Synthesis of pentacyclic compounds via intramolecular [3 + 2] photocycloaddition of cycloalkene linked naphthalenes

Article abstract of DOI:10.1016/j.jphotochem.2017.01.008

Intramolecular photocycloaddition reactions of cycloalkene linked naphthalenes lead to formation of pentacyclic compounds in a high yielding and stereoselective manner. Intramolecular [2 + 2] cycloadducts are formed initially in photoreactions of cycloalkene linked 1-cyanonaphthalenes. The initially formed intramolecular [2 + 2] cycloadducts absorb light at wavelengths used to promote the photochemical reactions and, as a result, they undergo efficient photocycloreversion to regenerate the starting substrates. In a less efficient competing process, the cycloalkene linked 1-cyanonaphthalenes react to form [3 + 2] intramolecular photoadducts, which do not absorb incident light under the conditions used. Consequently, these photoadducts become the major products in these processes. The relative configuration of the major diastereomers of the pentacyclic products formed from photoreactions of cyclopentene linked naphthalenes (cis-cis) differ from those (cis-trans) arising from the cyclooctene linked substrates. The results of theoretical calculations, which show that steric factors govern the preferred facial mode of intramolecular addition, are in good agreement with the stereochemical course of these photoreactions.

Full text of DOI:10.1016/j.jphotochem.2017.01.008

Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
Contents lists available at ScienceDirect
Journal of Photochemistry and Photobiology A:
Chemistry
journal homepage: www.elsevier.com/locate/jphotochem
Synthesis of pentacyclic compounds via intramolecular [3 + 2]
photocycloaddition of cycloalkene linked naphthalenes
*
Hajime Maeda , Tomoya Uesugi, Yasufumi Fujimoto, Hirofumi Mukae,
**
Kazuhiko Mizuno
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
A R T I C L E I N F O
A B S T R A C T
Article history:
Intramolecular photocycloaddition reactions of cycloalkene linked naphthalenes lead to formation of
Received 14 November 2016
Received in revised form 4 January 2017
Accepted 7 January 2017
pentacyclic compounds in
a high yielding and stereoselective manner. Intramolecular [2 + 2]
cycloadducts are formed initially in photoreactions of cycloalkene linked 1-cyanonaphthalenes. The
initially formed intramolecular [2 + 2] cycloadducts absorb light at wavelengths used to promote the
photochemical reactions and, as a result, they undergo efficient photocycloreversion to regenerate the
starting substrates. In a less efficient competing process, the cycloalkene linked 1-cyanonaphthalenes
react to form [3 + 2] intramolecular photoadducts, which do not absorb incident light under the
conditions used. Consequently, these photoadducts become the major products in these processes. The
relative configuration of the major diastereomers of the pentacyclic products formed from photo-
reactions of cyclopentene linked naphthalenes (cis-cis) differ from those (cis-trans) arising from the
cyclooctene linked substrates. The results of theoretical calculations, which show that steric factors
govern the preferred facial mode of intramolecular addition, are in good agreement with the
stereochemical course of these photoreactions.
Available online 17 January 2017
Keywords:
Photocycloaddition
Naphthalene
Cycloalkene
Exciplex
Pentacyclic compounds
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
of naphthalene or cyanonaphthalenes with cyclopentene [26,27],
cyclooctene [11,28], cyclohexadiene [33–36], and norbornadiene
Photocycloaddition reactions between unsaturated compounds
such as arenes, alkenes, alkadienes, and alkynes have been
extensively studied from both synthetic and mechanistic view-
points [1–10]. Moreover, photocycloaddition reactions of arenes
with cycloalkenes [11–30] or cycloalkadienes [31–42] has been
utilized to synthesize various types of polycyclic compounds. Most
of the previous studies have focused on reactions in which benzene
and its derivatives serve as the arene substrates [11–25,31,32].
Consequently, studies of photocycloaddition reactions between
cycloalkenes or cycloalkadienes and naphthalene derivatives are
limited [11,26–28,33–37]. Thus far, the only processes of this type
that have been described are those involving photocycloadditions
[37]. Unfortunately, the chemical yields and product selectivities of
these processes are not high. For example, intermolecular photo-
cycloaddition of 1-cyanonaphthalene with 1,2-dimethylcyclopen-
tene gives rise to two 1,2-[2 + 2] photocycloadducts while the
major product is 1-azetine derivative [26] (Scheme 1(a)). In
addition, photocycloaddition of naphthalene with trans-cyclo-
octene produces both 1,3-[3 + 2] and 1,4-[4 + 2] photocycloadducts
in low chemical yields, whereas cis-cyclooctene does not partici-
pate in a photoreaction carried out under the same irradiation
conditions [28] (Scheme 1(b)). In contrast to intermolecular
reactions, the intramolecular counterparts often take place with
high levels of regio- and stereo-selectivity owing to the close and
pre-established locations of the reactive centers [43–51]. As we
have described previously, photoreaction of alkene linked 1-
cyanonaphthalenes generate tetracyclic products as single stereo-
isomers in high yields [52–54] (Scheme 1(c)). In the current effort,
we carried out a study of intramolecular photoreactions of
naphthalenes containing linked cycloalkenes with the aim of
developing efficient and selective methods for the synthesis of
pentacyclic compounds. The results of this investigation are
described below.
* Corresponding author. Present address: Division of Material Chemistry,
Graduate School of Natural Science and Technology, Kanazawa University,
Kakuma-machi, Kanazawa, Ishikawa 920-1192, Japan.
** Corresponding author. Present address: Graduate School of Materials Science,
Nara Institute of Science and Technology (NAIST), 8916-5, Takayama-cho, Ikoma,
Nara 630-0192, Japan.
E-mail addresses: maeda-h@se.kanazawa-u.ac.jp (H. Maeda),
kmizuno@ms.naist.jp (K. Mizuno).
http://dx.doi.org/10.1016/j.jphotochem.2017.01.008
1010-6030/© 2017 Elsevier B.V. All rights reserved.

H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
199
Table 1
Effects of substituents and ring size of cycloalkenes on intramolecular photo-
cycloadditions of naphthalene derivatives.a
Entry
Substrate
R
n
[1] (mM)
Time (h)
Yieldsb (%)
2
3
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
CN
CN
CN
CN
H
H
H
H
1
2
3
4
1
2
3
4
30
30
10
5
10
10
20
5
25
10
7
20
300
300
300
70
74
85
20
0
0
0
51
61
0
<1
<1
76
0
<1
<1
0
1g
1h
a
Photoreactions of 1a–h (>280 nm light using Pyrex glass vessel, high-pressure
mercury lamp) were carried out in CH3CN under an argon atmosphere.
b
Isolated yields.
lacking the cyano group on the naphthalene ring are subjected to
photoreactions under the same conditions, photoproducts are not
formed ( < 1% yield) and starting materials are nearly completely
recovered even following prolonged periods of irradiation (entries
5–7). However, photoreaction of cyclooctene linked naphthalene
derivative 1h (R = H, n = 4) does take place to generate 3h in 76%
yield (entry 8).
The structures of the photoproducts produced in the above
reactions were determined by using spectral methods. Especially
informative information came from X-ray crystallographic analysis
of 2a [52], 2b, 2c, 3d and 3h (Fig. 1). The crystal structures
demonstrate that all ring fusions rising by formation of bonds to
the alkene carbons are cis and that the junctions originating by
formation of bonds to the allylic carbon differ depending on the
substrate in the following manner, cis in 2a–c and trans in 3d,h.
The unique behavior of cyclooctene linked cyanonaphthalene
1d prompted us to explore this photoreaction in more detail. We
observed that in the photoreaction an initial product was formed
efficiently and then it disappeared upon continued irradiation. In a
previous study, we showed that intramolecular photocycloaddi-
tion reactions proceed more slowly in benzene than in CH3CN [52].
Thus, to facilitate optimized formation of the initial photoproduct,
reaction of 1d was carried out in benzene. Photoreaction in this
solvent led to production of the initial product in 8% yield after 3 h
irradiation. The 1H NMR spectrum of this substance contains
resonances for two coupled vinyl hydrogens at 5.83 (d, J = 9.9 Hz,
1H) and 6.47 (d, J = 9.9 Hz, 1H) ppm and two resonances ascribable
to hydrogens on a cyclobutane ring at 2.53 and 2.58 ppm. Based on
these observations, the initially formed photoproduct was identi-
fied as the intramolecular [2 + 2] photocycloadduct 4d (Scheme 3,
R = CN, n = 4). Indeed, irradiation of a CH3CN solution of 4d led to
exclusive formation of 1d.
Scheme 1. Photocycloadditions of naphthalenes with alkenes.
2. Results and discussion
In the initial phase of this study, we explored the photochem-
istry of the cyclopentene linked 1-cyanonaphthalenes
1
(Scheme 2). Irradiation ( > 280 nm light) of a CH3CN solution
containing the 1-cyanonaphthalene derivative 1a (R = CN, n = 1) in
a Pyrex glass vessel under an argon atmosphere by using a high-
pressure mercury lamp gave rise to formation of the pentacyclic
product 2a as a single stereoisomer in 74% isolated yield (Scheme 2,
Table 1, entry 1) [52]. In a similar manner, photoreaction of the
cyclohexene-linked cyanonaphthalene 1b (R = CN, n = 2) also
produced the corresponding pentacyclic product 2b in 85% yield
(entry 2). However, photoreaction of the cycloheptene linked
substrate 1c (R = CN, n = 3) generated the corresponding product 2c
in only a 20% yield along with the stereoisomer 3c (51%) (entry 3).
Finally, photoreaction of the analogous cyclooctene linked
substrate 1d (R = CN, n = 4) exclusively produced stereoisomer 3d
(61%, entry 4). When related substances 1e–g (R = H, n = 1-3)
The time dependence of the photoreaction of 1d in CD3CN was
monitored by using 1H NMR spectroscopy (Fig. 2(a)). The results
show that 1d disappears within 20 min of the start of irradiation
and [2 + 2] photocycloadduct 4d is formed. The amount of 1d
decreases upon further irradiation and finally 3d is produced as the
only product. The time course of photoreaction of 1h, the
cyclooctene linked naphthalene that does not contain a cyano
group, was also monitored (Fig. 2(b)). The consumption of 1h was
found to be slower than that of 1d and no substance other than 3h
could be detected in the crude product mixture.
These results enabled us to propose the mechanistic pathway
shown in Scheme 3 for the intramolecular photocycloaddition
reactions. Upon irradiation, the cycloalkene linked 1-cyanonaph-
thalenes 1a-d undergo initial intramolecular 1,2-[2 + 2] photo-
cycloadditon to form 4 via the intermediacy of intramolecular
singlet exciplexes. Owing to the fact that 4 possesses a styrene
chromophore, it absorbs light in the >280 nm region used to
Scheme 2. Synthesis of pentacyclic compounds by using intramolecular photo-
cycloaddition.

200
H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
Fig. 1. ORTEP plots of X-ray crystallographic data of products.
Scheme 3. Possible mechanistic pathways for intramolecular photocycloaddition reactions.
promote these processes. Consequently, it undergoes cyclorever-
sion to form the starting material 1 as part of a photochemically
promoted equilibrium process. Formation of pentacyclic products
2 and 3 then takes place by a less efficient sequential 2,4-[3 + 2]
photocycloaddition of 1 by a biradical coupling pathway. Because 2
and 3 do not absorb light at >280 nm, they accumulate in the
reaction mixture.
In earlier reviews of intermolecular photocycloaddition reac-
tions [1,2], it was suggested that benzene derivatives and alkenes
bearing either electron-releasing or electron-withdrawing sub-
stituents favor reaction by [2 + 2] photocycloadditon (ortho)
pathways, whereas relatively simple alkenes and arenes undergo
[3 + 2] photocycloaddition (meta) process. The observation made in
the current study that photoreaction of 1h (R = H, n = 4) produce
only 3h and not 4h is in good agreement with the early
suggestions. However, it is unclear why photoreactions of 1e-g
(R = H, n = 1-3) are inefficient in contrast to that of 1h, although it is
possible that steric repulsion might interfere with close approach
of reaction centers.
(Scheme 4). First, all photoproducts formed in these processes
have a cis-relationship at the ring fusion formed by formation of
bonds to the alkene carbons (Ha, Hb). This result, is consistent with
observations made in studies of photoreactions of benzene
derivatives with cycloalkenes [7,15,18,19] and is likely caused by
a steric driven retention of the alkene cis-configuration and the
higher proportion of reactions via excited singlet rather than
triplet states. Second, the trans-orientation between benzylic
hydrogen Hc and Ha, observed in the products of these processes,
suggests that an exo mode of intramolecular addition is preferred
over the corresponding endo mode. This preference is likely guided
by steric hindrance rather orbital overlap interactions. This exo-
selectivity is consistent with observations made in studies of
photoreactions of cycloalkene linked benzenes 5 [24], although
intermolecular version of this process often give both exo and endo
products [7,15,18,19,21]. Finally, photoreactions of 1a-b generate
diastereomers that have different relative configurations from that
found in the product of reaction of 1d. This difference is associated
with the configuration of the stereogenic center in the product
derived from the allylic carbon.
The observed stereochemistry of 2 and 3 suggests that three
important factors are at work in these photochemical reactions

H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
201
We believe that the difference lies in the facial selectivity in
bonding of the cycloalkene to the 1-cyanonaphthalene moiety
(Scheme 5). The results of theoretical calculations using HF/3-
21G//PM3 indicate that products 2a and 3d are thermodynamically
more stable than 3a and 2d
(DDHf = 27 and 12 kcal/mol),
respectively. Therefore, it is anticipated that exciplexes that give
rise to 2a and 3d are more stable than those that form 3a and 2d,
respectively, owing to steric reason. (In Scheme 5, products in
parentheses are enantiomers. We use racemic compounds,
therefore, enantiomers are not distinguished, and we discuss only
relative configurations.)
3. Conclusion
In this study, we investigated intramolecular photocycloaddi-
tion reactions of cycloalkene linked 1-cyanonaphthalenes and
naphthalenes. The results show that in general these process lead
to efficient and stereoselective production of pentacyclic products.
In photoreactions of the 1-cyanonaphthalene-linked compounds
(R = CN), 1,2-[2 + 2], photocycloadducts are initially formed and
undergo cycloreversion to starting materials. This process is
followed by less efficient 2,4-[3 + 2] photocycloaddition of the
substrates to produce the observed pentacyclic products. Photo-
reactions of the linked naphthalenes bearing five to seven-
membered cycloalkenes (1e–g) are sluggish but that bearing
cyclooctene (1h) produces a pentacyclic product in high yield. The
result of theoretical calculation show that the stereochemical
outcomes of these reactions are governed by steric factors that
guide stereoselective intramolecular exciplex formation. Various
methods are available for the preparation of pentacyclic com-
pounds by using thermal [55–66], photochemical [67–71] and
transition-metal catalyzed reactions [72,73]. We believe that the
photocycloaddition route described above is a significant addition
to this list owing to the fact that processes are both efficient
stereoselective, they take place in one-step and they utilize a clean
energy source.
Fig. 2. Time-dependence of photoreactions of (a) 1d and (b) 1h in CD3CN.
Scheme 4. Stereochemistry of products.
Scheme 5. Explanation of the diastereoselectivities of photoreactions of 1a and 1d.

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H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
4. Experimental
4.1. Materials and equipment
residue was subjected to silica gel column chromatography
(eluent; hexane-AcOEt) followed by recrystallization from EtOH
to give 1-cyano-2-methylnaphthalene (11.9 g, 71.1 mmol, 79%
yield). Colorless solid; 1H NMR (300 MHz, CDCl3)
d 2.75 (s, 3H),
Acetonitrile was distilled from CaH2 and then from P2O5.
Benzene was distilled from CaH2 and then from Na. THF was
7.25–8.21 (m, 6H) ppm.
To a stirred CCl4 solution (50 mL) of 1-cyano-2-methylnaph-
thalene (8.10 g, 48.4 mmol) was added N-bromosuccinimide
(10.1 g, 56.7 mmol) and benzoyl peroxide (catalytic amount), and
the solution was stirred at reflux for 4 h. The solid was removed by
filtration. The filtrate was concentrated in vacuo. The residue was
subjected to silica gel column chromatography (eluent; hexane-
AcOEt) followed by recrystallization from EtOH to give 2-
bromomethyl-1-cyanonaphthalene (10.1 g, 41.0 mmol, 85% yield).
distilled from CaH2 and then from Na/Ph2C
O. 1H and 13C NMR
¼
spectra were recorded using a Varian MERCURY-300 (300 MHz and
75 MHz, respectively) spectrometer with Me4Si as an internal
standard. IR spectra were determined using a Jasco FT/IR-230
spectrometer. UV–vis spectra were recorded using a Jasco V-530
spectrophotometer. Mass spectra (EI) were taken on a SHIMADZU
GCMS-QP5050 operating in the electron impact mode (70 eV)
equipped with GC-17A and DB-5MS column (J&W Scientific Inc.,
Serial: 8696181). HPLC separations were performed on a recycling
preparative HPLC equipped with Jasco PU-2086 Plus, RI-2031 Plus
differential refractometer, Megapak GEL 201C columns (GPC) using
CHCl3 as an eluent. Column chromatography was conducted by
using Kanto-Chemical Co. Ltd., silica gel 60 N (spherical, neutral,
0.063–0.200 mm). X-ray crystallographic data were obtained using
a Rigaku RAXIS RAPID imaging plate area detector with graphite
monochromated Mo-Ka radiation. Structures were solved by using
direct methods (SIR92) and expanded by using Fourier techniques.
All calculations were performed using the Crystal Structure
crystallographic software package. Theoretical calculations using
HF/3-21G//PM3 were performed by using Spartan ’04 software
package for Windows.
Colorless solid; 1H NMR (300 MHz, CDCl3)
(m, 6H) ppm.
d 4.85 (s, 2H), 7.49–8.21
To a stirred suspension of NaH (60% in mineral oil, 88 mg,
2.2 mmol) in THF (30 mL) was slowly added THF (10 mL) solution of
3-(dicyanomethyl)cyclopentene (250 mg, 1.89 mmol) at 0 ꢀC under
argon atmosphere. The solution was stirred at room temperature
for 1 h. To the solution was added a THF (20 mL) solution of 2-
bromomethyl-1-cyanonaphthalene (492 mg, 2.0 mmol) at 0 ꢀC,
and the solution was stirred at room temperature for 1 h. Brine and
Et2O were added. The organic layer was dried over Na2SO4, filtered,
and concentrated in vacuo. The residue was subjected to silica gel
column chromatography (eluent; hexane:AcOEt = 5:1) followed by
recycling preparative HPLC (GPC, eluent; CHCl3) to give 1-cyano-2-
[2,2-dicyano-2-(cyclopent-2-en-1-yl)ethyl]naphthalene
329 mg, 1.11 mmol, 61% yield). Colorless solid; mp 135.5–
137.5 ꢀC; 1H NMR (300 MHz, CDCl3)
2.07–2.16 (m, 1H), 2.37–
(1a,
4.2. Preparation of 1-Cyano-2-[2,2-dicyano-2-(cyclopent-2-en-1-yl)
d
ethyl]naphthalene (1a)
2.56 (m, 2H), 2.65–2.76 (m, 1H), 3.46–3.52 (m, 1H), 3.58 (d,
J = 14.1 Hz,1H), 3.72 (d, J = 14.1 Hz,1H), 5.87–5.91 (m,1H), 6.22–6.26
(m, 1H), 7.63–7.76 (m, 3H), 7.94 (d, J = 8.1 Hz, 1H), 8.13 (d, J = 8.5 Hz,
To a stirred CCl4 (20 mL) solution of cyclopentene (2.94 g,
43.1 mmol) were added N-bromosuccinimide (8.06 g, 45.3 mmol)
and benzoyl peroxide (catalytic amount). The solution was stirred
at reflux for 1 h. The formed solid was removed by filtration. The
filtrate was concentrated in vacuo to give 3-bromocyclopentene,
which was used to further reaction without purification.
1H), 8.28 (dd, J = 8.4, 0.5 Hz, 1H) ppm; 13C NMR (75 MHz, CDCl3)
d
26.7, 32.7, 40.0, 43.8, 54.1, 111.9, 114.3, 114.5, 116.3, 125.7, 126.1,
126.5, 128.1, 128.5, 129.2, 132.5, 132.6, 133.5, 136.5, 138.7 ppm; IR
(KBr)
n
2219, 2246 cmꢁ1; MS (EI) m/z 297 (M+).
To a stirred suspension of NaH (60% in mineral oil, 2.60 g,
65.0 mmol) in THF (10 mL) was slowly added a THF (5 mL) solution
of malononitrile (5.70 g, 86.2 mmol) at 0 ꢀC under argon atmo-
sphere. The suspension was stirred for 1 h at room temperature. A
THF (5 mL) solution of 3-bromocyclopentene was slowly added at
0 ꢀC and the solution was stirred for 2 h at room temperature. Et2O
and brine were added and the organic layer was separated, dried
over Na2SO4, filtered, and concentrated in vacuo. The residue was
subjected to silica gel column chromatography (eluent; hexane-
AcOEt) to give 3-(dicyanomethyl)cyclopentene (0.889 g,
4.3. Preparation of 1-Cyano-2-[2,2-dicyano-2-(cyclohex-2-en-1-yl)
ethyl]naphthalene (1b)
To a stirred CCl4 solution (20 mL) of cyclohexene (5.18 g,
63.1 mmol) were added N-bromosuccinimide (11.4 g, 63.8 mmol)
and benzoyl peroxide (catalytic amount), and the solution was
stirred at reflux for 3 h. The solid was removed by filtration. The
filtrate was concentrated in vacuo to give 3-bromocyclohexene,
which was used in the further reaction without purification.
To a stirred suspension of NaH (60% in mineral oil, 2.68 g,
67.0 mmol) in THF (10 mL) was slowly added a THF (5 mL) solution
of malononitrile (4.02 g, 60.9 mmol) at 0 ꢀC under argon asto-
sphere. The suspension was stirred for 1 h at room temperature. A
THF (5 mL) solution of 3-bromocyclohexene was slowly added at
0 ꢀC, and the solution was stirred for 3 h at room temperature. Et2O
and brine were added. The organic layer was separated, dried over
Na2SO4, filtered, and concentrated in vacuo. The residue was
subjected to silica gel column chromatography (eluent; hexane-
AcOEt) to give 3-(dicyanomethyl)cyclohexene (1.33 g, 9.06 mmol,
6.73 mmol, 16% yield). Black liquid; 1H NMR (300 MHz, CDCl3)
d
1.55–1.90 (m, 1H), 2.27–2.52 (m, 2H), 2.55–2.68 (m, 1H), 3.35–3.43
(m, 1H), 3.66 (d, J = 6.0 Hz, 1H), 5.70–5.74 (m, 1H), 6.12–6.16 (m, 1H)
ppm.
To a stirred CCl4 (60 mL) solution of 2-methylnaphthalene
(20.1 g, 141 mmol), Fe powder (catalytic amount) and I2 (catalytic
amount) were slowly added a CCl4 (10 mL) solution of Br2 (22.5 g,
7.2 mL, 141 mmol) at 0 ꢀC. The solution was stirred for 3 h. Sat
Na2S2O3 aq was added. The organic layer was washed with brine,
dried over Na2SO4, filtered, and concentrated in vacuo. The residue
was subjected to silica gel column chromatography (eluent;
hexane) to give 1-bromo-2-methylnaphthalene (29.3 g, 133 mmol,
15% yield). Black oil; 1H NMR (300 MHz, CDCl3)
d 1.58–1.63 (m, 2H),
1.86 (m, 1H), 2.07–2.13 (m, 3H), 2.80–2.87 (m, 1H), 3.64 (d,
J = 3.3 Hz, 1H), 5.65 (m, 1H), 6.07 (m, 1H) ppm.
94% yield). Brown liquid; 1H NMR (300 MHz, CDCl3)
d
2.58 (s, 3H),
Reaction of 2-bromomethyl-1-cyanonaphthalene with 3-
(dicyanomethyl)cyclohexene was carried out in a manner that is
similar to that used for the preparation of 1a to give 1-cyano-2-
[2,2-dicyano-2-(cyclohex-2-en-1-yl)ethyl]naphthalene (1b) in
7.26–8.24 (m, 6H) ppm.
A
mixture of 1-bromo-2-methylnaphthalene (20.2 g,
91.3 mmol), CuCN (22.6 g, 252 mmol), N-methylpyrrolidone
(50 mL) was stirred at 200 ꢀC for 40 min. After the mixture was
cooled to room temperature, 25% NH3 aq (40 mL) and CHCl3 were
added. The separated organic layer was concentrated in vacuo. The
77% yield. 1H NMR (300 MHz, CDCl3)
d 1.56–1.82 (m, 2H), 1.96–
2.06 (m, 1H), 2.10–2.18 (m, 2H), 2.23–2.33 (m, 1H), 2.92–3.01 (m,
1H), 3.66 (s, 2H), 5.84–5.91 (m, 1H), 6.15–6.23 (m, 1H), 7.62–7.76

H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
203
(m, 3H), 7.94 (d, J = 8.1 Hz, 1H), 8.12 (d, J = 8.6 Hz, 1H), 8.28 (d,
(5.67 g, 30.0 mmol) was slowly added at ꢁ78 ꢀC, and the solution
was stirred for 30 min at ꢁ78 ꢀC then for 1 h at room temperature.
Et2O and brine were added. The organic layer was separated, dried
over Na2SO4, filtered, and concentrated in vacuo. The residue was
subjected to silica gel column chromatography (eluent; hexane:
AcOEt = 5:1) followed by distillation under reduced pressure to
give 3-(dicyanomethyl)cyclooctene (1.43 g, 8.21 mmol, 27% yield).
J = 7.8 Hz, 1H) ppm; IR (KBr)
n
2220 cmꢁ1; MS (EI) m/z (relative
intensity) 81 (100), 166 (97), 311 (16, M+).
4.4. Preparation of 1-Cyano-2-[2,2-dicyano-2-(cyclohept-2-en-1-yl)
ethyl]naphthalene (1c)
To a stirred CCl4 solution (50 mL) of cycloheptene (3.88 g,
40.4 mmol) were added N-bromosuccinimide (7.25 g, 40.7 mmol)
and benzoyl peroxide (catalytic amount), and the solution was
stirred under reflux for 1 h. The solid was removed by filtration. The
filtrate was concentrated in vacuo to give 3-bromocycloheptene,
which was used in the further reaction without purification.
To a stirred suspension of NaH (60% in mineral oil, 1.94 g,
48.4 mmol) in THF (30 mL) was slowly added a THF (10 mL)
solution of malononitrile (3.17 g, 47.9 mmol) at 0 ꢀC under argon
atmosphere. The suspension was stirred for 40 min at room
temperature. A THF (10 mL) solution of 3-bromocycloheptene was
slowly added at 0 ꢀC, and the solution was stirred for 2 h at room
temperature. Et2O and brine were added. The organic layer was
separated, dried over Na2SO4, filtered, and concentrated in vacuo.
The residue was subjected to silica gel column chromatography
(eluent; hexane-AcOEt) to give 3-(dicyanomethyl)cycloheptene
(3.39 g, 21.2 mmol, 53% yield). Pale yellow liquid; 1H NMR
Dark brown oil; bp 152 ꢀC/6 mmHg; 1H NMR (300 MHz, CDCl3)
d
0.85–2.21 (m, 10H), 3.18 (m, 1H), 3.70 (d, J = 5.7 Hz, 1H), 5.41 (dd,
J = 10.5, 8.7 Hz, 1H), 6.00 (ddd, J = 9.9, 8.7, 8.4 Hz, 1H) ppm; 13C NMR
(75 MHz, CDCl3)
d 25.2, 26.5, 27.0, 28.7, 29.1, 33.8, 38.5, 112.1 (2C),
125.9, 134.6 ppm; IR (neat)
n 723, 758, 1449, 2254, 2857,
3018 cmꢁ1; MS (EI) m/z (relative intensity) 67 (100), 109 (21),
174 (3, M+).
To a stirred suspension of NaH (60% in mineral oil, 0.178 g,
4.44 mmol) in THF (50 mL) was slowly added THF (20 mL) solution
of 3-(dicyanomethyl)cyclooctene (0.516 g, 2.96 mmol) at 0 ꢀC
under argon atmosphere. The solution was stirred at 0 ꢀC for 1 h.
To the solution was added
a THF (20 mL) solution of 2-
bromomethyl-1-cyanonaphthalene (1.25 g, 5.07 mmol, see prepa-
ration of 1a) at 0 ꢀC, and the solution was stirred at room
temperature for 1 h. Brine and benzene were added. The organic
layer was dried over Na2SO4, filtered, and concentrated in vacuo.
The residue was subjected to silica gel column chromatography
(eluent; benzene) gave 1-cyano-2-[2,2-dicyano-2-(cyclooct-2-en-
1-yl)ethyl]naphthalene (1d, 0.632 g, 1.86 mmol, 63% yield) Color-
(300 MHz, CDCl3)
d 1.35–2.44 (m, 8H), 2.95 (s, 1H), 3.70 (d,
J = 6.0 Hz, 1H), 5.55–5.61 (m, 1H), 6.02–6.11 (m, 1H) ppm.
To a stirred suspension of NaH (60% in mineral oil, 0.433 g,
10.8 mmol) in THF (20 mL) was slowly added a THF (10 mL) solution
of 3-(dicyanomethyl)cycloheptene (1.46 g, 9.11 mmol) at 0 ꢀC under
argon atmosphere, and the solution was stirred for 40 min at room
temperature. To the solution was slowly added a THF (10 mL)
less blocks; mp 182–184 ꢀC; 1H NMR (300 MHz, CDCl3)
d 1.35–1.46
(m, 2H), 1.55–1.81 (m, 5H), 2.18–2.29 (m, 3H), 3.20 (m, 1H), 3.54 (d,
J = 14.1 Hz, 1H), 3.77 (d, J = 14.1 Hz,1H), 5.62 (dd, J = 10.4, 9.3 Hz,1H),
6.12 (ddd, J = 10.4, 8.7, 8.5 Hz, 1H), 7.63–7.77 (m, 3H), 7.95 (d,
J = 7.6 Hz,1H), 8.13 (d, J = 8.5 Hz,1H), 8.30 (d, J = 8.5 Hz,1H) ppm; 13
C
solution
of
2-bromomethyl-1-cyanonaphthalene
(2.56 g,
NMR (75 MHz, CDCl3)
d 25.2, 27.0, 27.5, 29.2, 33.0, 41.1, 43.8, 44.2,
10.4 mmol, see preparation of 1a) at 0 ꢀC, and the solution was
stirred for 2 h at room temperature. Brine and Et2O were added.
The organic layer was dried over Na2SO4, filtered, and concentrated
in vacuo. The residue was subjected to silica gel column
chromatography (eluent; hexane-AcOEt) followed by recrystalli-
zation from EtOH to give 1-cyano-2-[2,2-dicyano-2-(cyclohept-2-
en-1-yl)ethyl]naphthalene (1c, 0.595 g, 1.83 mmol, 20% yield).
112.0, 113.9, 114.7, 116.2, 124.7, 125.7, 126.5, 128.0, 128.4, 129.2,
132.4,132.6,133.4,135.7,136.5 ppm; IR (KBr) n 756, 835,1415, 2218,
2857, 2931 cmꢁ1; MS (EI) m/z (relative intensity) 67 (100), 109 (26),
166 (86), 231 (20), 339 (6, M+); Anal. Calcd for C23H21N3: C, 81.39;
H, 6.24; N, 12.38. Found: C, 81.38; H, 6.23; N, 12.21.
4.6. Preparation of 2-[2,2-Dicyano-2-(cyclopent-2-en-1-yl)ethyl]
naphthalene (1e)
Colorless needle; mp 168–170 ꢀC; 1H NMR (300 MHz, CDCl3)
d
1.38–1.46 (m, 1H), 1.65–1.83 (m, 3H), 2.12–2.37 (m, 4H), 3.04–3.06
(m, 1H), 3.61 (d, J = 14.1 Hz, 1H), 3.73 (d, J = 14.1 Hz, 1H), 5.89–5.94
(m, 1H), 6.15–6.23 (m, 1H), 7.63–7.77 (m, 3H), 7.96 (d, J = 8.1 Hz, 1H)
8.14 (d, J = 8.7 Hz, 1H), 8.29 (d, J = 9.0 Hz, 1H) ppm; 13C NMR
To a stirred CCl4 (70 mL) solution of 2-methylnaphthalene
(20.2 g, 142 mmol) were added N-bromosuccinimide (26.9 g,
151 mmol) and benzoyl peroxide (catalytic amount), and the
solution was stirred for 2 h under reflux. The solid was removed by
filtration. The filtrate was concentrated in vacuo to give 2-
(bromomethyl)naphthalene (31.2 g, 141 mmol, 99% yield), which
was used in the further reaction without purification. Brown solid,
(75 MHz, CDCl3)
d 25.7, 28.3, 30.15, 30.22, 39.3, 44.2, 47.1, 112.0,
114.3, 114.7, 116.3, 125.7, 126.5, 128.0, 128.1, 128.5, 129.2, 132.5,
132.6, 133.5, 136.4, 136.5 ppm; MS (EI) m/z (relative intensity) 142
(100, C11H10), 325 (19, M+); IR (KBr)
n .
2222 cmꢁ1
1H NMR (300 MHz, CDCl3)
7.84 (m, 4H) ppm.
d 4.67 (s, 2H), 7.26–7.52 (m, 3H), 7.80–
4.5. Preparation of 1-Cyano-2-[2,2-dicyano-2-(cyclooct-2-en-1-yl)
ethyl]naphthalene (1d)
To a stirred suspension of NaH (60% in mineral oil, 0.233 g,
5.83 mmol) in THF (20 mL) was slowly added a THF (5 mL) solution
of 3-(dicyanomethyl)cyclopentene (0.789 g, 5.97 mmol, see prepa-
ration of 1a) at 0 ꢀC under argon atmosphere, and the suspension
was stirred at room temperature for 30 min. To the solution was
slowly added a THF (5 mL) solution of 2-(bromomethyl)naphtha-
lene (1.34 g, 6.06 mmol) at 0 ꢀC, and the solution was stirred for 2 h
at room temperature. Et2O and brine were added. The organic layer
was separated, dried over Na2SO4, filtered, and concentrated in
vacuo. The residue was subjected to silica gel column chromatog-
raphy (eluent; hexane-AcOEt) followed by recrystallization from
EtOH to give 2-[2,2-dicyano-2-(cyclopent-2-en-1-yl)ethyl]naph-
thalene (1e, 0.910 g, 3.34 mmol, 56% yield). Pale yellow solid; mp
To a stirred CCl4 solution (150 mL) of cyclooctene (8.82 g,
80.0 mmol) were added N-bromosuccinimide (15.1 g, 84.8 mmol)
and benzoyl peroxide (catalytic amount), and the solution was
stirred under reflux for 3 h. The solid was removed by filtration. The
filtrate was concentrated in vacuo to give 3-bromocyclooctene
(13.92 g, 73.6 mmol, 92% yield), which was used in the further
reaction without purification. Brown oil; 1H NMR (300 MHz, CDCl3)
d
1.29–1.46 (m, 2H), 1.48–1.72 (m, 4H), 1.94–2.29 (m, 4H), 4.95 (m,
1H), 5.60 (ddd, J = 6.2, 1.5, 1.2 Hz, 1H), 5.76 (dd, J = 6.9, 1.5 Hz, 1H).
To a stirred suspension of NaH (60% in mineral oil, 2.21 g,
55.0 mmol) in THF (50 mL) was slowly added a THF (20 mL)
solution of malononitrile (3.95 g, 60.0 mmol) at 0 ꢀC under argon
atmosphere. The suspension was stirred for 40 min at room
temperature. A THF (20 mL) solution of 3-bromocyclooctene
108–109 ꢀC; 1H NMR (300 MHz, CDCl3)
d 2.06 (m, 1H), 2.32–2.43
(m, 1H), 2.47–2.51 (m, 1H), 2.66–2.68 (m, 1H), 3.35–3.36 (m, 3H),
5.82–5.86 (m, 1H), 6.19–6.23 (m, 1H), 7.48–7.53 (m, 3H), 7.86–7.89

204
H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
(m, 4H) ppm; 13C NMR (75 MHz, CDCl3)
76.7, 77.1, 77.5, 126.4, 126.5, 126.6, 127.4, 127.7, 128.0, 128.7, 129.5,
d
26.7, 32.6, 41.7, 41.7, 53.3,
column chromatography (eluent; benzene) to give 2-[2,2-dicyano-
2-(cyclooct-2-en-1-yl)ethyl]naphthalene (1h, 1.52 g, 4.83 mmol,
43% yield). Colorless powder; mp 154–156 ꢀC; 1H NMR (300 MHz,
129.7, 138.1 ppm; IR (KBr)
n
2246 cmꢁ1; MS (EI) m/z (relative
intensity) 142 (100, C11H10), 272 (16, M+).
CDCl3) d 1.24–1.37 (m, 2H), 1.51–1.70 (m, 4H), 2.01 (m, 1H), 2.19 (m,
1H), 2.95 (m, 1H), 3.30 (d, J = 13.5 Hz, 1H), 3.46 (d, J = 13.5 Hz, 1H),
5.57 (dd, J = 10.2, 10.2 Hz, 1H), 6.11 (ddd, J = 9.3, 9.0, 8.4 Hz, 1H),
7.49–7.52 (m, 3H), 7.81–7.87 (m, 4H) ppm; 25.2, 27.0, 27.6, 29.3,
32.9, 42.0, 42.1, 44.0, 114.8, 115.2, 125.4, 126.4, 126.5, 127.6, 127.7,
4.7. Preparation of 2-[2,2-Dicyano-2-(cyclohex-2-en-1-yl)ethyl]
naphthalene (1f)
To a stirred suspension of NaH (60% in mineral oil, 0.246 g,
10.3 mmol) in THF (10 mL) was slowly added a THF (5 mL) solution
of 3-(dicyanomethyl)cyclohexene (1.00 g, 6.85 mmol, see prepara-
tion of 1b) at 0 ꢀC under argon atmosphere, and the solution was
stirred for 1 h at room temperature. To the solution was slowly
added a THF (5 mL) solution of 2-(bromomethyl)naphthalene
(1.51 g, 6.84 mmol, see preparation of 1e) at 0 ꢀC, and the solution
was stirred for 3 h at room temperature. Brine and Et2O were
added. The organic layer was dried over Na2SO4, filtered, and
concentrated in vacuo. The residue was subjected to silica gel
column chromatography (eluent; hexane-AcOEt) followed by
recrystallization from EtOH to give 2-[2,2-dicyano-2-(cyclohex-
2-en-1-yl)ethyl]naphthalene (1f, 1.01 g, 3.51 mmol, 51% yield). Pale
127.9, 128.5, 129.4, 129.7, 133.0, 133.1, 135.1 ppm; IR (KBr) n 758,
824, 1149, 2245, 2857, 2938 cmꢁ1; MS (EI) m/z (relative intensity)
67 (20),141 (100),142 (21), 314 (4, M+); Anal. Calcd for C22H22N2: C,
84.04; H, 7.05; N, 8.91. Found: C, 83.94; H, 6.93; N, 8.90.
4.10. General procedure for photoreaction
A dry acetonitrile solution containing the substrate (5–30 mM,
see Table 1) was placed in a cylindrical Pyrex vessel (f= 8 mm). The
solution was degassed by argon bubbling for 15 min and then the
vessel was sealed. The solution was irradiated by using a 300 W
high pressure mercury lamp (Eikosha, PIH-300) at room tempera-
ture. The temperature of the solution was kept around room
temperature by use of circulated cooling water during irradiation.
yellow solid; mp 123–124 ꢀC; 1H NMR (300 MHz, CDCl3)
d 1.52–
1.72 (m, 2H), 1.98 (m, 1H), 2.12 (m, 2H), 2.19 (m, 1H), 2.82 (m, 1H),
3.38 (s, 2H), 5.84 (m, 1H), 6.16 (m, 1H), 7.49–7.53 (m, 3H), 7.84–7.90
4.10.1. (2aS*,4aS*,4bS*,8bS*,8cR*,8dR*,8eS*)-3,4,4a,4b,8d,8e-
Hexahydrobenzo[f]cyclopropa[cd]pentaleno[1,6-ab]pentalene-2,2,8b
(1H,2aH)-tricarbonitrile (2a)
(m, 4H) ppm; 13C NMR (75 MHz, CDCl3)
d
21.5, 25.0, 26.0, 40.5, 42.3,
44.9,115.0,122.5,126.5,126.6,127.4,127.7,128.0,128.7,129.6,129.8,
133.1, 132.2, 134.4 ppm; IR (KBr)
n
2243 cmꢁ1; MS (EI) m/z (relative
Colorless solid; mp 189–190 ꢀC; 1H NMR (300 MHz, CDCl3)
d
intensity) 142 (100, C11H10), 286 (12, M+).
1.79–2.17 (m, 4H), 2.37–2.45 (m, 1H), 2.74–2.81 (m, 2H), 3.09 (d,
J = 14.1 Hz, 1H), 3.22–3.27 (m, 1H), 3.41 (d, J = 5.0 Hz, 1H), 3.85 (d,
J = 5.1 Hz, 1H), 7.06–7.09 (m, 1H), 7.19–7.28 (m, 2H), 7.41–7.44 (m,
4.8. Preparation of 2-[2,2-Dicyano-2-(cyclohept-2-en-1-yl)ethyl]
naphthalene (1g)
1H) ppm; 13C NMR (75 MHz, CDCl3)
d
23.0, 25.8, 35.0, 37.4, 37.7,
41.7, 49.2, 50.1, 51.3, 54.6, 64.8, 114.6, 115.1, 117.0, 123.8, 125.7, 127.4,
To a stirred suspension of NaH (60% in mineral oil, 0.462 g,
11.6 mmol) in THF (20 mL) was slowly added a THF (5 mL) solution
of 3-(dicyanomethyl)cycloheptene (1.51 g, 9.44 mmol, see prepa-
ration of 1c) at 0 ꢀC under argon atmosphere, and the solution was
stirred for 50 min at room temperature. To the solution was slowly
added a THF (5 mL) solution of 2-(bromomethyl)naphthalene
(2.28 g, 10.3 mmol, see preparation of 1e) at 0 ꢀC, and the solution
was stirred for 2 h at room temperature. Brine and Et2O were
added. The organic layer was dried over Na2SO4, filtered, and
concentrated in vacuo. The residue was subjected to silica gel
column chromatography (eluent; hexane-AcOEt) followed by
recrystallization from EtOH to give 2-[2,2-dicyano-2-(cyclohept-
2-en-1-yl)ethyl]naphthalene (1 g, 1.64 g, 5.46 mmol, 58% yield).
128.1, 135.9, 142.5 ppm; IR (KBr)
297 (M+).
n
2232, 2251 cmꢁ1; MS (EI) m/z
4.10.2. (2aS*,5aS*,5bS*,9bS*,9cR*,9dR*,9eS*)-4,5,5a,5b,9d,9e-
Hexahydro-3H-benzo[4,5]cyclopropa[1,6]pentaleno[1,2,3-cd]indene-
2,2,9b(1H,2aH)-tricarbonitrile (2b)
Colorless solid; 1H NMR (300 MHz, CDCl3)
d 1.01–1.22 (m, 3H),
1.79–1.88 (m, 1H), 1.96–2.08 (m, 2H), 2.10–2.20 (m, 1H), 2.40 (t,
J = 6.7 Hz,1H), 2.66–2.72 (m,1H), 2.87 (s, 2H), 3.30 (d, J = 4.9 Hz,1H),
3.76 (d, J = 5.1 Hz, 1H), 7.04–7.07 (m, 1H), 7.21–7.32 (m, 2H), 7.48–
7.50 (m, 1H) ppm; 13C NMR (75 MHz, CDCl3)
d
21.7, 26.3, 29.4, 35.4,
38.5, 42.3, 43.4, 44.8, 47.1, 50.4, 53.6, 60.4, 113.0, 115.3, 117.1, 123.5,
123.8, 128.1, 128.3, 135.2, 144.9 ppm; IR (KBr)
2231 cmꢁ1; MS (EI)
m/z (relative intensity) 141 (100), 311 (8, M+).
n
Colorless solid; mp 138–140 ꢀC; 1H NMR (300 MHz, CDCl3)
d 1.35–
1.42 (m, 1H), 1.62–1.73 (m, 2H), 2.07–2.16 (m, 2H), 2.23–2.33 (m,
1H), 2.84 (m, 1H), 3.40 (dd, J = 4.2, 4.1 Hz, 2H), 5.84–5.89 (m, 1H),
6.12–6.21 (m, 1H), 7.64–7.53 (m, 3H) 7.84–7.88 (m, 4H) ppm; 13C
4.10.3. (2aS*,6aS*,6bS*,10bS*,10cR*,10dR*,10eS*)-5,6,6a,6b,10d,10e-
Hexahydrobenzo[4,5]cyclopropa[1,6]pentaleno[1,2,3-cd]azulene-
2,2,10b(1H,2aH)-tricarbonitrile (2c)
NMR (75 MHz, CDCl3)
d 25.7, 28.3, 30.1, 30.3, 40.9, 44.6, 45.7, 115.0,
115.2, 126.5, 126.6, 127.5, 127.7, 128.0, 128.6, 128.7, 129.5, 129.7,
Colorless block; mp 251–253 ꢀC; 1H NMR (300 MHz, CDCl3)
d
133.1, 133.2, 135.9 ppm; IR (KBr)
n
2245 cmꢁ1; MS (EI) m/z (relative
1.39–1.53 (m, 2H), 1.75–2.20 (m, 7H), 2.39 (dd, J = 5.7, 3.6 Hz, 1H),
2.78–2.85 (m, 3H), 3.44 (d, J = 5.1 Hz, 1H), 3.63 (d, J = 5.4 Hz, 1H),
7.07–7.10 (m, 1H), 7.21–7.31 (m, 2H), 7.44–7.47 (m, 1H) ppm; 13C
intensity) 142 (100, C11H10), 300 (13, M+).
4.9. Preparation of 2-[2,2-Dicyano-2-(cyclooct-2-en-1-yl)ethyl]
NMR (75 MHz, CDCl3)
d 22.7, 26.1, 27.1, 30.7, 40.7, 41.0, 40.7, 48.0,
naphthalene (1h)
51.97, 52.02, 60.3, 60.8, 114.9, 115.5, 117.0, 123.6, 123.7, 128.0, 128.3,
135.4, 145.7 ppm; IR (KBr)
n
2233 cmꢁ1; MS (EI) m/z (relative
To a stirred suspension of NaH (60% in mineral oil, 0.678 g,
17.0 mmol) in THF (7 mL) was added 3-(dicyanomethyl)cyclo-
octene (0.516 g, 2.96 mmol, see preparation of 1d) at 0 ꢀC under
argon atmosphere. The solution was stirred at 0 ꢀC for 30 min. To
the solution was added a THF (5 mL) solution of 2-(bromomethyl)
naphthalene (2.50 g, 11.3 mmol, see preparation of 1e) at 0 ꢀC, and
the solution was stirred at room temperature for 1.5 h. Brine and
Et2O were added. The organic layer was dried over Na2SO4, filtered,
and concentrated in vacuo. The residue was subjected to silica gel
intensity) 142 (100, C11H10), 325 (19, M+).
4.10.4. (2aR*,6aS*,6bS*,10bS*,10cR*,10dR*,10eS*)-5,6,6a,6b,10d,10e-
Hexahydrobenzo[4,5]cyclopropa[1,6]pentaleno[1,2,3-cd]azulene-
2,2,10b(1H,2aH)-tricarbonitrile (3c)
Colorless block; mp 255–257 ꢀC; 1H NMR (300 MHz, CDCl3)
d
1.30–1.62 (m, 3H), 1.66–1.89 (m, 4H), 2.04–2.19 (m, 2H), 2.61–2.79
(m, 3H), 3.02 (d, J = 14.7 Hz, 1H), 3.25 (d, J = 5.1 Hz, 1H), 3.67 (d,
J = 5.1 Hz, 1H), 7.04–7.08 (m, 1H), 7.19–7.28 (m, 2H), 7.44–7.47 (m,

H. Maeda et al. / Journal of Photochemistry and Photobiology A: Chemistry 337 (2017) 198–206
205
1H) ppm; 13C NMR (75 MHz, CDCl3)
40.5, 42.0, 47.9, 52.3, 53.2, 57.5, 60.0, 113.9, 114.8 (2C), 117.7, 122.8,
d
26.3, 27.4, 28.5, 31.3, 32.5,
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123.9, 127.4, 128.5, 133.8, 149.6 ppm; IR (KBr)
n
2231 cmꢁ1; MS (EI)
m/z (relative intensity) 142 (100, C11H10), 325 (7, M+).
4.10.5. (4bS*,4cS*,10R*,10aR*,10cS*,10dS*)-4c,5,6,7,8,9,10,10a,10c,10d-
Decahydro-4bH-10,10b-ethanobenzo[a]cycloocta[f]cyclopropa[cd]
pentalene-10c,12,12-tricarbonitrile (3d)
Colorless needle; mp 247–249 ꢀC; 1H NMR (300 MHz, CDCl3)
d
1.06–2.15 (m, 13H), 2.71–2.79 (m, 1H), 2.95 (d, J = 14.1 Hz, 1H), 3.23
(d, J = 6.0 Hz,1H), 3.67 (d, J = 4.8 Hz,1H), 7.10 (d, J = 6.6 Hz,1H), 7.23–
7.32 (m, 2H), 7.48 (d, J = 8.1 Hz,1H) ppm; 13C NMR (75 MHz, CDCl3)
d
24.1, 26.0, 29.1, 30.9, 32.4, 35.4, 41.2, 42.9, 46.3, 49.6, 50.0, 51.6, 60.3,
63.7, 113.7, 114.4, 117.1, 123.6, 123.7, 128.0, 128.3, 134.7, 146.6 ppm;
IR (KBr)
n
771, 944, 1459, 1477, 2230, 2253, 2901, 2931 cmꢁ1; MS
(EI) m/z (relative intensity) 141 (100), 339 (2, M+).
4.10.6. (4bS*,4cS*,10R*,10aR*,10cS*,10dS*)-4c,5,6,7,8,9,10,10a,10c,10d-
Decahydro-4bH-10,10b-ethanobenzo[a]cycloocta[f]cyclopropa[cd]
pentalene-12,12-dicarbonitrile (3h)
Colorless needle; mp 183–186 ꢀC; 1H NMR (300 MHz, CDCl3)
d
1.10–2.03 (m, 13H), 2.48–2.73 (m, 4H), 3.48 (d, J = 4.8 Hz, 1H), 7.03–
7.28 (m, 3H), 7.31 (d, J = 1.2 Hz,1H) ppm; 13C NMR (75 MHz, CDCl3)
d
24.2, 26.2, 29.3, 31.2, 32.7, 39.4, 41.0, 43.1, 43.9, 44.4, 49.0, 49.7, 60.7,
64.0, 114.7, 115.4, 123.1, 124.0, 126.1, 126.8, 140.8, 147.7 ppm; IR
(KBr)
n
747, 934, 1458, 1473, 2250, 2911, 2934 cmꢁ1; MS (EI) m/z
(relative intensity) 67 (23), 141 (100), 314 (6, M+).
4.10.7. 7,8,9,10,11,12,12a,12b-Octahydro-6bH-6a,7-ethanocycloocta
[3,4]cyclobuta[1,2-a]naphthalene-12b,13,13-tricarbonitrile (4d)
Colorless plates; mp 214–216 ꢀC; 1H NMR (300 MHz, CDCl3)
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d
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1.06–2.14 (m, 13H), 2.53 (s, 1H), 2.58 (s, 1H), 5.83 (d, J = 9.9 Hz, 1H),
6.47 (d, J = 9.9 Hz, 1H), 7.11 (d, J = 8.1 Hz, 1H), 7.23–7.30 (m, 2H), 7.48
(d, J = 8.4 Hz, 1H) ppm; 13C NMR (75 MHz, CDCl3)
d
24.1, 24.2, 24.6,
26.7, 30.6, 42.8, 45.1, 48.6, 48.7, 49.2, 52.7, 59.5, 114.5, 114.6, 120.0,
125.9, 126.1, 128.3, 128.6, 128.9, 129.2, 129.4, 129.6 ppm; IR (KBr)
n
793, 1450, 1459, 2226, 2251, 2856, 2934 cmꢁ1; MS (EI) m/z (relative
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Acknowledgements
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This study was partially supported financially by Grants-in-Aid
for Scientific Research on Priority Areas “Advanced Molecular
Transformations of Carbon Resources” (18037063, 19020060 in the
Area No. 444 to K. M.) and Scientific Research (C) (23550058 and
26410049 to K. M., 20550049, 23550047, and 26410040 to H. M.)
from the Ministry of Education, Culture, Sports, Science, and
Technology (MEXT) of Japan. H. M. is grateful for financial support
from Mitsubishi Chemical Corporation Fund and The Mazda
Foundation, A-STEP (Adaptable and Seamless Technology Transfer
Program through target-driven R&D, JST), and the Kanazawa
University SAKIGAKE project.
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