyl ester
4.1.1.10. 5,5a,6,7,8,9,10,11,11a,12-Decahydro-5,12-di-
phenyl-5,12-epoxycycloocta[b]naphthalene (5c). 1H NMR
(400 MHz, CDCl3) d 0.46–0.54 (m, 2H), 1.29–1.38 (m,
2H), 1.42–1.62 (m, 8H), 2.95–3.01 (m, 2H), 7.04 (dd,
1
(5b). H NMR (400 MHz, CDCl3) d 3.52 (s, 6H), 4.15 (s,
2H), 7.18–7.28 (m, 4H), 7.39–7.49 (m, 6H), 7.69–7.78 (m,
4H); 13C NMR (100 MHz, CDCl3) d 51.7, 54.2, 121.9,

8468
Y. Kuninobu et al. / Tetrahedron 63 (2007) 8463–8468
ꢀ
Kiss-Szikszai, A.; Antus, S.; Kurtan, T.; van Ree, T. Eur. J.
Org. Chem. 2006, 3498–3506.
125.3, 126.8, 127.2, 128.3, 128.5, 136.5, 145.4, 170.1; IR
(Nujol, n/cmꢁ1) 1763 (m), 1745 (s), 1730 (s), 1661 (w),
1595 (w), 1459 (s), 1377 (s), 1340 (w), 1303 (w), 1271
(m), 1199 (s), 1161 (m), 1023 (w), 1004 (m), 984 (m), 939
(m), 912 (w), 761 (m), 740 (w), 700 (m), 646 (w).
ꢀ
ꢀ
2. (a) Svoboda, J.; Novotna, V.; Kozmik, V.; Glogarova, M.;
Weissflog, W.; Diele, S.; Pelzl, G. J. Mater. Chem. 2003, 13,
2104–2110; (b) Reddy, R. A.; Baumeister, U.; Keith, C.;
Tschierske, C. J. Mater. Chem. 2007, 17, 62–75.
3. Asao, N.; Takahashi, K.; Lee, S.; Kasahara, T.; Yamamoto, Y.
J. Am. Chem. Soc. 2002, 124, 12650–12651.
4. Sato, Y.; Tamura, T.; Mori, M. Angew. Chem., Int. Ed. 2004, 43,
2436–2440.
4.1.3. Synthesis of naphthalene derivatives via intra-
molecular Diels–Alder reaction. A mixture of aromatic
ketimine 1 (0.500 mmol), aldehyde 2 (1.00 mmol), mole-
˚
cular sieves (4 A, 200 mg), [ReBr(CO)3(THF)]2 (10.6 mg,
0.0125 mmol), and toluene (1.0 mL) was stirred at 115 ꢀC
for 24 h. Then, acetic acid (3.0 mL) and sulfuric acid
(1.0 mL) were added, and the mixture was stirred at room
temperature for 1.5 h. The crude product was extracted
with hexane and purified by column chromatography on
silica gel to give naphthalene derivative 4.
5. Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S. J. Am. Chem. Soc.
2003, 125, 15762–15763.
6. Lin, M.-Y.; Maddirala, S. J.; Liu, R.-S. Org. Lett. 2005, 7,
1745–1748.
7. Iwasawa, N.; Shido, M.; Maeyama, K.; Kusama, H. J. Am.
Chem. Soc. 2000, 122, 10226–10227.
8. For the reviews, see: (a) Kakiuchi, F.; Murai, S. Top.
Organomet. Chem. 1999, 3, 47–79; (b) Guari, Y.; Sabo-
Etiienne, S.; Chaudret, B. Eur. J. Inorg. Chem. 1999,
1047–1055; (c) Dyker, G. Angew. Chem., Int. Ed. 1999, 38,
1698–1712; (d) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev.
2002, 102, 1731–1769.
4.1.3.1. 5-Phenyl-2,3-dihydro-1H-cyclopenta[a]naph-
thalene (4l). 1H NMR (400 MHz, CDCl3) d 2.31 (tt,
J¼7.5, 7.5 Hz, 2H), 3.17 (t, J¼7.4 Hz, 2H), 3.34 (t,
J¼7.4 Hz, 2H), 7.37–7.45 (m, 3H), 7.50–7.54 (m, 5H),
7.87–7.92 (m, 2H); 13C NMR (100 MHz, CDCl3) d 24.5,
31.3, 33.9, 124.4, 124.6, 124.8, 125.8, 126.7, 127.0, 128.2,
130.2, 130.6, 139.0, 131.1, 140.4, 141.3; IR (Nujol,
n/cmꢁ1) 1591 (m), 1573 (w), 1493 (m), 1461 (s), 1439 (s),
1395 (w), 1377 (m), 1344 (w), 1075 (m), 1031 (m), 883
(m), 785 (m), 760 (s), 705 (s). Anal. Calcd for C19H16: C,
93.40; H, 6.60. Found: C, 93.55; H, 6.54.
9. We have already reported on rhenium-catalyzed synthesis of cy-
clic compounds. See: (a) Kuninobu, Y.; Kawata, A.; Takai, K.
J. Am. Chem. Soc. 2005, 127, 13498–13499; (b) Kuninobu,
Y.; Tokunaga, Y.; Kawata, A.; Takai, K. J. Am. Chem. Soc.
2006, 128, 202–209; (c) Kuninobu, Y.; Nishina, Y.; Shouho,
M.; Takai, K. Angew. Chem., Int. Ed. 2006, 45, 2766–2768;
(d) Kuninobu, Y.; Nishina, Y.; Takai, K. Org. Lett. 2006, 8,
2891–2893; (e) Kuninobu, Y.; Nishina, Y.; Nakagawa, C.;
Takai, K. J. Am. Chem. Soc. 2006, 128, 12376–12377.
10. (a) Wittig, G.; Krebs, A. Chem. Ber. 1961, 94, 3260–3275; (b)
Sasaki, T.; Kanematsu, K.; Hayakawa, K.; Sugiura, M. J. Am.
Chem. Soc. 1975, 97, 355–360; (c) Dodge, J. A.; Bain, J. D.;
Chamberlin, A. R. J. Org. Chem. 1990, 55, 4190–4198.
11. Isobenzofuran derivatives are useful compounds as building
blocks of bioactive compounds. See: (a) Pichon, N.;
Harrison-Marchard, A.; Mailliet, P.; Maddaluno, J. J. Org.
Chem. 2004, 69, 7220–7227; (b) Myers, A. G.; Tom, N. J.;
Fraley, M. E.; Cohen, S. B.; Madar, D. J. J. Am. Chem. Soc.
1997, 119, 6072–6094; (c) Berkowitz, D. B.; Choi, S.;
Maeng, J.-H. J. Org. Chem. 2000, 65, 847–860; (d)
Sutherland, H. S.; Higgs, K. C.; Taylor, N. J.; Rodrigo, R.
Tetrahedron 2001, 57, 309–317.
4.1.3.2. 5-Octyl-2,3-dihydro-1H-cyclopenta[a]naph-
thalene (4m). H NMR (400 MHz, CDCl3) d 0.91–0.95
1
(m, 3H), 1.23–1.58 (m, 10H), 1.78 (tt, J¼7.8, 7.5 Hz, 2H),
2.26 (tt, J¼7.5, 7.5 Hz, 2H), 3.07 (t, J¼7.8 Hz, 2H), 3.12
(t, J¼7.5 Hz, 2H), 3.27 (t, J¼7.5 Hz, 2H), 7.30 (m, 1H),
7.43–7.55 (m, 2H), 7.83 (d, J¼7.5 Hz, 2H), 8.06 (d,
J¼7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 14.1, 22.7,
24.4, 29.3, 29.6, 31.1, 31.2, 31.9, 33.4, 33.9, 123.3, 124.4,
124.5, 125.0, 125.3, 130.8, 130.8, 137.4, 137.7, 140.5; IR
(Nujol, n/cmꢁ1) 1594 (w), 1515 (w), 1464 (s), 1377 (m),
1029 (w), 875 (w), 754 (m), 722 (w). Anal. Calcd for
C21H28: C, 89.94; H, 10.06. Found: C, 89.87; H, 10.00.
Acknowledgements
12. Isobenzofuran derivatives are useful compounds as building
blocks of functional materials. See: (a) Sharp, J. T.; Skinner,
C. E. D. Tetrahedron Lett. 1986, 27, 869–872; (b) Maindron,
T.; Dodelet, J. P.; Lu, J.; Hlil, A. R.; Hay, A. S.; D’Iorio, M.
Synth. Met. 2002, 130, 247–255; (c) For quencher of singlet
oxygen: Nishide, N.; Miyoshi, N. Life Sci. 2002, 72, 321–
328; (d) For green EL devices: Li, J. Y.; Hong, Z. R.; Wang,
P. F.; Lee, C. S.; Wong, N. B.; Kwong, H. L.; Lee, S. T. Thin
Solid Films 2004, 446, 111–116.
13. For the Diels–Alder reactions of isobenzofuran derivatives,
see: (a) Christopfel, W. C.; Miller, L. L. J. Org. Chem. 1986,
51, 4169–4175; (b) Binger, P.; Wedemann, P.; Goddard, R.;
Brinker, U. H. J. Org. Chem. 1996, 61, 6462–6464; (c) Ernet,
T.; Maulitz, A. H.; Wurthwein, E.-U.; Haufe, G. J. Chem.
Soc., Perkin Trans. 1 2001, 1929–1938; (d) Mikami, K.;
Ohkuma, H. Org. Lett. 2002, 4, 3355–3357; (e) Luo, Y.;
Herndon, J. W. Organometallics 2005, 24, 3099–3103.
14. Jayanth, T. T.; Jeganmohan, M.; Cheng, C.-H. J. Org. Chem.
2004, 69, 8445–8450.
Financial support by a Grant-in-Aid for Scientific Research
on Priority Areas (no. 18037049, ‘Advanced Molecular
Transformations of Carbon Resources’) from the Ministry
of Education, Culture, Sports, Science, and Technology of
Japan, and for Young Scientists (B) (no. 18750088) from
Japan Society for the Promotion of Science, and Okayama
Foundation for Science and Technology is gratefully
acknowledged. We thank Dr. Teruhiko Nitoda (The MS Lab-
oratory of Faculty of Agriculture, Okayama University) for
acquiring HR-MS spectra.
References and notes
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€
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