In Situ-Generated Halogen-Bonding Complex Enables Atom Transfer Radical Addition (ATRA) Reactions of Olefins

Article abstract of DOI:10.1021/acs.joc.0c01135

Although organic-based photocatalysts provide an inexpensive, environmentally friendly alternative, many are incapable of absorption within the visible wavelength range; this ultimately influences their effectiveness. Photocatalytic reactions usually proc

Full text of DOI:10.1021/acs.joc.0c01135

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Article
In Situ-Generated Halogen-Bonding Complex Enables Atom-
Transfer Radical Addition (ATRA) Reactions of Olefins
Kazuki Matsuo, Eiji Yamaguchi, and Akichika Itoh
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01135 • Publication Date (Web): 15 Jul 2020
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The Journal of Organic Chemistry
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In Situ-Generated Halogen-Bonding Complex Enables Atom-Transfer
Radical Addition (ATRA) Reactions of Olefins
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Kazuki Matsuo, Eiji Yamaguchi*, Akichika Itoh*
Gifu Pharmaceutical University, 1-25-4, Daigaku-Nishi, Gifu, Gifu 501-1196, Japan
E-mail: yamaguchi@gifu-pu.ac.jp; itoha@gifu-pu.ac.jp
Keywords; photocatalysis, CT complex, halogen bonding, atom transfer radical addition, carbon radical
Br
N
cat.
CBr3
+
CBr4
450 nm LED
ABSTRACT: Although organic based photocatalysts provide an inexpensive, environmentally friendly
alternative, many are incapable of absorption within the visible wavelength range; this ultimately
influences their effectiveness. Photocatalytic reactions usually proceed via single electron transfer (SET)
or energy transfer (ET) processes from the photoexcited molecules to the various substrates. In our study,
the carbohalogenation of olefins was accomplished by combining CBr4 and 4-Ph-pyridine under
irradiation. The atom transfer radical addition reaction of olefins was catalyzed by an in situ formed
photocatalyst via halogen bonding to afford a variety of products in moderate to good yields. Essential to
the reaction is the formation of a CT complex with the haloalkene, which triggers charge separation
processes and, ultimately, leads to the formation of the C-centered radical. While taking advantage of
relatively inexpensive, readily available, and environmentally friendly reagents, the indirect activation of
the substrate via the photoexcited catalyst paves the way for more efficient routes, especially for otherwise
challenging chemical syntheses.
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Introduction
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Over the past decade, visible light photocatalysis has been extensively researched for the activation of
small molecules. This process is often used to synthesize or functionalize a myriad of organic molecules
that were previously difficult to access due to challenging or even impossible chemical transformations.1–3
Most of the photocatalysts that have been developed so far are expensive and often use rare transition
metals (e.g., ruthenium [Ru(bpy)3]2+ or iridium [Ir(bpy)(ppy)2]+ complexes); in a few cases, several other
metal-based photocatalysts that incorporate heavy metals such as copper and bismuth have been
reported.4–6 Indeed, transition metal-based photocatalysts possess a long-lived metal-to-ligand charge
transfer (MLCT) state, making them ideal as chemical reagents.7,8 On the other hand, alternative and
complementary methods of the above-mentioned methodology based on utilizing an organic photocatalyst
have been actively developed.9 Transition metal-based or organic photocatalyst undergo photocatalytic
reactions via single electron transfer (SET) or energy-transfer (ET) processes from the photoexcited
catalyst to the various substrates/reactants.10,11 In these cases, the photoexcited catalyst can indirectly
activate the substrate/reactant. Therefore, the development of photocatalysts that enable direct
substrate/reactant activation is expected to lead to the creation of more efficient catalysts for chemical
synthesis.
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In this context, we have reported copper based photoredox complex catalyzed an atom-transfer radical
addition (ATRA) reaction.12,13 In the course of our study, we have found that combining CBr4 with a
catalytic amount of 2,2-bipyridyl under 400 nm LED irradiation furnished the 1,2-addition product
through ATRA reaction with styrene (Scheme 1a).14
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Scheme 1. (a) Preliminary results for the ATRA reaction between styrene and CBr4. (b) In situ-formed
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CT complex via halogen bonding between pyridine and haloalkane/halogen.
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Since the reagents employed for this reaction did not show any absorption capabilities around the visible
region, we hypothesized that the in situ-formed active species may have acted as a photocatalyst under
these light conditions. From that point of view, we focused on developing a in situ-generated photocatalyst
based on halogen bonding which is relatively stable nonbonding interaction between the electrophilic
region of the halogen atom and the nucleophilic region of the reacting molecules.15–20 It is known that
complexation between an amine or pyridine and a halogen atom results in the formation of charge-transfer
complexes that respond to visible light, thus generated complex triggers photoinitiated charge separation,
thus leading to the formation of C-centered radicals (Scheme 1b).21 On the other hand, the use of halogen
bonding for photocatalysis is unreliable due to the instability of the cations or cation radical species that
are generated during the charge separation state by the photoexcitation of the CT complex; in the case of
using amine as a halogen bonding acceptor, decomposition often occurs immediately under the reaction
conditions.21a In 2019, Czekelius et al. performed photocatalytic perfluoroalkylation of alkenes mediated
via the in situ-formed phosphine–alkyl iodide EDA complex.22,23 However, a photocatalysis through
halogen bonding employing a catalytic amount of amine has not been developed, and the methodology
has long been desired.
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Herein, we report the use of an in situ-generated photocatalyst that utilizes halogen bonding to enable
the photocatalytic transformation of olefins via ATRA reactions (Scheme 2).
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Scheme 2. This work
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Results and Discussion
We first investigated the catalysis of N-heteroaromatics via the ATRA reaction between styrene (1a) and
CBr4 irradiated with a 3W LED light source (Table 1). When the reaction was performed using bipyridyl
as the catalyst under 450 nm LED irradiation, the corresponding product 3a was obtained in 1% yield
(Entry 1). Using phenanthroline as the catalyst improved the yield to 42% (Entry 2). To our delight, 1a
could be functionalized into the corresponding 3a at 450 nm using 5.0 mol% pyridine instead of the
bidentate bipyridyl-type catalyst (Entry 3). We then examined the effect of the substituents on the pyridine
ring. Here, introducing electron-donating substituents such as an N,N-dimethyl amino group onto the
pyridine ring gave 3a in lower yield (Entry 4). However, replacing the functional group with an electron-
deficient moiety such as a cyano or an acetyl group improved the yield of the product, and these results
indicated that the pyridines bearing electron withdrawing group tend to promote the desired reaction.
(Entries 5 and 6). While 4-phenylpyridine showed excellent catalytic activity when compared to the
aforementioned catalyst and gave the product in 57% yield (Entry 8), a significant drop in yield was noted
when 2-phenylpyridine was used as the catalyst (Entry 7).24 Additionally, the efficiency of the light source
was evaluated by comparing for the ATRA reaction of 1a. Under the optimized reaction conditions with
5.0 mol% catalyst loading, various wavelengths ranging from 400 to 500 nm were examined. We found
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that when the reaction was conducted under shorter wavelengths, i.e., between 400 and 420 nm, the yield
of 3a decreased slightly (Entries 9–11). However, using longer wavelengths resulted in a significant drop
in yield (Entries 12 and 13). Therefore, 450 nm was chosen as the optimal wavelength for this reaction.25
Finally, the load of 1a was increased to 150 mol%, which resulted in the highest reaction yield of 70 %
(NMR) and 62 % (isolated yield) (Entry 14). A set of control experiments revealed that light and pyridine
were necessary for reactivity (Entries 15 and 16).
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Table 1. Optimization of the ATRA reaction between styrene and CBr4
Br
cat. (5.0 mol%)
CBr4
Ph
Ph
1a
DCM (0.1 M)
X nm LED, Ar, 20 h
CBr3
3a
2a
100 mol%
entry
1
1a (mol%)
100
cat.
LED (nm)
450
yield (%)
1
2,2-Bipyridyl
phenanthroline
Pyridine
2
100
450
42
3
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450
42
4
100
DMAP
450
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5
100
4-CN-pyridine
4-Ac-pyridine
2-Ph-pyridine
4-Ph-pyridine
4-Ph-pyridine
4-Ph-pyridine
4-Ph-pyridine
4-Ph-pyridine
450
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6
100
450
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7
100
450
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8
100
450
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9
100
400
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100
410
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100
420
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100
470
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100
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4-Ph-pyridine
4-Ph-pyridine
4-Ph-pyridine
w/o cat.
500
2
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450
dark
450
70 (62)
NR
NR
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1
Yields were determined via H NMR analysis of the crude reaction mixture using 1,1,2,2-tetrachloroethane as an internal
standard. The values in parentheses are the isolated yields.
With the optimized conditions in hand, we subjected various olefins to the ATRA reaction (Table 2) and
found that this reaction was applicable for a wide range of styrene-bearing alkyl (1b–e), halo (1f–h) and
cyano (1k) groups. Under the optimal conditions, 4-nitrostyrene (1j) did not react with CBr4, due to 1j
could act as a quencher for complex formed.26 However, the use of 4-MeO-substituted styrene (1i)
predominantly resulted in the polymerization of styrene because of the increased reactivity of the
stabilized olefin radical.27 It was also determined that 2-vinylnaphthalene was well tolerated under the
aforementioned reaction conditions. Using internal olefins such as indene (1n) and stilbene (1p) resulted
in low yields, whereas β-methylstyrene (1o) gave no product at all.
Next, aliphatic olefins were subjected to this optimized ATRA reaction. As noted, aliphatic olefins tended
to give better yields than their styrene counterparts. Moreover, the gram scale reaction of 1q gave
corresponding product in 78% yield, although prolonged reaction time to 40 h was required. A linear,
alkene-bearing, unprotected alcohol (1s), an acetate (1t), a branched (1u), a TIPS-protected alcohol (1v),
an amine (1w), and an ester (1aa) were all tolerated under these reaction conditions and gave the
corresponding product in moderate to good yields. Interestingly, the primary alkyl bromide (1x) was a
good substrate and gave the product in 88% yield without any decomposition of the C–Br bond. Although
the use of an allylbenzene (1y) as a substrate resulted in reduced yield, the phenyl butene (1z) furnished
the product in high yield. Notably, a cyclic alkene such as norbornene (1ab) smoothly furnished the
product with excellent selectivity. On the other hand, while the reaction proceeded using cyclooctene as
the starting material, the 1,2-addition and 1,4-addition products were obtained in 64% and 20%,
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respectively. Previous reports on ATRA reactions between cyclooctene and CBr4 revealed that the
formation of the 1,4-addition product proceeded through a 1,5-hydrogen shift before the radical had been
trapped.28,29 When a conjugated diene such as isoprene (1ad) was used as the substrate, two regioisomers,
namely, 3ad and 3ad’, were generated in moderate yield with a regioisomeric ratio of 88:12. The radical
addition/cyclization trapping experiments were conducted using diallyl malonate (1ae).30 The reaction
between 1ae and CBr4 gave the product 3ae in 75% yield with high diastereoselectivity. These
experiments revealed that the ATRA reaction was initiated through a radical addition to olefins.
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Table 2. Substrate scope for the atom-transfer radical addition of styrenes and CBr4.
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The diastereomeric ratio was determined via 1H NMR analysis of the crude reaction mixture.
a 4 mmol of 2 was used.
Further experiments were conducted to gain mechanistic insight into the catalyst’s mode of action. At
first, UV–Vis spectra of the solution containing 4-phenylpyridine, styrene, and CBr4 alone as well as an
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equimolar mixture of 4-phenylpyridine with CBr4 were obtained. Styrene, 4-phenylpyridine, and CBr4 did
not show any absorption bands around the visible region (Figure 1 top). In contrast, the UV–Vis spectrum
of the equimolar mixture of 4-phenylpyridine and CBr4 had a new absorption band at 444 nm, which
indicated that charge-transfer absorption had occurred between pyridine and CBr4 via halogen bonding.
Moreover, the newly formed absorption band was also measured using 4-phenylpyridine with various
concentrations of CBr4 (Figure 1 bottom).31 The broad band between 400 and 500 nm was concentration
dependent on CBr4, indicating pronounced halogen bonding interactions between CBr4 and 4-
phenylpyridine. Thus, catalysis could have been initiated through the formation of the CT complex
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between pyridine and CBr4, followed by photoexcitation to generate the active species.
3
CBr4
styrene
4-ph-py
4-ph-py + CBr4 (1.0 equiv)
2
1
0
200
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450
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600
wavelength (nm)
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0.500
0.400
0.300
0.200
0.100
0.000
4-ph-py
4-ph-py + CBr4 (0.1 equiv)
4-ph-py + CBr4 (0.2 equiv)
4-ph-py + CBr4 (0.3 equiv)
4-ph-py + CBr4 (0.5 equiv)
4-ph-py + CBr4 (1.0 equiv)
4-ph-py + CBr4 (5.0 equiv)
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wavelength (nm)
Figure 1. Study of the halogen-bond adduct. top) UV–Vis spectra of styrene (1a), CBr4 (2), 4-ph-py, and
a 1:1 mixture of 2 with 4-ph-py. The concentration of 1a, 2, and 4-ph-py in DCM was 1.0 mM each,
whereas the mixture of 2 and 4-ph-py was 0.1 M. bottom) UV–Vis spectra of 4-ph-py (0.1 M in DCM)
with different equivalents of CBr4 in DCM after irradiation at 450 nm for 1 h.
Further mechanistic investigations were also conducted (Scheme 3). The reaction between 1a and 2a under
the optimized conditions in oxygen resulted in no reaction (Eq. 1). This result indicated that the
photoexcited active species was quenched by a triplet oxygen molecule.32 Furthermore, radical trapping
experiments gave no desired product, whereas the use of TEMPO, galvinoxyl, and DMPO under the
optimized conditions proceeded via the radical intermediate (Eq. 2). In the case of using TEMPO as a
radical scavenger, TEMPO adduct was determined by ESI-MS. Finally, competition experiments using
styrene (1a) and decene (1q) were conducted (Eq. 3); the products obtained from styrene 3a and decene
3q were obtained in 55% and 10% yield, respectively. This result was consistent with previous reports in
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which the electron-deficient radical tended to react faster with the styrene analogs than with their aliphatic
counterparts.33
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Based on the literature reports and our experimental evidence, it was postulated that the reaction between
CBr4 and 4-phenylpyridine proceeded via the formation of the charge-transfer complex, I, before
photoexcitation at 450 nm (Scheme 4). The photoexcitation of I led to a homolysis of C–Br bond that
generated the radical, II, and the tribromomethyl radical, II’. The resulting C-centered radical, II’, was
then reacted with the olefins to generate the radical intermediate, III, which subsequently reacted with II
to furnish the desired ATRA product (route I). Another possibility is a radical chain mechanism where the
generated III reacts with CBr4 to give ATRA product and regenerate II’ (route 2).
Scheme 3. Controlled experiments for mechanistic studies
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Scheme 4. Possible mechanism for the ATRA reaction of olefins
Conclusion
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ATRA reactions of olefins catalyzed by an in situ-formed photocatalyst via halogen bonding were
investigated. Carbohalogenation of olefins with carbon tetrabromide afforded a variety of products in
moderate to good yields when irradiated at 450 nm. The photocatalysts from our study revealed that a CT
complex between pyridines and CBr4 was a crucial intermediate in the subsequent charge separation
processes that led to the formation of the C-centered radical.
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The activation of the substrate via halogen bonding to form the CT complex is a novel activation method
that can be used for challenging synthetic routes since halogen bond acceptors such as pyridine are
relatively inexpensive and readily available. Continued efforts are focused on extending this new
methodology to other classes of compounds for photocatalysis, including alkyl halides with amines or
phosphines.
■Experimental Section General considerations
General Information
Unless otherwise noted, all reactants or reagents including dry solvents were obtained from commercial
suppliers and used as received.
Analytical thin-layer chromatography (TLC) was carried out using 0.25 mm commercial silica gel plates
(Merck silica gel 60 F254). Flash column chromatography was performed with Kanto silica gel 60N
(Spherical, Neutral, 40-50 mm). Visualization of the developed chromatogram was performed by UV
lamp (254 nm) and vanillin or basic potassium permanganate stain. NMR spectra were recorded on a
JEOL ECA 500 spectrometer (500 MHz for 1H NMR, 125 MHz for 13C NMR and 470 MHz for 19F NMR),
and are internally referenced to residual protio solvent signals or TMS (note: CDCl3 referenced at δ 7.26
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and 77.0 ppm respectively, TMS referenced at δ 0 and 0 ppm respectively). Data for 1H NMR are reported
as follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br = broad, dd = doublet of doublets, ddd = doublet of doublet of doublets, td = triplet of
13
doublets), coupling constant (Hz), integration, and assignment. Data for C{1H} NMR are reported in
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terms of chemical shifts (δ ppm). IR spectra were recorded on a Perkin Elmer Spectrum 100 FTIR
spectrometer and are reported in terms of frequency of absorption (cm–1). High-resolution mass spectra
(HRMS) were obtained on a JEOL JMS-T100TD (TOF Mass Analyzer) and are reported as m/z (M+H+,
relative intensity). Melting points were measured on a Yanagimoto micro melting point apparatus without
correlation.
General Procedure for Atom-Transfer Radical Addition
A Pyrex® test tube (12.5 cm × 1.6 cm) containing a mixture of alkene 1 (1.5 equiv, 0.15 mmol),
carbontetrabromide 2 (1.0 equiv, 0.1 mmol) and 4-phenylpyridine (0.05 equiv, 0.005 mmol) in
dichloromethane (1.0 mL) was degassed via FPT cycling for three times and backfilled with Ar. The tube
was placed ca. 0.5 cm from 3W 450 nm LED. The resulting solution was stirred at ambient temperature
for 20 h. The residue was filtrated through Celite, washed with CHCl3, concentrated in vacuo. The
resulting mixture was purified by flash column chromatography on silica gel (n-hexane) to give desired
product 3.
Scale up reaction of 1q
100 mL flask containing a mixture of alkene 1q (1.5 equiv, 6.0 mmol), carbontetrabromide 2 (1.0 equiv,
4.0 mmol) and 4-phenylpyridine (0.05 equiv, 0.2 mmol) in dichloromethane (40 mL) was degassed via
FPT cycling for three times and backfilled with Ar. The tube was placed ca. 0.5 cm from 3W 450 nm LED
x 4. The resulting solution was stirred at ambient temperature for 40 h. The residue was filtrated through
Celite, washed with CHCl3, concentrated in vacuo. The resulting mixture was purified by flash column
chromatography on silica gel (n-hexane) to give desired product 3q (78% yield, 1.46 g, 3.12 mmol) as a
coloress oil.
Characterization Data
1,3,3,3-Tetrabromopropyl)benzene (3a): Following the general procedure, 3a was
obtained from a flash column chromatography (n-hexane) as a white crystalline solid
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(62% yield, 26.8 mg, 0.062 mmol). TLC (SiO2): Rf = 0.54 (n-hexane). 1H NMR (500 MHz, CDCl3) δ
7.49 (d, J = 7.5 Hz, 2H), 7.37 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.5 Hz, 1H), 5.33 (dd, J = 7.5 Hz, 4.0 Hz,
1H), 4.12 (dd, J = 15.5 Hz, 4.0 Hz, 1H), 4.06 (dd, J = 15.5 Hz, 7.5 Hz, 1H). 13C{1H} NMR (125 MHz,
CDCl3) δ 140.8, 128.94, 128.87, 128.1, 66.4, 50.0, 35.0. NMR spectra of the 3a were consistent with the
reported one.14j
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1-Methyl-4-(1,3,3,3-Tetrabromopropyl)benzene (3b): Following the general
procedure, 3b was obtained from a flash column chromatography (n-hexane) as
a colorless oil (42% yield, 18.7 mg, 0.042 mmol). TLC (SiO2): Rf = 0.59 (n-
hexane). 1H NMR (500 MHz, CDCl3) δ 7.37 (d, J = 7.5 Hz, 2H), 7.17 (d, J = 7.5
Hz, 2H), 5.32 (dd, J = 7.5 Hz, 4.0 Hz, 1H), 4.11 (dd, J = 15.5 Hz, 4.0 Hz, 1H), 4.05 (dd, J = 15.5 Hz, 7.5
Hz, 1H), 2.34 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 139.0, 137.8, 130.0, 128.0, 66.4, 50.3, 35.2,
21.3. NMR spectra of the 3b were consistent with the reported one.13c
1-Methyl-3-(1,3,3,3-Tetrabromopropyl)benzene (3c): Following the general
procedure, 3c was obtained from a flash column chromatography (n-hexane) as a
colorless oil (34% yield, 15.2 mg, 0.034 mmol). TLC (SiO2): Rf = 0.59 (n-
hexane). 1H NMR (500 MHz, CDCl3) δ 7.29-7.23 (m, 3H), 7.12 (d, J = 7.5 Hz,
1H), 5.29 (dd, J = 7.5 Hz, 4.0 Hz, 1H), 4.11 (dd, J = 15.5 Hz, 4.0 Hz, 1H), 4.05 (dd, J = 15.5 Hz, 7.5 Hz,
1H), 2.37 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 140.8, 138.6, 129.7, 128.73, 128.72, 125.2, 66.4,
50.2, 35.2, 21.4. NMR spectra of the 3c were consistent with the reported one.12
1-Methyl-2-(1,3,3,3-Tetrabromopropyl)benzene (3d): Following the general
procedure, 3d was obtained from a flash column chromatography (n-hexane) as a
colorless oil (29% yield, 12.9 mg, 0.029 mmol). TLC (SiO2): Rf = 0.57 (n-hexane).
1H NMR (500 MHz, CDCl3) δ 7.53 (d, J = 6.9 Hz, 1H), 7.26 (dt, J = 7.5 Hz, 6.9 Hz,
1H), 7.20 (dt, J = 7.5 Hz, 6.9 Hz, 1H), 7.15 (d, J = 7.5 Hz, 1H), 5.56 (br, 1H), 4.21-4.13 (m, 2H), 2.50 (s,
3H). 13C{1H} NMR (125 MHz, CDCl3) δ 139.1, 135.3, 130.8, 128.6, 128.1, 126.8, 66.2, 45.9, 35.3, 19.5.
NMR spectra of the 3d were consistent with the reported one.12
1-Methyl-4-(1,3,3,3-Tetrabromopropyl)benzene (3e): Following the general
procedure, 3e was obtained from a flash column chromatography (n-hexane) as
a yellow crystalline solid (61% yield, 29.8 mg, 0.061 mmol). TLC (SiO2): Rf =
0.61 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.41 (d, J = 8.6 Hz, 2H), 7.37
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(d, J = 8.6 Hz, 2H), 5.32 (dd, J = 7.5 Hz, 4.0 Hz, 1H), 4.12 (dd, J = 16.0 Hz, 4.0 Hz, 1H), 4.04 (dd, J =
7.5 Hz, 16.0 Hz, 1H), 1.31 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3) δ 152.2, 137.8, 127.7, 125.8, 66.5,
50.2, 35.2, 34.7, 31.3. NMR spectra of the 3e were consistent with the reported one.12
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1-Fluoro-4-(1,3,3,3-Tetrabromopropyl)benzene (3f): Following the general
procedure, 3f was obtained from a flash column chromatography (n-hexane) as a
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colorless oil (33% yield, 14.8 mg, 0.033 mmol). TLC (SiO2): Rf = 0.56 (n-hexane).
1H NMR (500 MHz, CDCl3) δ 7.48 (dd, J = 7.5 Hz, 5.2 Hz, 2H), 7.06 (t, J = 8.0 Hz, 2H), 5.34 (dd, J =
8.0 Hz, 3.4 Hz, 1H), 4.10 (dd, J = 15.5 Hz, 3.4 Hz, 1H), 4.01 (dd, J = 15.5 Hz, 8.0 Hz, 1H). 13C{1H} NMR
(125 MHz, CDCl3) δ 163.7, 161.8, 136.6, 136.5, 130.1, 130.0, 116.0, 115.8, 66.4, 49.1, 34.7. 19F NMR
(100 MHz, CDCl3) δ -111.9. NMR spectra of the 3f were consistent with the reported one.12
1-Chloro-4-(1,3,3,3-Tetrabromopropyl)benzene (3g): Following the general
procedure, 3g was obtained from a flash column chromatography (n-hexane) as a
white crystalline solid (66% yield, 30.7 mg, 0.066 mmol). TLC (SiO2): Rf = 0.61
(n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.43 (d, J = 8.6 Hz, 2H), 7.34 (d, J =
8.6 Hz, 2H), 5.30 (dd, J = 8.3 Hz, 3.7 Hz, 1H), 4.10 (dd, J = 15.5 Hz, 3.4 Hz, 1H), 4.01 (dd, J = 15.5 Hz,
8.3 Hz, 1H). C{1H} NMR (125 MHz, CDCl3) δ 139.2, 134.8, 130.0, 129.1, 66.2, 48.9, 34.6. NMR
13
spectra of the 3g were consistent with the reported one.12
1-Bromo-4-(1,3,3,3-Tetrabromopropyl)benzene (3h): Following the general
procedure, 3h was obtained from a flash column chromatography (n-hexane) as a
white crystalline solid (30% yield, 15.3 mg, 0.030 mmol). TLC (SiO2): Rf = 0.57
(n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.50 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.3 Hz, 2H), 5.29 (dd, J
= 8.3 Hz, 3.7 Hz, 1H), 4.10 (dd, J = 15.5 Hz, 3.7 Hz, 1H), 4.01 (dd, J = 15.5 Hz, 8.3 Hz, 1H). 13C{1H}
NMR (125 MHz, CDCl3) δ 139.7, 132.1, 129.8, 122.9, 66.2, 48.9, 34.6. NMR spectra of the 3h were
consistent with the reported one.12
1-Cyano-4-(1,3,3,3-Tetrabromopropyl)benzene (3k): Following the general
procedure, 3g was obtained from a flash column chromatography (n-hexane) as a
coloress oil (36% yield, 16.4 mg, 0.036 mmol). TLC (SiO2): Rf = 0.10 (n-hexane).
1H NMR (500 MHz, CDCl3) δ 7.68 (d, J = 8.6 Hz, 2H), 7.62 (d, J = 8.6 Hz, 2H),
5.32 (dd, J = 8.6 Hz, 3.4 Hz, 1H), 4.12 (dd, J = 15.5 Hz, 3.4 Hz, 1H), 4.02 (dd, J = 15.5 Hz, 8.6 Hz, 1H).
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13C{1H} NMR (125 MHz, CDCl3) δ 145.6, 132.7, 129.0, 118.2, 112.8, 65.9, 47.9, 34.1. NMR spectra of
the 3k were consistent with the reported one.34
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1-Chloromethyl-4-(1,3,3,3-Tetrabromopropyl)benzene (3I): Following the
general procedure, 3l was obtained from a flash column chromatography (n-
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hexane) as a colorless oil (45% yield, 21.6 mg, 0.045 mmol). TLC (SiO2): Rf
= 0.26 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.49 (d, J = 7.8 Hz, 2H), 7.40 (d, J = 7.8 Hz, 2H), 5.33-
5.32 (m, 1H), 4.58 (s, 2H), 4.12 (dd, J = 15.5 Hz, 1.7 Hz, 1H), 4.04 (dd, J = 15.5 Hz, 7.5 Hz, 1H). 13C{1H}
NMR (125 MHz, CDCl3) δ 140.9, 138.2, 129.1, 128.5, 66.3, 49.3, 45.6, 34.8. NMR spectra of the 3l were
consistent with the reported one.12
2-(1,3,3,3-Tetrabromopropyl)naphthalene (3m): Following the general
procedure, 3m was obtained from a flash column chromatography (n-hexane) as
a white crystalline solid (37% yield, 17.9 mg, 0.037 mmol). TLC (SiO2): Rf =
0.51 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.90-7.88 (m, 2H), 7.85-7.82 (m, 2H), 7.63 (d, J = 8.6
Hz, 1H), 7.53-7.50 (m, 2H), 5.54 (t, J = 5.2 Hz, 1H), 4.18 (d, J = 5.2 Hz, 2H). 13C{1H} NMR (125 MHz,
CDCl3) δ 137.7, 133.3, 132.9, 129.1, 128.2, 127.7, 127.3, 126.9, 126.7, 125.4, 66.1, 50.7, 35.0. FTIR
(ATR) 3391, 3054, 3024, 2928, 2163, 1913, 1709, 1632, 1600, 1509, 1470, 1440, 1416, 1371, 1271, 1220,
1201, 1174, 1158, 1126, 1089, 1050, 1018, 1002, 986, 964, 942, 907, 892, 857, 816, 772, 756, 737, 703,
+
660 cm-1. HRMS m/z (DART) calcd for C13H11Br4 (M+H)+ 482.7589, found 482.7612. m.p. 84.2-86.2
ºC.
1-Bromo-2-tetrabromomethyl-2,3-dihydro-1H-inden (3n): Following the general
procedure, 3n was obtained from a flash column chromatography (n-hexane) as a
coloress oil {58% yield, 25.7 mg, 0.058 mmol (dr = 15 : 1)}. TLC (SiO2): Rf = 0.55
(n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.44 (dd, J = 8.3 Hz, 4.6 Hz, 1H), 7.30 (dd, J = 4.6 Hz, 3.7
Hz, 2H), 7.23 (dd, J = 8.3 Hz, 3.7 Hz, 2H), 5.65 (d, J = 3.1 Hz, 1H), 4.20 (ddd, J = 9.2 Hz, 4.0 Hz, 3.1
Hz, 1H), 3.60 (dd, J = 17.5 Hz, 9.2 Hz, 1H), 3.25 (dd, J = 17.5 Hz, 4.0 Hz, 1H). 13C{1H} NMR (125 MHz,
CDCl3) δ 141.9, 140.6, 129.5, 127.9, 126.0, 124.5, 71.7, 55.1, 45.5, 38.3. NMR spectra of the 3n were
consistent with the reported one.12
(1,3,3,3-Tetrabromo-2-phenylpropyl)benzene (3p): Following the general
procedure, 3p was obtained from a flash column chromatography (n-hexane) as a
colorless oil {23% yield, 11.7 mg, 0.023 mmol, 79:21 d.r. (from Z isomer)}. TLC
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(SiO2): Rf = 0.19 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.59 (br, 1H), 7.47-7.37 (m, 5H), 7.32-7.21
(m, 4H), 5.94 (d, J = 5.8 Hz, 1H), 4.38 (d, J = 5.8 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 140.7,
138.1, 128.9, 128.71, 128.68, 128.4, 127.7, 71.9, 55.0, 42.9. FTIR (ATR) 3062, 3030, 1601, 1496, 1453,
1339, 1185, 1157, 177, 1033, 977, 915, 853, 825, 778, 761, 725, 698 cm-1. HRMS m/z (DART) calcd for
C15H12Br3 (M-Br)+ 428.8484, found 428.8479.
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1,1,1,3-Tetrabromoundecane (3q): Following the general procedure, 3q was
obtained from a flash column chromatography (n-hexane) as a coloress oil (82% yield,
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38.4 mg, 0.082 mmol). TLC (SiO2): Rf = 0.64 (n-hexane). H NMR (500 MHz,
CDCl3) δ 4.20 (dt, J = 7.2 Hz, 4.6 Hz, 1H), 3.83 (dd, J = 11.5 Hz, 4.6 Hz, 1H), 3.55 (dd, J = 11.5 Hz, 5.2
13
Hz, 1H), 2.11-1.93 (m, 2H), 1.63-1.47 (m, 2H), 1.33-1.25 (m, 11H), 0.89 (t, J = 6.9 Hz, 3H). C{1H}
NMR (125 MHz, CDCl3) δ 66.9, 52.1, 39.7, 36.4, 31.8, 29.4, 29.2, 28.7, 27.3, 22.6, 14.1. NMR spectra
of the 3q were consistent with the reported one.12
1,1,1,3-Tetrabromotridecane (3r):Following the general procedure, 3r was obtained
from a flash column chromatography (n-hexane) as a coloress oil (83% yield, 41.2 mg,
0.083 mmol). TLC (SiO2): Rf = 0.64 (n-hexane).1H NMR (500 MHz, CDCl3) δ 4.20
(dt, J = 4.6 Hz, 4.0 Hz, 1H), 3.84 (dd, J = 16.0 Hz, 4.0 Hz, 1H), 3.55 (dd, J = 16.0 Hz, 4.6 Hz, 1H), 2.11-
1.93 (m, 2H), 1.63-1.56 (m, 1H), 1.54-1.47 (m, 1H), 1.37-1.27 (m, 14H), 0.88 (t, J = 5.7 Hz, 3H). 13C{1H}
NMR (125 MHz, CDCl3) δ 66.9, 52.1, 39.7, 36.4, 31.9, 29.6, 29.5, 29.4, 29.3, 28.7, 27.3, 22.7, 14.1.
NMR spectra of the 3r were consistent with the reported one.35
5,7,7,7-Tetrabromoheptan-1-ol (3s): Following the general procedure, 3s was
obtained from a flash column chromatography (n-hexane : ethyl acetate = 2:1) as a
coloress oil (84% yield, 35.9 mg, 0.084 mmol). TLC (SiO2): Rf = 0.40 (n-hexane :
ethyl acetate = 2:1). 1H NMR (500 MHz, CDCl3) δ 4.22 (dq, J = 4.6 Hz, 4.0 Hz, 1H), 3.85 (dd, J = 16.0
Hz, 4.0 Hz, 1H), 3.70 (t, J = 5.2 Hz, 2H), 3.56 (dd, J = 16.0 Hz, 4.6 Hz, 1H), 2.16-1.99 (m, 2H), 1.75-1.60
(m, 4H), 1.40 (s, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 66.8, 62.6, 51.7, 39.4, 36.2, 31.7, 23.7. NMR
spectra of the 3s were consistent with the reported one.6
1,1,1,3-Tetrabromo-4-acetoxybutane (3t): Following the general procedure, 3t was
obtained from a flash column chromatography (n-hexane : ethyl acetate = 10:1) as a
coloress oil (72% yield, 30.8 mg, 0.072 mmol). TLC (SiO2): Rf = 0.38 (n-hexane : ethyl acetate = 10:1).
1H NMR (500 MHz, CDCl3) δ 4.53 (dd, J = 11.5 Hz, 5.2 Hz, 1H), 4.42-4.33 (m, 2H), 3.75 (dd, J = 20.6
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Hz, 5.2 Hz, 1H), 3.70 (dd, J = 20.6 Hz, 11.8 Hz, 1H), 2.14 (s, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ
170.3, 66.8, 63.1, 45.5, 35.1, 20.8. NMR spectra of the 3t were consistent with the reported one.12
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1,1,1,3-Tetrabromo-4-acetoxy-4-methylbutane (3u): Following the general
procedure, 3u was obtained from a flash column chromatography (n-hexane : ethyl
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acetate = 10:1) as a coloress oil (42% yield, 18.6 mg, 0.042 mmol, 55:45 d.r.). TLC
(SiO2): Rf = 0.25 (n-hexane : ethyl acetate = 10:1). 1H NMR (500 MHz, CDCl3) δ 5.20 (dq, J = 9.2 Hz,
6.3 Hz, 1H), 4.23 (ddd, J = 9.2 Hz, 5.5 Hz, 3.7 Hz, 1H), 3.68 (dd, J = 16.3 Hz, 3.7 Hz, 1H), 3.63 (dd, J =
16.3 Hz, 5.5 Hz, 1H), 2.11 (s, 3H), 1.43 (d, 3H). 13C{1H} NMR (125 MHz, CDCl3) δ 170.1, 71.7, 62.3,
51.1, 35.9, 21.2, 17.2. FTIR (ATR) 2927, 2847, 1742, 1372, 1231, 1058, 946 cm-1. HRMS m/z (DART)
calcd for C7H11Br4O2 (M+H)+ 442.7487, found 442.7471.
1,1,1,3-Tetrabromo-4-((triisopropylsilyl)oxy)butane (3v): Following the
general procedure, 3v was obtained from a flash column chromatography (n-
hexane) as a coloress oil (32% yield, 17.3 mg, 0.032 mmol). TLC (SiO2): Rf = 0.60 (n-hexane). 1H NMR
(500 MHz, CDCl3) δ 4.23-4.19 (m, 1H), 4.10 (dd, J = 10.9 Hz, 5.7 Hz, 1H), 3.95 (dd, J = 10.9 Hz, 5.7
Hz, 1H), 3.91 (dd, J = 10.9 Hz, 2.9 Hz, 1H), 3.58 (dd, J = 10.9 Hz, 5.7 Hz, 1H), 1.13-1.07 (m, 21H).
13C{1H} NMR (125 MHz, CDCl3) δ 67.2, 62.6, 50.2, 36.4, 18.0, 12.0. FTIR (ATR) 2943, 2866, 1740,
1462, 1370, 1229, 1217, 1111, 1065, 999, 945, 882, 791, 685 cm-1. HRMS m/z (DART) calcd for
C13H27Br4OSi (M+H)+ 542.8559, found 542.8555.
1,1,1,3-Tetrabromo-4-((tert-butoxycarbonyl)amino)butane (3w): Following
the general procedure, 3w was obtained from a flash column chromatography (n-
hexane : ethyl acetate = 10:1) as a coloress oil (52% yield, 25.2 mg, 0.052 mmol). TLC (SiO2): Rf = 0.22
(n-hexane : ethyl acetate = 10:1). 1H NMR (500 MHz, CDCl3) δ 5.03 (br, 1H), 4.29-4.28 (m, 1H), 3.78-
3.57 (m, 1H), 1.46 (s, 9H). 13C{1H} NMR (125 MHz, CDCl3) δ 155.6, 80.2, 63.9, 50.4, 47.5, 35.5, 28.3.
FTIR (ATR): 3348, 2977, 1694, 1511, 1392, 1367, 1252, 1166, 1076, 942, 720 cm-1. HRMS m/z
+
(DART) calcd for C9H16Br4NO2 (M+H)+ 485.7909, found 485.7923.
1,1,1,3,7-Pentabromoheptane (3x): Following the general procedure, 3x was obtained
from a flash column chromatography (n-hexane) as a coloress oil (88% yield, 43.1 mg,
0.088 mmol). TLC (SiO2) Rf = 0.35 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 4.21
(dq, J = 4.6 Hz, 4.0 Hz, 1H), 3.85 (dd, J = 16.0 Hz, 4.0 Hz, 1H), 3.55 (dd, J = 16.0 Hz, 4.6 Hz, 1H), 3.44
(t, J = 6.3 Hz, 2H), 2.17-2.10 (m, 1H), 2.05-1.87 (m, 3H), 1.84-1.76 (m, 1H), 1.73-1.64 (m, 1H). 13C{1H}
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NMR (125 MHz, CDCl3) δ 66.7, 51.3, 38.7, 36.0, 33.1, 31.7, 26.0. FTIR (ATR) 2940, 2864, 1733, 1455,
1430, 1248, 1187, 1005, 939, 721 cm-1. HRMS m/z (DART) calcd for C7H11Br4 (M-Br)+ 410.7589, found
410.7574.
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(2,4,4,4-Tetrabromobutyl)benzene (3y): Following the general procedure, 3y was
obtained from a flash column chromatography (n-hexane) as a coloress oil (30% yield,
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13.4 mg, 0.030 mmol). TLC (SiO2): Rf = 0.38 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.34-7.26 (m,
5H), 4.39-4.35 (m, 1H), 3.85 (dd, J = 4.6 Hz, 4.0 Hz, 1H), 3.67 (dd, J = 11.5 Hz, 4.6 Hz, 1H), 3.53 (dd, J
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= 9.2 Hz, 5.2 Hz, 1H), 3.23 (dd, J = 9.2 Hz, 5.2 Hz, 1H). C{1H} NMR (125 MHz, CDCl3) δ 137.4,
129.4, 128.6, 127.3, 65.8, 51.5, 46.0, 35.9. NMR spectra of the 3y were consistent with the reported one.6
(3,5,5,5-Tetrabromopentyl)benzene (3z): Following the general procedure, 3z was
obtained from a flash column chromatography (n-hexane) as a coloress oil (84%
yield, 38.6 mg, 0.084 mmol). TLC (SiO2) Rf = 0.40 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 7.32-7.20
(m, 5H), 4.18 (ddt, J = 9.7 Hz, 4.6 Hz, 4.0 Hz, 1H), 3.88 (dd, J = 16.0 Hz, 4.0 Hz, 1H), 3.57 (dd, J = 16.0
Hz, 4.6 Hz, 1H), 2.98 (ddd, J = 13.8 Hz, 9.2 Hz, 4.6 Hz, 1H), 2.82 (ddd, J = 13.8 Hz, 8.0 Hz, 5.7 Hz, 1H),
2.44 (dddd, J = 13.8 Hz, 9.2 Hz, 6.9 Hz, 4.0 Hz, 1H), 2.28 (dddd, J = 14.3 Hz, 9.7 Hz, 5.2 Hz, 4.6 Hz,
1H). 13C{1H} NMR (125 MHz, CDCl3) δ 140.2, 128.6, 126.3, 66.8, 51.3, 41.1, 35.9, 33.6. NMR spectra
of the 3z were consistent with the reported one.6
1,1,1,3-Tetrabromo-4,4-bis(carboxymethoxy)butane (3aa): Following the
general procedure, 3aa was obtained from a flash column chromatography (n-
hexane : ethyl acetate = 10:1) as a coloress oil (43% yield, 21.5 mg, 0.043 mmol).
TLC (SiO2): Rf = 0.12 (n-hexane : ethyl acetate = 10:1). 1H NMR (500 MHz, CDCl3) δ 4.27-4.22 (m,
1H), 3.92 (dd, J = 16.0 Hz, 4.0 Hz, 1H), 3.86 (dd, J = 10.9 Hz, 4.0 Hz, 1H), 3.80 (s, 1H), 3.77 (s, 1H),
13
3.59 (dd, J = 16.0 Hz, 10.9 Hz, 1H), 2.89-2.83 (m, 1H), 2.45-2.38 (m, 1H). C{1H} NMR (125 MHz,
CDCl3) δ 168.9, 168.6, 67.0, 53.0, 52.9, 50.3, 48.7, 38.4, 35.0. NMR spectra of the 3aa were consistent
with the reported one.12
2-Bromo-3-(tribromomethyl)bicyclo[2.2.1]heptane (3ab): Following the general
procedure, 3ab was obtained from a flash column chromatography (n-hexane) as a
coloress oil (90% yield, 38.0 mg, 0.090 mmol, 94:6 d.r.) TLC (SiO2): Rf = 0.50 (n-
hexane). 1H NMR (500 MHz, CDCl3) δ 4.11 (ddd, J = 9.7 Hz, 5.7 Hz, 1.2 Hz, 1H), 2.88 (d, J = 5.7 Hz,
1H), 2.67 (d, J = 1.2 Hz, 2H), 2.34 (d, J = 10.9 Hz, 1H), 2.09 (dd, J = 12.6 Hz, 10.9 Hz, 1H), 1.63 (dd, J
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= 12.6 Hz, 9.2 Hz, 2H), 1.44 (t, J = 10.9 Hz, 1H), 1.34 (d, J = 10.9 Hz, 1H). 13C{1H} NMR (125 MHz,
CDCl3) δ 74.0, 56.7, 46.0, 44.2, 44.1, 35.3, 30.2, 24.2. NMR spectra of the 3ab were consistent with the
reported one.14j
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1-Bromo-4-(tribromomethyl)cyclooctane (3ac): Following the general procedure,
3ac was obtained from a flash column chromatography (n-hexane) as a coloress oil
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{64% yield, 28.0 mg, 0.064 mmol, 58:42 d.r. (from 1-octene)}. TLC (SiO2): Rf =
0.49 (n-hexane). 1H NMR (500 MHz, CDCl3) δ 4.49-4.44 (m, 1H, H2 (trans)), 4.42-4.37 (m, 1H, H1
(cis)), 2.75-2.70 (m, 1H), 2.66-2.54 (m, 2H), 2.49-2.32 (m, 5H), 2.25-2.12 (m, 4H), 2.09-1.96 (m, 3H),
1.93-1.88 (m, 1H), 1.86-1.56 (m, 8H), 1.53-1.38 (m, 2H). 13C{1H} NMR (125 MHz, CDCl3) δ 60.4, 60.2,
55.8, 55.7, 55.3, 54.9, 37.9, 36.5, 34.8, 33.0, 32.13, 32.07, 31.3, 29.8, 28.3, 27.8, 25.6, 23.0. FTIR (ATR):
3412, 2963, 2921, 2849, 2695, 2163, 1981, 1721, 1460, 1443, 1436, 1423, 1373, 1361, 1347, 1328, 1281,
1245, 1229, 1208, 1175, 1155, 1119, 1099, 1073, 1043, 1005, 975, 944, 913, 856, 833, 820, 774, 762,
697, 673 cm-1. HRMS m/z (DART) calcd for C9H14Br3 (M-Br)+ 358.8640, found 358.8627. NMR spectra
of the 3ac were consistent with the reported one.29
1,1,1,5-Tetrabromo-3-methyl-3-pentene (3ad, 3ad’): Following
the general procedure, 3ad and 3ad’ was obtained from a flash
column chromatography (n-hexane) as a coloress oil {48% yield,
19.0 mg, 0.048 mmol, 3ad:3ad’ = 88:12 (from isoprene)}. TLC (SiO2): Rf = 0.44 (n-hexane). 1H NMR
(500 MHz, CDCl3) δ 5.97 (t, J = 8.6 Hz, 1H), 4.04 (d, J = 8.6 Hz, 2H), 3.82 (s, 2H), 2.08 (s, 3H). 13C{1H}
NMR (125 MHz, CDCl3) δ 137.1, 130.3, 67.0, 39.2, 27.5, 17.8. FTIR (ATR): 2922, 2853, 1736, 1650,
1437, 1377, 1306, 1229, 1203, 1090, 1020, 981, 935, 871, 788, 700 cm-1. HRMS m/z (DART) calcd for
C6H9Br4 (M+H)+ 396.7432, found 396.7443.
3-(Bromomethyl)-4-(2,2,2-tribromoethyl)-dimethylcyclopentene-1,1-carboxyl-
ate (3ae): Following the general procedure, 3ae was obtained from a flash column
chromatography (n-hexane : ethyl acetate = 10:1) as a coloress oil {75% yield, 40.5
mg, 0.075 mmol, 92:8 d.r. (from 1ae)}. TLC (SiO2): Rf = 0.11 (n-hexane : ethyl
acetate = 10:1). 1H NMR (500 MHz, CDCl3) δ 3.77 (s, 6H), 3.57 (dd, J = 5.7 Hz, 4.6 Hz, 1H), 3.35 (dd,
J = 10.9 Hz, 4.6 Hz, 1H), 3.30 (dd, J = 10.3 Hz, 9.5 Hz, 1H), 3.09 (dd, J = 9.5 Hz, 6.3 Hz, 1H), 2.80-2.74
(m, 2H), 2.61 (dd, J = 7.5 Hz, 6.9 Hz, 1H), 2.57-2.51 (m, 1H), 2.40 (dd, J = 14.3 Hz, 9.2 Hz, 1H), 2.37
(dd, J = 14.3 Hz, 5.7 Hz, 1H). 13C{1H} NMR (125 MHz, CDCl3) δ 172.6, 172.5, 58.6, 57.8, 53.1, 44.4,
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43.3, 39.5, 39.4, 38.3, 33.6. FTIR (ATR): 3461, 3001, 2952, 2844, 1727, 1434, 1369, 1257, 1244, 1199,
1165, 1111, 1068, 1028, 964, 937, 912, 875, 854, 822, 722, 690, 669, cm-1. HRMS m/z (DART) calcd
for C12H17Br4O4 (M+H)+ 540.7855, found 540.7861.
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■ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.0000.
1H, 13C{1H} and 19F NMR spectra, UV/Vis and FL and PL spectra, and full detailed optimization study
experiments (PDF).
■AUTHOR INFORMATION
Corresponding Author
Correspondence to E.Y. and A.I.
Eiji Yamaguchi (yamaguchi@gifu-pu.ac.jp)
Akichika Itoh (itoha@gifu-pu.ac.jp)
Competing interests
The authors declare no competing interests.
■ACKNOWLEDGMENT
This work was supported by the Sumitomo Foundation, and JSPS KAKENHI Grant number: 18K14871.
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