Synthesis of silicon-containing macrocyclic compounds by using intramolecular [2+2] photocycloaddition reactions of bis-dimethylsilyl-linked styrenes and stilbenes

Article abstract of DOI:10.1016/j.jphotochem.2018.06.038

A method for the synthesis of silicon-containing macrocyclic compounds, using intramolecular [2 + 2] photocycloaddition reactions of bis-dimethylsilyl-linked styrene or stilbene derivatives, is described. Photoirradiation of benzene solutions of o- and m-

Full text of DOI:10.1016/j.jphotochem.2018.06.038

JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
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Journal of Photochemistry & Photobiology A: Chemistry
journal homepage: www.elsevier.com/locate/jphotochem
Synthesis of silicon-containing macrocyclic compounds by using
intramolecular [2+2] photocycloaddition reactions of bis-dimethylsilyl-
linked styrenes and stilbenes
Hajime Maeda⁎, Ko-ichi Nishimura, Ryu-ichiro Hiranabe, 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
Keywords:
A method for the synthesis of silicon-containing macrocyclic compounds, using intramolecular [2 + 2] photo-
cycloaddition reactions of bis-dimethylsilyl-linked styrene or stilbene derivatives, is described. Photoirradiation
of benzene solutions of o- and m-bis(dimethylsilylmethyl)benzene derivatives, containing two styrene units,
promotes efficient formation of intramolecular [2 + 2] photocycloadducts. In contrast, photoreaction of the
corresponding para-substituted analog generates only dimers. Photoreactions of bis(dimethylsilylmethyl)ben-
zene derivatives, possessing two stilbene units produce intramolecular [2 + 2] photocycloadducts along with
products of cis-trans photoisomerization. The efficiencies of these intramolecular photoreactions depend on the
distances between two double bonds undergoing [2 + 2] cycloaddition. Triplet-sensitized photoreactions of the
stilbene derivatives lead to cis-trans isomerization exclusively. Finally, photoreactions of the stilbene derivatives
in the presence of molecular oxygen produce phenanthrene derivatives as side products.
Photocycloaddition
Macrocyclic compounds
Silicon
Styrene
Stilbene
1. Introduction
reagents prepared from o-, m-, and p-xylylene dichloride 1a-c react with
chlorodimethylsilane to produce the respective hydrosilanes 2a-c,
Intramolecular photocycloaddition reactions of styrenes and stil-
benes have been extensively studied because they serve as useful
methods for the synthesis of cyclic organic compounds [1–10]. We have
also reported that intramolecular photocycloaddition reactions of
styrenes and stilbenes tethered by silicon containing chains can be used
to prepare cyclic compounds that possess silyl moieties within the rings
[11–15]. Silicon-containing medium-size and macrocyclic compounds,
prepared by using a variety of protocols, have attracted recent attention
owing their structural properties and guest-inclusion abilities [16–26].
In the effort described below, intramolecular photocycloaddition reac-
tions of bis-dimethylsilyl-linked styrenes and stilbenes were explored to
demonstrate their use in the preparation of silicon-containing macro-
cyclic compounds.
which are chlorinated using PdCl2/CCl4 to form chlorosilanes 3a-c.
Magnesium promoted coupling reactions between 3a-c and p-(chlor-
omethyl)styrene produce the target substances bearing styrene units
4a-c. Finally, Heck reactions of 4a-b with iodobenzene generate the
target substrates, trans,trans-5a-b, bearing trans-stilbene units.
UV absorption spectra of 4a-c in 1.0 × 10–4 M CH2Cl2 solutions are
displayed in Fig. 1. Absorption band of styrene (λmax = 290 nm [27])
shifts to longer wavelengths region (λmax = 300 nm) when silylmethyl
groups are present on the benzene ring.
In the initial phase of this study, intramolecular photocycloaddition
reaction of the ortho positioned bis-styrene containing substrate 4a was
explored. For this purpose, a benzene solution of 4a (0.02 M) in a Pyrex
vessel was degassed by using argon bubbling and then irradiated using
a 300 W high pressure mercury lamp (> 280 nm) for 24 h. The crude
photolysate was concentrated and subjected to silica gel column chro-
matography. This process led to isolation of the intramolecular [2 + 2]
photocycloadduct 6a in 36% yield (Scheme 2, Table 1, entry 1). The 1H
NMR spectrum of 6a contains two multiplets centered at 2.42 ppm (4 H)
and 3.93 ppm (2 H), which are assigned to methylene and methine
2. Results and discussion
The bis(dimethylsilylmethyl)benzene derivatives containing two
styrene or stilbene units, that are the focus of this study, were prepared
employing the routes outlined in Scheme 1. In the pathways, Grignard
⁎
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).
https://doi.org/10.1016/j.jphotochem.2018.06.038
Received 8 May 2018; Received in revised form 21 June 2018; Accepted 22 June 2018
Availableonline23June2018
1010-6030/©2018ElsevierB.V.Allrightsreserved.

H. Maeda et al.
JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
Table 1
Effect of photosensitizers on the photoreaction of 4a.a
Entry Solvent
Photosensitizer
Absorption of
photosensitizer
(nm)
Isolated
yield of
6a (%)
b
1
2
Benzene
Benzene
None
–
36
18
1,4-Dicyanonaphthalene
(0.25 equiv)
323 [32]
3
4
5
Benzene
Benzene
Benzophenone (1 equiv)
Michler's ketone (1 equiv) 580 [34]
344 [33]
Trace
Trace
Trace
Acetonitrile p-Dicyanobenzene (0.25
equiv) + Phenanthrene
(0.25 equiv)
346 [35]
a
[4a] = 0.02 M, Pyrex vessel, irradiated by using a 300 W high pressure
mercury lamp at rt for 24 h.
b
Absorption maximum of photosensitizer at the longest wavelength.
next. We observed that photoreaction of this substrate, carried out in
the presence of 1,4-dicyanonaphthalene working as a single electron
transfer (SET) or singlet triplex photosensitizer [12,28] generates, 6a in
a decreased 18% yield (Table 1, entry 2). Photoreactions of 4a, pro-
moted by using benzophenone or Michler's ketone as triplet energy
transfer photosensitizers [11,13] (entries 3,4), or in the presence of p-
dicyanobenzene and phenanthrene as SET photoredox sensitizers
[29–31] (entry 5), produce 6a in only negligible yields. The above re-
sults suggest that the ideal method for photocycloaddition reaction
producing 6a involves direct irradiation of 4a.
Scheme 1. Preparation of bis(dimethylsilylmethyl)benzene derivatives con-
Our attention next turned to photochemical studies with the meta-
and para-substituted derivatives 4b and 4c (Scheme 3). Direct irradia-
tion of a benzene solution of 4b gave rise to formation of the in-
tramolecular [2 + 2] photocycloadduct 6b in 25% yield along with the
[2 + 2] photodimer 7 in 16% yield. 1H NMR spectroscopic analysis
indicates that the stereochemistry of the cyclobutane ring in 6b
(3.94 ppm), like that in 6a, is cis. In contrast, 7 is a mixture of (cis,cis),
(cis,trans) and (trans,trans) stereoisomers, because methine protons on
cyclobutane rings are observed at both 3.96–4.02 ppm (cis) and
2.82–2.93 ppm (trans). Photoreaction of the para-substituted derivative
4c does not produce an intramolecular [2 + 2] photocycloadduct and
only a mixture of stereoisomeric [2 + 2] photodimers 8 are formed in
78% yield, whose methine protons appear at 3.76 ppm (cis) and
3.14 ppm (trans). In order to determine if photocycloaddition reaction
of the remaining two styrene units in 8 would take place, the isolated
product was subjected to irradiation for 24 h. However, this substance
remains unreacted under these conditions, likely a consequence of the
spatially remote orientation of the two styrene units that prevents their
interaction.
taining two styrene or stilbene units.
Fig. 1. UV absorption spectra of 4a-c (1.0 × 10−4 M in CH2Cl2).
Next, light promoted reactions of trans,trans-5a-b, bearing two
stilbene units, were conducted by using a Xenon lamp with a > 290 nm
UV-29 cut filter (Scheme 4). Photoreactions take place under these
conditions to generate mixtures of stereoisomeric pairs of respective
intramolecular [2 + 2] photocycloadducts cis,trans,cis-9a-b and cis,-
cis,trans-9a-b, along with mixtures of the respective stereoisomeric
products cis,trans-5a-b and cis,cis-5a-b. Unlike the photoreactions of
4b-c, dimerized products were not observed. The stereochemistry of 9b
was determined by using 1H NMR spectroscopy (Fig. 2). Based on
molecular symmetry considerations and the observed up-field shift of
cyclobutane ring methine protons by vicinal phenyl group, two doublet-
like resonances at 4.33 (2 H) and 4.39 ppm (2 H) are assigned as cis,-
trans,cis stereoisomer. In a similar manner, four triplets (1H each) in the
3.64–4.02 ppm region in the 1H NMR spectrum are assigned as cis,-
cis,trans stereoisomer.
Scheme 2. Intramolecular photocycloaddition reaction of bis(dimethylsi-
lylmethyl)benzene derivative 4a containing two styrene units.
protons on the cyclobutane ring, respectively. In earlier studies of in-
tramolecular photocycloaddition of styrenes, resonances of methine
protons on cis-disposed 1,2-diarylcyclobutanes appear at 3.8–4.0 ppm
in their 1H NMR spectra, while those on trans-disposed 1,2-diarylcy-
clobutanes appear at upper fields as a consequence of the benzene ring
current effect [2,5,6]. Based on these data, the stereochemistry on cy-
clobutane ring of 6a is assigned to cis-orientation.
The time dependencies of product distributions in photoreactions of
trans,trans-5a-b in benzene-d6 were monitored by using 1H NMR
spectroscopy (Figs. 3 and 4). The results show that at short irradiation
times, cis-trans isomerization takes place on both substrates to form
cis,trans-5a-b and cis,cis-5a-b. At longer irradiation times, [2 + 2]
The use of photosensitizers to promote reaction of 4a was explored
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JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
Scheme 3. Intramolecular [2 + 2] photocycloaddition reactions of bis(dimethylsilylmethyl)benzene derivatives 4b and 4c having two styrene units.
intramolecular photocycloadducts 9a-b are then formed. We believe
that the [2 + 2] cycloaddition processes occur via excited singlet states
of the stilbene containing substrates with retention of double bond
configuration. Thus, based on this assumption, cis,trans,cis-9a-b and
cis,cis,trans-9a-b are produced by intramolecular [2 + 2] photo-
cycloaddition of the respective trans,trans-5a-b and cis, trans-5a-b
substrates. The observation that formation of cis, trans, cis-9a-b takes
place faster than that of cis, cis, trans-9a-b and that the all-cis isomer is
not generated appears to be a consequence of the higher reactivity of
the trans-stilbene reactants over the cis-stilbene analogs [36]. In addi-
tion, the fact that photocycloaddition of ortho derivative 5a giving 9a
proceeds faster than that of the meta derivative 5b giving 9b is likely a
result of the higher efficiency of reactions of the substrate that possesses
a shorter distance between the two double bonds.
of the bis-stilbene containing substrates, triplet sensitization experi-
ments were carried out. For this purpose, benzene-d6 solutions of
trans,trans-5a-b in the presence of 2 equiv of pyrene as a triplet pho-
tosensitizer were irradiated with > 360 nm light, and the progress of
the reactions was monitored by using 1H NMR spectroscopy (Scheme
5). The results show that intramolecular [2 + 2] photocycloadducts are
not formed even after a 24 h irradiation period. However, cis-trans
photoisomerization of the substrates occurs under these conditions to
form respective photostationary state (PSS) mixtures of trans,trans-5a-
b:cis,trans-5a-b:cis,cis-5a-b in 1:3:6 ratios. Thus, cis-trans isomeriza-
tion is the only pathway followed in photoreactions of the excited tri-
plet states of these substances [37,38], generated by energy transfer
from the triplet excited state of pyrene (ET = 48 kcal/mol [39]) to the
mono-substituted stilbenes (ET = 45–49 kcal/mol [40,41]).
To understand photochemical properties of the excited triplet states
The effects of molecular oxygen on these photoreactions were
Scheme 4. Intramolecular [2 + 2] photocycloaddition reactions of bis(dimethylsilylmethyl)benzene derivatives trans,trans-5a-b having two stilbene units.
474

H. Maeda et al.
JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
Fig. 2. 1H NMR (300 MHz) spectrum of a mixture of cis,trans,cis-9b and cis,-
cis,trans-9b in CDCl3.
Scheme 6. Photoreactions of trans,trans-5a-b in the presence of dioxygen.
photolysates, which are ascribable to H-4 and H-5 hydrogens on the
phenanthrene ring. Although the phenanthrene ring containing pro-
ducts were not separated and characterized, it is likely that they have
structures represented by 10a-b and 11a-b and that they arise by a
photoelectrocyclization-oxidation pathway [42]. Formation of phe-
nanthrene products in the photoreaction of 5b (meta) was faster than
that of 5a (ortho). Since photocyclization to phenanthrene competes
with photocycloaddition, 5a has higher reaction rate of photo-
cycloaddition than 5b, instead, 5a has lower reaction rate of photo-
cyclization to give phenanthrene derivatives.
Analysis of the UV absorption and fluorescence spectra of trans,-
trans-5a-b (2.0 × 10–5 M in CH2Cl2, Figs. 5 and 6) show that their
spectral characteristics are similar to those of trans-stilbene. Although
the absorption and fluorescence maxima of trans,trans-5a-b are shifted
to longer wavelengths by respective 10–11 and 19 nm as compared to
those of trans-stilbene, the photochemical properties of these substrates
are associated with free stilbene chromophores. Therefore, there is no
need to consider that energy and electron transfer processes with bis
(silylmethyl)benzene chains are involved.
Fig. 3. Time-dependency of product distributions in photoreaction of trans,-
trans-5a in benzene-d6 ([trans,trans-5a]0 = 0.02 M).
3. Conclusion
In the study described above, we explored the viability of a new
method for the synthesis of silicon-containing macrocyclic compounds,
which utilizes intramolecular photocycloaddition reactions of sub-
strates containing styrene and stilbene reaction centers tethered by bis
(dimethylsilylmethyl)benzene chains. The efficiencies and product
distributions were determined for reactions promoted under direct ir-
radiation, SET-sensitized and energy transfer-sensitized conditions. The
Fig. 4. Time-dependency of product distributions in photoreaction of trans,-
trans-5b in benzene-d6 ([trans,trans-5b]0 = 0.02 M).
Scheme 5. Pyrene-sensitized cis-trans photoisomerization of 5a-b.
explored next. We observed that irradiation of O2-purged benzene-d6
solutions of trans,trans-5a-b with > 290 nm light promotes formation
of not only mixtures of stereoisomers of the reactants and in-
tramolecular [2 + 2] photocycloadducts, but also mixtures of phenan-
threne ring containing products (Scheme 6). Evidence for the existence
of phenanthrene products in the mixtures comes from the observation
of resonances at 8.5–9.0 ppm in 1H NMR spectra of the crude
Fig. 5. UV absorption spectra of trans,trans-5a-b and trans-stilbene (2.0 × 10–5
M in CH2Cl2).
475

H. Maeda et al.
JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
from EtOH to produce trans,trans-1,2-bis{[4-(2-phenylvinyl)phe-
nylmethyl]dimethylsilylmethyl}benzene (trans,trans-5a, 186 mg, 26%
yield). Colorless solid; mp 142–144 °C; 1H NMR (300 MHz, CDCl3) δ
–0.08 (s, 12 H), 1.93 (s, 4 H), 2.09 (s, 4 H), 6.88–6.95 (m, 4 H), 6.96 (d,
J = 8.2 Hz, 4 H), 7.00 (d, J = 16.9 Hz, 2 H), 7.07 (d, J = 16.5 Hz, 2 H),
7.23 (t, J = 7.0 Hz, 2 H), 7.34 (t, J = 7.2 Hz, 4 H), 7.36 (d, J = 8.2 Hz,
4 H), 7.47 (d, J = 7.1 Hz, 4 H) ppm; 13C NMR (75 MHz, CDCl3) δ –3.36,
22.30, 25.81, 124.06, 126.23, 126.39, 127.04, 127.17, 128.37, 128.52,
128.56, 128.93, 133.15, 136.30, 137.49, 139.68 ppm.
4.3. Preparation of trans,trans-5b
Fig. 6. Fluorescence spectra of trans,trans-5a-b and trans-stilbene (2.0 × 10–5
M in CH2Cl2).
To an argon-purged, stirred CH3CN (10 mL) solution of 1,
3-bis[(4-vinylphenylmethyl)dimethylsilylmethyl]benzene (4b, 4.96 g,
11.6 mmol [14,15]) and iodobenzene (5.08 g, 24.9 mmol) were added
Et3N (8 mL) and Pd(OAc)2 (50 mg, 0.22 mmol). The solution was stirred
at reflux for 12 h and filtered to remove Pd catalysts. To the filtrate
were added benzene and H2O. The organic layer was separated, dried
over Na2SO4 and concentrated in vacuo, giving a residue that was
subjected to silica gel column chromatography (benzene:AcOEt = 5:1)
followed by recycling preparative HPLC (GPC) and recrystallization
from EtOH to produce trans,trans-1,3-bis{[4-(2-phenylvinyl)phe-
nylmethyl]dimethylsilylmethyl}benzene (trans,trans-5b, 2.5 g, 34%
yield). Colorless solid; mp 97–100 °C; 1H NMR (300 MHz, CDCl3) δ
–0.05 (s, 12 H), 2.06 (s, 4 H), 2.12 (s, 4 H), 6.62 (s, 1 H), 6.73 (dd,
J = 7.5, 1.6 Hz, 2 H), 6.97 (d, J = 8.1 Hz, 4 H), 7.02 (d, J = 16.4 Hz,
2 H), 7.08 (t, J = 7.4 Hz, 1 H), 7.08 (d, J = 16.9 Hz, 2 H), 7.23 (t,
J = 10.5 Hz, 2 H), 7.34 (t, J = 6.7 Hz, 4 H), 7.37 (d, J = 8.2 Hz, 4 H),
7.49 (d, J = 7.1 Hz, 4 H) ppm; 13C NMR (75 MHz, CDCl3) δ –3.56,
25.23, 25.40, 124.01, 126.21, 126.36, 127.00, 127.16, 127.95, 127.97,
128.37, 128.51, 128.59, 133.11, 137.49, 139.52, 139.68 ppm; IR (KBr)
results show that intramolecular [2 + 2] photocycloaddition reactions
occur in the direct irradiation processes to generate silicon-containing
macrocyclic products. The efficiencies of these cycloaddition reactions
were found to strongly depend on the distances between two styrene or
stilbene double bonds. In addition, the results show that cis-trans pho-
toisomerization takes place in photoreactions of the stilbene deriva-
tives, and that cis-trans isomerization is the sole pathway followed in
triplet-sensitized photoreactions. A competing reaction that produces
phenanthrene derivatives occurs when dioxygen is present in stilbene
containing solutions being directly irradiated. Overall, the in-
tramolecular photocycloaddition protocol appears to be a valuable
strategy for synthesis of silicon-containing macrocyclic compounds.
4. Experimental section
4.1. Materials and equipment
836, 1074, 1249, 1597, 2956 cm−1
.
THF was distilled from CaH2 and then from Na/Ph2C=O. CH3CN
was distilled from P2O5 and then from CaH2. Benzene was distilled from
CaH2 and then from Na. Other chemicals were purchased and used after
purification by distillation or recrystallization. Compounds 4a-c were
prepared using literature procedures [14,15]. Melting points were de-
termined on a Yanagimoto Micro Melting Point apparatus, Yanaco MP-
500. 1H and 13C NMR 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 Shimadzu UV-
160 A spectrophotometer. Fluorescence spectra were recorded using a
Jasco FP-6300 spectrophotometer. Mass spectra (EI) were recorded on a
SHIMADZU GCMS-QP5050 operating in the electron impact mode
(70 eV) equipped with GC-17 A and DB-5MS column (J&W Scientific
Inc., Serial: 8696181). HPLC separations were performed on a recycling
preparative HPLC equipped with Jasco PU-986 pump, Shodex RI-72
differential refractometer, Megapak GEL 201Cp and 201CP columns
(GPC), using CHCl3 as an eluent. Column chromatography was con-
ducted by using Kanto-Chemical Co. Ltd., silica gel 60 N (spherical,
neutral, 0.063–0.200 mm).
4.4. Photoreactions
Photoreactions shown in Schemes 2 and 3 and summarized in
Table 1 were carried out by using a benzene (8 mL) solution of substrate
(4a-c, 0.02 M) in a cylindrical Pyrex tube (φ = 8 mm). The solution was
degassed by argon bubbling for 10 min and then the vessel was sealed.
The solution was irradiated (> 280 nm) by using a 300 W high-pressure
mercury lamp (Eikosha, PIH-300) at rt, maintained by using circulated
cooling water.
Experiments shown in Schemes 4–6, and summarized in Figs. 3 and
4 were carried out by using a benzene (8 mL) or benzene-d6 (0.6 mL)
solution of substrate (trans,trans-5a-b, 0.02 M) in a cylindrical Pyrex
tube (φ = 8 mm) or a NMR tube (Wilmad 528-PP-8, φ = 5 mm). The
solution was degassed by argon bubbling for 10 min and then the vessel
was sealed. The solution was irradiated by using a 500 W Xenon lamp
(M. Watanabe & Co., Ltd., WACOM Hx-500) with UV-29 (> 290 nm) or
UV-36 (> 360 nm, Scheme 5) filters.
The crude photolysates were separated and purified by using silica
gel column chromatography and/or recycling preparative HPLC.
4.2. Preparation of trans,trans-5a
4.4.1. (2S*,5R*)-11,11,20,20-Tetramethyl-11,20-disilapentacyclo
[20.2.2.26,9.013,18.02,5]octacosa-6,8,13(18),14,16,22,24,25,27-nonaene
(6a)
To an argon-purged, stirred CH3CN (1 mL) solution of 1,2-bis[(4-
vinylphenylmethyl)dimethylsilylmethyl]benzene
(4a,
504 mg,
1.2 mmol [14,15]) and iodobenzene (491 mg, 2.4 mmol) were added
Et3N (1 mL) and Pd(OAc)2 (5 mg, 0.022 mmol). The solution was stirred
at reflux for 12 h and filtered to remove Pd catalysts. To the filtrate
were added benzene and H2O. The organic layer was separated, dried
over Na2SO4 and concentrated in vacuo, giving a residue that was
subjected to silica gel column chromatography (benzene:AcOEt = 5:1)
followed by recycling preparative HPLC (GPC) and recrystallization
Colorless oil; 1H NMR (300 MHz, CDCl3) δ –0.19 (s, 6 H), –0.13 (s,
6 H), 1.85 (s, 4 H), 2.03 (s, 4 H), 2.40–2.44 (m, 4 H), 3.93–3.94 (m,
2 H), 6.74 (d, J = 8.1 Hz, 4 H), 6.81 (d, J = 8.1 Hz, 4 H), 6.87–6.96 (m,
4 H) ppm; 13C NMR (75 MHz, CDCl3) δ –3.85, –3.67, 21.37, 23.52,
45.17, 123.75, 127.04, 127.78, 129.60, 135.74, 136.72, 136.89 ppm;
MS (EI) m/z (relative intensity, %) 73 (82), 207 (52), 292 (100), 454
(M+, 20).
476

H. Maeda et al.
JournalofPhotochemistry&PhotobiologyA:Chemistry364(2018)472–477
4.4.2. (2S*,5R*)-11,11,19,19-Tetramethyl-11,19-disilapentacyclo
[19.2.2.26,9.113,17.02,5]octacosa-6,8,13(28),14,16,21,23,24,26-nonaene
(6b)
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Colorless oil; 1H NMR (300 MHz, CDCl3) δ 0.04 (s, 6 H), 0.08 (s,
6 H), 1.87 (m, 8 H), 2.40–2.42 (m, 4 H), 3.94 (m, 2 H), 6.20 (s, 1 H),
6.69 (dd, J = 7.5, 1.6 Hz, 2 H), 6.82 (m, 8 H), 7.04 (t, J = 7.5 Hz, 1 H)
ppm; 13C NMR (75 MHz, CDCl3) δ –2.24, –2.09, 23.56, 23.74, 24.17,
45.36, 123.45, 127.52, 128.00, 128.07, 129.39, 136.90, 137.05,
139.33 ppm. MS (EI) m/z (relative intensity, %) 73 (100), 221 (44), 291
(45), 454 (M+, 45).
4.4.3. 11,11,19,19,34,34,42,42-Octamethyl-11,19,34,42-tetrasilanonacyclo
[42.2.2.229,32.221,24.26,9.136,40.113,17.025,28.02,5]pentacontahexa-6,8,13,15,
17(51),21,23,29,31,36(56),37,39,44,46,47,49,52,54-octadecaene (7)
This product could not be isolated, however, was assigned and
quantified by δ 2.82–2.93 ppm (multiplet, benzylic hydrogen on trans-
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1.51–2.51 (m, 16H, cis + trans), 3.14 (dt-like, J = 15.6, 6.7 Hz, 2H,
trans), 3.76 (quint-like, J = 7.6 Hz, 2H, cis), 5.19 (d-like, J = 11.0 Hz,
2H, cis + trans), 5.71 (d-like, J = 17.6 Hz, 2H, cis + trans), 6.15–7.31
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4.4.5. (2S*,3R*,4S*,5R*)-11,11,19,19-Tetramethyl-3,4-diphenyl-11,
19-disilapentacyclo[19.2.2.26,9.113,17.02,5]octacosa-6,8,13(28),14,16,21,
23,24,26-nonaene (cis,trans,cis-9b)
1H NMR (300 MHz, C6D6) δ –0.05 (s, 6 H), –0.01(s, 6 H), 1.84 (s,
8 H), 4.33 (d, J = 6.5 Hz, 2 H), 4.39 (d, J = 6.5 Hz, 2 H), 6.08 (s, 1 H),
6.62 (d, J = 7.7 Hz, 2 H), 6.81(d, J = 8.1 Hz, 4 H), 6.94 (d, J = 8.1 Hz,
4 H), 6.98–7.17 (m, 11 H) ppm.
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This investigation was supported financially by the Corporation of
Innovative Technology and Advanced Research in Evolutional Area
(CITY AREA) from the Wakayama Technology Promotion Foundation.
This investigation was also supported financially by a Grant-in-Aid for
Scientific Research (KAKENHI) on Priority Areas 'Multi-Element Cyclic
Compounds' (13029101 and 14044092), ‘Molecular Nano Dynamics’
(17034056), ‘Advanced Molecular Transformations of Carbon
Resources’ (18037063), and Young Scientists (B) (16750039) from the
Ministry of Education, Culture, Sports, Science and Technology of
Japan.
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