Reaction of arylhydrazines with diaryl ditellurides in the air: Insight into bimolecular homolytic substitution on tellurium via Aryl–Te bond cleavage

Article abstract of DOI:10.1002/hc.21471

The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was studied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution (S_H2) reaction with a phenyl radical generated from phenylhydrazine in the air, to afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthesis, a one-pot synthesis of unsymmetrical diaryl tellurides was developed by the S_H2 reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The selectivity of mono-/di-substitution and the reactivity of arylhydrazines depend on the nature of the substituents on the arylhydrazines, that is, electron-donating or -withdrawing group.

Full text of DOI:10.1002/hc.21471

Received: 29 September 2018
DOI: 10.1002/hc.21471
Revised: 22 November 2018
Accepted: 22 November 2018
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S H O R T C O M M U N I C AT I O N
Reaction of arylhydrazines with diaryl ditellurides in the air:
Insight into bimolecular homolytic substitution on tellurium via
Aryl–Te bond cleavage
Yuki Yamamoto
Akiya Ogawa
|
Fumiya Sato
|
Shintaro Kodama
|
Akihiro Nomoto
|
Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture
University, Sakai, Osaka, Japan
Abstract
The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was stud-
ied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution
Correspondence
(
SH2) reaction with a phenyl radical generated from phenylhydrazine in the air, to
Akiya Ogawa and Shintaro Kodama,
Department of Applied Chemistry,
Graduate School of Engineering, Osaka
Prefecture University, Sakai, Osaka, Japan.
Emails: ogawa@chem.osakafu-u.ac.jp and
s-kodama@chem.osakafu-u.ac.jp
afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthe-
sis, a one-pot synthesis of unsymmetrical diaryl tellurides was developed by the SH2
reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The
selectivity of mono-/di-substitution and the reactivity of arylhydrazines depend on
the nature of the substituents on the arylhydrazines, that is, electron-donating or
Funding information
JSPS KAKENHI, Grant/Award Number:
JP16H04138 and JP16K17882; Ministry
of Education, Culture, Sports, Science and
Technology
-
withdrawing group.
1
|
INTRODUCTION
The S 2 reaction at the tellurium atom has been ap-
H
Organotellurium compounds have served as important syn-
plied to the synthetic reactions such as carbotelluration of
[1–9]
[21–23]
[24]
thetic intermediates,
and especially, diorganyl tellurides
alkynes,
group-transfer imidoylation, and living rad-
[25–28]
have been used as carbon nucleophile sources through a
ical polymerization.
These reactions are generally in-
[
10–12]
tellurium-lithium exchange reaction.
In addition, a rela-
duced by a radical initiator such as AIBN and V-40, and bond
[13]
1
2
1
tively weaker carbon–tellurium bond (48 kcal/mol) makes
organotellurium compounds fascinating in radical chemis-
cleavage of unsymmetrical tellurides, R TeR (R = aryl,
2
3
R = alkyl, acyl) occurs typically on an alkyl C –Te bond or
sp
[
14]
2
2
try.
For example, organotelluro groups can be easily re-
an acyl C –Te bond rather than an aromatic C –Te bond
sp sp
[15]
duced with tin hydrides to be replaced by hydrogen.
In
to generate new alkyl or acyl radicals. In contrast, the gener-
ation of aryl radicals from symmetrical and unsymmetrical
diaryl tellurides has largely been unexplored.
1
1
radical chemistry, diorganyl ditellurides (R TeTeR ) act as
[16]
excellent carbon radical trapping agents (eq. 1). Diorganyl
1
2
tellurides (R TeR ) have been used for a bimolecular homo-
Recently, we have developed two types of aryl radical
lytic substitution (S 2) reaction with a carbon radical to gen-
generation methods. One is a photoinduced decomposition
H
[17–20]
[29]
erate a new carbon radical (eq. 2).
of triarylbismuthines
and the other is an air-induced de-
[30–34]
composition of arylhydrazines.
In the latter method,
⋅
R +R TeTeR →R TeR +R Te
1
1
1
1
⋅
(1)
(2)
arylhydrazine hydrochlorides can be employed as an aryl
radical source, and by using this method, we successfully
⋅
1
2
1
R +R TeR →R TeR +R
2⋅
developed the arylation of aminoheterocycles and aromatic
Dedicated to 82nd birthday of Professor Naomichi Furukawa.
[30,31]
diamines,
the synthesis of unsymmetrical diaryl sulfides
Heteroatom Chemistry. 2018;e21471.
https://doi.org/10.1002/hc.21471
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
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1 of 8

2
of 8
YAMAMOTO eT Al.
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[
32,33]
and selenides,
and the aryl iodide synthesis by the trap-
yield of 3a (entry 6 vs entry 7). Slightly decrease of the tem-
perature (25°C) somewhat improved the yield of 3a (87%,
entry 8). This reaction did not proceed in the absence of a
base or air (entries 9–10). When a slightly excess amount of
1a (0.6 mmol) was used, 3a was obtained in excellent yield
(93% NMR yield; 84% isolated yield, entry 11).
[34]
ping of aryl radicals with I . On the basis of these studies,
2
we have investigated the reaction of arylhydrazine hydrochlo-
rides with diaryl ditellurides to synthesize symmetrical and
unsymmetrical diaryl tellurides. Surprisingly, we have found
1
2
that in situ generated diaryl tellurides (Ar TeAr ) can also un-
dergo an S 2 reaction with aryl radicals (generated from aryl-
Keeping the optimized reaction conditions in mind, we
next investigated to synthesize unsymmetrical diaryl tellu-
rides from 4-methoxyphenylhydrazine hydrochloride (1b)
and diphenyl ditelluride (2) (Scheme 1). Fortunately, the de-
sired unsymmetrical telluride 4a was obtained as the major
product in 42% yield, along with symmetrical tellurides 3b
H
1
2
hydrazines) at the tellurium atom to generate Ar · or Ar ·.
Herein, we report an S 2 reaction of diaryl ditellurides with
H
arylhydrazines in the air to afford unsymmetrical or symmet-
rical diaryl tellurides.
(
18%) and 3a (8%). The formation of 3b and 3a strongly
2
RESULTS AND DISCUSSION
suggests that the bimolecular homolytic substitution (S 2)
|
H
reaction between the formed diaryl telluride (4a) and the
Initially, we examined the synthesis of symmetrical diaryl
tellurides such as diphenyl telluride (3a) by the model re-
action of phenylhydrazine hydrochloride (1a) with diphenyl
ditelluride (2) in the presence of base in the air (Table 1). As
aryl radical (p-MeO-C H •) might take place competitively:
6
4
p-MeO-C H • attacks 4a to form 3b and Ph•, which then
6
4
attacks 2 to form 3a.
Table 2 represents the optimization of the synthesis of
unsymmetrical diaryl tellurides. When the reaction was
conducted in refluxing MeOH, both the yield and product
selectivity of the desired product 4a were improved (entries
1-3). The results encouraged us to examine the influence of
solvents to this unsymmetrical diaryl telluride synthesis. A
variety of alcohols were examined (entries 3–7), and the use
1
a decomposes in the presence of base in the air to generate a
phenyl radical, the influence of base was firstly investigated.
When an inorganic base was used for this reaction, 3a was
obtained in moderate yield (entries 1–3). NaHCO as a weak
3
base did not work well for this diphenyl telluride synthesis
(
entry 4). When NaOH as a strong base was used, 3a was
i
obtained in 82% yield (entry 5). Interestingly, when Et N was
of PrOH led to the formation of unsymmetrical telluride 4a
3
used, the desired reaction proceeded smoothly to afford 3a
in good yield (83%, entry 6). The use of a bulky base such
as N,N-diisopropylethylamine (DIPEA) resulted in a similar
in 44% yield (75% selectivity). When benzene and toluene
as nonpolar solvents were used, 4a was obtained in 35%
and 23% yields, respectively (entries 8–9). The reaction
TABLE 1 Optimization of reaction
NHNH
2
• HCl
Te
Base (1.5 mmol)
MeOH (3.0 mL)
Te
conditions for the synthesis of diphenyl
+
2
telluride (3a)
3
0 °C, 3 h, air
1
a (0.5 mmol)
2 (0.25 mmol)
3a
Entry
Base
Yield (%)a
1
2
3
4
5
6
7
LiOH˙H O
63
66
60
15
82
83
85
87
2
Cs CO
2
3
K CO
2
3
NaHCO3
NaOH
Et N
3
DIPEA
b
8
Et N
3
b
9
1
1
None
N.D.
3
93 (84)
0b,c
1
Et N
3
b,d
Et N
3
a
1
The yield was calculated based on 2 and determined by H NMR using 1,3,5-trioxane as an internal standard
(
isolated yield).
At 25°C.
b
c
Under argon atmosphere.
d
Hydrazine hydrochloride 1a (0.6 mmol) was used.

YAMAMOTO eT Al.
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NHNH • HCl
Te
Et N (3.0 equiv.)
3
2
+
MeOH (3.0 mL)
2
MeO
MeO
2
5 °C, 3 h, air
1
b (0.5 mmol)
2 (0.25 mmol)
SCHEME 1 Reaction of
Te
Te
Te
4
-methoxyphenylhydrazine hydrochloride
+
+
a
with diaryl ditelluride. The yield was
MeO
OMe
caluculated based on 2 and determined by
4a (42%a)
3b (18%a)
3a (8%a)
1
H NMR (1,3,5-trioxane, CDCl )
3
TABLE 2 Optimization of reaction conditions for the synthesis of unsummetrical diaryl tellurides
NHNH
2
• HCl
Te
Et N (1.5 mmol)
3
+
solvent (3.0 mL)
temp., time, air
MeO
2
1b (0.5 mmol)
2 (0.25 mmol)
Te
Te
Te
+
+
MeO
MeO
OMe
4a
3b
3a
Yield (%)a
4a
Selectivity
b
Entry
Solvent
Temp. (°C)
1b (mmol)
Time (h)
3b
3a
4a (%)
1
2
3
4
5
6
7
8
9
MeOH
MeOH
MeOH
EtOH
25 °C
0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.8
1.0
3
3
3
3
3
3
3
3
3
3
3
3
3
6
24
6
6
6
42
22
52
10
44
23
39
35
23
14
50
10
34
54
50
54
60
57
18
18
19
36
10
6
6
14
9
3
16
2
10
13
15
20
33
46
8
12
7
N.D.
5
64
42
67
22
75
74
75
57
60
82
61
83
65
74
63
60
52
48
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
reflux
i
PrOH
t
BuOH
4
7
n
BuOH
benzene
toluene
THF
12
6
N.D.
16
N.D.
8
10
11
12
13
14
15
16
17
18
CH CN
3
AcOEt
1,4-dioxane
i
PrOH
6
i
PrOH
15
16
22
17
i
PrOH
i
PrOH
i
PrOH
a
1
The yield was calculated based on 2 and determined by H NMR (1,3,5-trioxane, CDCI ).
3
b
Selectivity 4a (%) = 100 × 4a / (4a + 3b + 3a).
proceeded even when some aprotic solvents were used, but
the yields and selectivities were lower than those in the case
excess amount of 1b decreased the selectivity of 4a (entries
16–18 vs entry 14).
i
of PrOH (entries 10–13). As to the reaction time, the yield
In these reactions, symmetrical diaryl tellurides 3b and
and the selectivity of 4a were improved by prolonging the
3a were generally formed as by-products. This strongly sug-
reaction time for 6 h (entries 14 and 15 vs entry 5). Using
gests the S 2 reaction also occurred at the tellurium of diaryl
H

4
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YAMAMOTO eT Al.
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NHNH • HCl
2
Te
Et N (0.9 mmol)
3
+
iPrOH (3.0 mL),
reflux, 3 h, air
MeO
MeO
1
b (0.3 mmol)
3a (0.3 mmol)
SCHEME 2 Reaction of
Te
Te
arylhydrazine hydrochloride with diaryl
+
+ recovery 3a (41%)
a
telluride. The yield was calculated
MeO
OMe
1
based on 3a and determined by H NMR
4
a (45%a)
3b (9%a)
(
1,3,5-trioxane, CDCl )
3
NHNH • HCl
Te
Et
3
N (1.5 mmol)
Te
2
SCHEME 3 Synthesis of symmetical
+
i
a
iPrOH (3.0 mL)
diaryl telluride 3a in PrOH. The yield was
2
1
25 °C, 3 h, air
calculated based on 2 and determined by H
3a (94%)a
1
a (1.0 mmol)
2 (0.25 mmol)
NMR (1,3,5-trioxane, CDCl )
3
tellurides. Therefore, we next paid attention to the S 2 reac-
was obtained in 45% yield along with 9% of 3b and 41% of 3a
H
tion using diaryl telluride such as Ph Te as a carbon radical
(recovered). The result clearly indicates that the S 2 reaction
2
H
trapping reagent (Scheme 2).
on the tellurium of diphenyl telluride can occur successfully.
Thus, we next examined the synthesis of unsymmetrical
diaryl telluride using diphenyl telluride (3a) generated in
situ from diphenyl ditelluride (2). As indicated in Scheme 3,
3a can be obtained in high yield by changing the solvent
To clarify whether the bimolecular homolytic substitu-
tion (S 2) reaction occurs on the tellurium of diaryl tellu-
H
ride, we carried out the reaction using equimolar amounts of
4
-methoxyphenylhydrazine hydrochloride (1b) and diphenyl
i
i
telluride (3a) in the presence of Et N in refluxing PrOH in
from MeOH (Table 1, entry 11) to PrOH in the reaction of
3
the air for 3 hours. As a result, unsymmetrical telluride 4a
phenylhydrazine hydrochloride (1a) with 2. Therefore, the
TABLE 3 Optimization of
NHNH
2
• HCl
Te
Et
3
N (1.5 mmol)
Te
reaction conditions for the one-pot
synthesis of unsymmetrical diaryl
telluride
+
iPrOH (3.0 mL)
2
2
5 °C, 3 h, air
3
a
1
a (1.0 mmol)
2 (0.25 mmol)
NHNH
2
• HCl
Te
Te
+
MeO
Et N (1.5 mmol)
reflux, time, air
1b (x mmol)
MeO
MeO
OMe
3
4a
3b
Te
+
3
a
Yield (%)a
4a
Entry
1b (mmol)
Time (h)
3b
3a
1
2
3
4
5
6
0.5
0.6
1.0
1.0
1.0
1.0
6
6
1
2
4
41
60
58
72 (50 )
71
62
5
12
16
26 (6 )
34
56
47
38
30
21
23
b
b
24
32
a
1
The yield was calculated based on 2 and determined by H NMR (1,3,5-trioxane, CDCI ).
3
b
Isolated yield.

YAMAMOTO eT Al.
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a result, the yield of 4a was improved (60%). When a similar
reaction was conducted using further excess amounts of 1b
for 1 hour, a similar result was obtained (entry 3 vs entry 2).
Prolonging the reaction time resulted in increase in both the
yields of 4a and 3b (entries 4–5). However, the yield of 3b
was not further increased even prolonging the reaction time
stability
>
Te
Te
MeO
MeO
OMe
I
II
(
24 hours) (entry 6). Comparing the methods using Ph Te (in
2
reactivity
>>
situ generated) vs (PhTe) (Table 3, entry 4 vs Table 2, entry
2
>
1
7), the one-pot reaction was more advantageous in terms of
MeO
O N
2
the higher yield of unsymmetrical diaryl telluride 4a.
III
IV
Keeping the diaryl telluride synthesis using phenylhy-
drazine bearing an electron-donating group such as p-MeO
group in mind, we next examined a similar one-pot reaction
of diphenyl telluride (3a) with arylhydrazine hydrochlorides
FIGURE 1 Reactivity of radical species and stability of S 2 key
H
species
unsymmetrical diaryl telluride synthesis might be simplified
bearing an electron-withdrawing group like p-NO (1c).
2
i
by a one-pot reaction in PrOH via the generation of the sym-
However, the S 2 reaction of in situ generated 3a with 1c did
H
metrical diphenyl telluride 3a, and the subsequent reaction
with arylhydrazine hydrochlorides (Table 3).
not proceed, and only 3a was obtained in 96% yield.
The selectivity of unsymmetrical/symmetrical diaryl
Thus, the one-pot synthesis of unsymmetrical diaryl tellu-
ride 4a using 4-methoxyphenylhydrazine hydrochloride (1b)
and diphenyl ditelluride (2) was investigated in detail. When
the stoichiometric reaction of 1b with in situ generated 3a
was carried out for 6 h, the desired unsymmetrical telluride
tellurides and the influence of the substituents on the S 2
H
reaction between 3a and substituted phenyl radicals can
be explained by the stability of radical species, as shown
in Figure 1. In general, radical species are stabilized by an
electron-withdrawing group and destabilized by an electron-
donating one. In the case of p-MeO group, species I is more
stable than species II; therefore, unsymmetrical diaryl tellu-
ride 4a was obtained as the major product. In terms of the
4
a was obtained in 41% yield along with 3b (5%) (entry 1).
Since 56% of 3a was recovered in this reaction, we next ex-
amined the reaction using excess amounts of 1b (entry 2). As
NHNH
2
• HCl
Te
Et N (1.5 mmol)
Te
3
+
MeOH (3.0 mL)
reflux, 24 h, air
O
2
N
2
2
O N
a
b
4
b (58% (48% ))
1
c (0.5 mmol)
2 (0.25 mmol)
a
SCHEME 4 Reaction of arylhydrazines bearing electron-withdrawing groups with diphenyl ditelluride. The yield was calculated based on 2
1
b
and determined by H NMR (1,3,5-trioxane, CDCl ). Isolated yield
3
SCHEME 5 A plausible reaction
pathway for the synthesis of unsymmetrical
diaryl tellurides

6
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YAMAMOTO eT Al.
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reactivity of radical species generated from arylhydrazine hy-
drochlorides, species III is much more reactive than species
IV; therefore, the reaction proceeded smoothly with 1b and
did not proceed with 1c.
4
EXPERIMENTAL PROCEDURE
|
Unless otherwise stated, all starting materials and solvents
were purchased from commercial sources and used without
Since the S 2 reaction on the tellurium of diphenyl tel-
1
H
further purification. H NMR spectra were recorded on JEOL
luride did not proceed with 1c, we next examined the syn-
thesis of unsymmetrical diaryl telluride by the reaction of
diphenyl ditelluride (2) with arylhydrazine hydrochloride
JNM-ECS400 (400 MHz) FT NMR system or JEOL JNM-
ECX400 (400 MHz) FT NMR system in CDCl with Me Si
3
4
13
as an internal standard. C NMR spectra were recorded on
bearing electron-withdrawing group like -NO (1c). As we
125
2
JEOL JNM-ECX400 (100 MHz). Te NMR spectra were
expected, the reaction of 1c with 2 successfully afforded the
unsymmetrical diaryl telluride 4b in 48% isolated yield, and
interestingly, no bis(p-nitrophenyl) telluride was obtained
recorded on JEOL JNM-ECX400 (126 MHz).
(Scheme 4).
4
.1
Synthesis of diphenyl telluride (3a)
[35]
|
Based on these mechanistic considerations, a possible
(
Table 1, entry 11)
pathway for this diaryl telluride synthesis is proposed, as
Phenylhydrazine hydrochloride (1a) (86.8 mg, 0.6 mmol),
shown in Scheme 5. Phenylhydrazine hydrochloride (1a)
diphenyl ditelluride (2) (102.4 mg, 0.25 mmol), Et N
3
reacts with Et N to generate phenylhydrazine A, which is
3
(
0.21 mL, 1.5 mmol), and MeOH (3.0 mL) were added to a
oxidized by air to convert to phenyl radical C. Trapping C
round-bottomed flask, and the reaction mixture was stirred
at 25 °C for 3 hours under air. After the reaction was com-
plete, the resulting mixture was transferred into a round-
bottom flask using MeOH (5 mL) and concentrated under
reduced pressure. The residue was purified by column chro-
by diphenyl ditelluride (2) affords diphenyl telluride (3a).
4
-Methoxyphenyl hydrazine hydrochloride (1b) is con-
verted into the corresponding aryl radical C’ in the same
way. Then, the S 2 reaction between C’ and 3a occurs to
H
afford the desired unsymmetrical telluride 4a and phenyl
matography (eluent: hexane) to give diphenyl telluride (3a)
radical C.
1
(
118.5 mg, 84% yield) as a pale-red oil; H NMR (400 MHz,
CDCl ): δ 7.69 (d, J = 7.8 Hz, 4H), 7.27 (t, J = 7.3 Hz, 2H),
3
1
3
1
7
.20 (t, J = 7.6 Hz, 4H); C{ H} NMR (100 MHz, CDCl ):
3
3
CONCLUSION
|
125
δ 138.1, 129.6, 128.0, 114.8; Te NMR (126 MHz, CDCl ):
3
δ 691.3.
In summary, the reaction of aryl radicals generated from
arylhydrazines in the air, with diaryl ditelluride or diaryl
telluride was investigated in detail. Symmetrical diphenyl
telluride could be synthesized conveniently by the reac-
tion of phenylhydrazine with diphenyl ditelluride. Based
on this symmetrical diaryl telluride synthesis, the one-pot
reaction of arylhydrazines with in situ generated diphe-
nyl telluride in the air was examined. The selectivity of
the reaction products (unsymmetrical/symmetrical diaryl
tellurides) and the reactivity of the arylhydrazine hydro-
chlorides were found to be dependent on the stability of
radical species. In the case of arylhydrazine hydrochloride
bearing electron-donating group, unsymmetrical diaryl tel-
luride was preferentially synthesized. Using arylhydrazine
hydrochloride bearing electron-withdrawing group, the in
situ generated aryl radical was not reactive enough to un-
4
.2
hydrochloride (1b) with diphenyl telluride (3a)
Scheme 2)
Reaction of 4-methoxyphenylhydrazine
|
(
4
-Methoxyphenylhydrazine hydrochloride (1b) (52.4 mg,
0
.3 mmol), diphenyl telluride (3a) (84.5 mg, 0.3 mmol),
i
Et N (0.13 mL, 0.9 mmol), and PrOH (3.0 mL) were added
3
to a round-bottomed flask, and the reaction mixture was re-
fluxed for 3 h under air. After the reaction was complete,
the resulting mixture was transferred into a round-bottom
flask using MeOH (5 mL) and concentrated under reduced
1
pressure. The yield of the products was confirmed by H
NMR spectroscopy (internal standard: 1,3,5-trioxane,
CDCl ).
3
dergo the S 2 reaction, whereas the aryl radical could be
H
trapped by diphenyl ditelluride to afford an unsymmetrical
diaryl telluride with no formation of any by-products such
as symmetrical diaryl tellurides.
We are now investigating the effects of the substituents of di-
aryl tellurides on these reaction conditions in detail. We believe
that our studies on the bimolecular homolytic substitution at the
tellurium atom of diaryl tellurides lead to new approaches of aryl
radical chemistry using diaryl tellurides as aryl sources.
4
.3
One-pot synthesis of unsymmetrical
|
[35]
diaryl tellurides (Table 3, entry 4)
Phenylhydrazine hydrochloride (1a) (144.6 mg, 1.0 mmol),
diphenyl ditelluride (2) (102.4 mg, 0.25 mmol), Et N
3
i
(0.21 mL, 1.5 mmol), and PrOH (3.0 mL) were added
to a round-bottomed flask, and the reaction mixture was
stirred at 25 °C for 3 hours under air. After the reaction,

YAMAMOTO eT Al.
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4
1
-methoxyphenylhydrazine hydrochloride (1b) (174.6 mg,
ORCID
.0 mmol) and Et N (0.21 mL, 1.5 mmol) were added to
3
Shintaro Kodama
org/0000-0003-4190-9539
https://orcid.
the reaction mixture and refluxed for 2 hours under air.
After the reaction was complete, the resulting mixture was
transferred into a round-bottom flask using MeOH (5 mL)
and concentrated under reduced pressure. The residue was
REFERENCES
[
purified by preparative TLC on silica gel (eluent: CHCl /
3
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a; H NMR (400 MHz, CDCl ): δ 7.73 (d, J = 9.2 Hz,
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4975.
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b; H NMR (400 MHz, CDCl ): δ 7.62 (d, J = 8.7 Hz,
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(
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25
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ACKNOWLEDGMENTS
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007, 63, 11959.
This work was supported by JSPS KAKENHI Grant
Numbers JP16H04138 (to A.O.) and JP16K17882 (to
S.K.) and also supported by the Nanotechnology Platform
Program of the Ministry of Education, Culture, Sports,
Science and Technology (MEXT), Japan. The authors ac-
knowledge Dr. Shin-ichi Kawaguchi (Saga University), Dr.
Toshihide Taniguchi (Seika Corporation), and Dr. Takumi
Mizuno (Osaka Research Institute of Industrial Science and
Technology) for their contribution at the initial stage of this
work.
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