A new preparative method of aryl sulfonate esters by using cyclic organobismuth reagents

Article abstract of DOI:10.3987/com-07-s(w)63

A new method for the preparation of aryl sulfonate esters by using a cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good to high yields by treating 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoicacid (m-CPBA)and various sulfonic acids in dichloromethane.

Full text of DOI:10.3987/com-07-s(w)63

HETEROCYCLES, Vol. 74, 2007
771
HETEROCYCLES, Vol. 74, 2007, pp. 771 - 790. © The Japan Institute of Heterocyclic Chemistry
Received, 1st September, 2007, Accepted, 26th October, 2007, Published online, 30th October, 2007. COM-07-S(W)63
A NEW PREPARATIVE METHOD OF ARYL SULFONATE ESTERS BY
USING CYCLIC ORGANOBISMUTH REAGENTS
Naoto Sakurai and Teruaki Mukaiyama*
Center for Basic Research, The Kitasato Institute, 6-15-5 (TCI) Toshima, Kita-ku,
Tokyo 114-0003, Japan and Kitasato Institute for Life Sciences, Kitasato
University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan
E-mail; mukaiyam@abeam.ocn.ne.jp
th
Dedicated to Prof. Dr. Ekkehard Winterfeldt on the occasion of his 75 birthday
Abstract – A new method for the preparation of aryl sulfonate esters by using a
cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good
to high yields by treating 10-arylphenothiabismine 5,5-dioxides,
m-chloroperoxybenzoic acid (m-CPBA) and various sulfonic acids in
dichloromethane.
INTRODUCTION
1
Syntheses and reactions of organobismuth reagents were intensively studied by Barton et al. in 1980−90,
and in recent years, pentavalent organobismuth reagents are reported effective for N-arylation of
2
3
pyridin-2(1H)-ones, O-phenylation of tertiary alcohols and oxidative coupling reaction of carbonyl
4
compounds from our laboratory. Among these reactions, a ligand coupling reaction of pentavalent
organobismuth reagents is a very fundamental one, for example aryl halides or acetates were obtained by
5
the ligand coupling of triaryl bismuth dihalides or diacetates (Scheme 1). On the other hand, Suzuki et al.
also
reported
that
the
cyclic
pentavalent
bismuth
dichloride
such
as
λ
1
0-dichloro-10-(4’-methylphenyl)phenothia-10 5-bismine 5,5-dioxide is quite unstable for refluxing
CH
2
Cl
2
to give 4-chlorotoluene quantitatively via reductive elimination whereas cyclic bismuth part
6
remained unchanged (Scheme 2). Although there are hardly any ligand coupling reactions of pentavalent
bismuth disulfonates reported, an example of a coupling reaction of cyclic pentavalent organobismuth
7
ditosylates in situ to form aryl tosylates was very recently reported from our laboratory.

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HETEROCYCLES, Vol. 74, 2007
Aryl sulfonate esters are ubiquitous in the field of organic synthesis and are very attractive both as the
8
protected phenolic hydroxyl group and as the key intermediates of various synthetic reactions. For
example, aryl triflates are often used in transition-metal-catalyzed cross-coupling reactions and
9
alkoxycarbonylation, and even tosylates or mesylates are recently shown to be applicable to those
10
reactions.
Aryl sulfonate esters are prepared generally by treating phenols with the corresponding sulfonyl chlorides
1
1
or sulfonic anhydrides in the presence of organic bases such as pyridine or triethylamine. It is also
known that aryl triflates or mesylates are prepared after thermal decomposition of arenediazonium salts in
12
the corresponding sulfonic acids. However, these aryl triflates or mesylates were obtained by the
reaction carried out in a sulfonic acids solvent under harsh reaction conditions. To the best of our
knowledge, no general procedures for preparing the aryl arenesulfonates by using the corresponding
sulfonic acids have been reported yet. In this paper, we would like to describe the extended scope and
limitation of the present synthetic method.
Δ
Ar BiX
Ar BiX
ArX
(X = halogen, OAc)
3
2
2
Scheme 1
O
O
O
O
S
S
Δ
Cl
CH Cl
Bi
2
2
Bi
Cl
Cl
Cl
Scheme 2
RESULTS AND DISCUSSION
In the first place, the effects of oxidants and reaction conditions were examined. A model reaction was
carried out by using 10-phenylphenothiabismine 5,5-dioxide (1a) and 1.1 equiv. of oxidants in the
presence of p-toluenesulfonic acid in CH
hydroperoxide or benzoyl peroxide was used as an oxidant, the expected phenyl tosylate was not obtained
Entries 1 and 2). On the other hand, the desired phenyl tosylate was obtained in 49 or 87% yields
2 2
Cl , whose results are summarized in Table 1. When tert-butyl
(
respectively when an oxidant such as peracetic acid or m-CPBA was used (Entries 3 and 4) and the
reaction proceeded sluggishly at room temperature (Entry 5). When the amount of TsOH·H O was
2
reduced to 1.1 equiv., the yield of 2a decreased to 63% yield (Entry 6). Therefore, it was found that the

HETEROCYCLES, Vol. 74, 2007
773
amount of TsOH·H
equiv. of TsOH·H O was used (Entry 7). On the other hand, 2a was not obtained at all when sodium
p-toluenesulfonate was used (Entry 8).
2
O should be needed more than 2 equiv., and the best result was obtained when 2.8
2
Table 1. Reactions of 1a with various oxidants
O
O
S
oxidant (1.1 equiv.)
TsOH•H O
PhOTs
2a
2
−
78 to 0 °C, 10 min,
Bi
then reflux, 4 h, CH Cl
1a
2
2
Ph
Entry
Equiv. of TsOH•H O
Oxidant
tBuOOH
Yield / %
2
2.2
2.2
2.2
2.2
2.2
1.1
2.8
2.8c
NDb
ND
49
1
2
(PhCOO)2
3
CH COOOH
3
4
5a
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
b
87
48
6
63
7
91
8
ND
a
c
Reaction was carried out at rt for 30 h. Not Detected.
Sodium p-toluenesulfonate was used.
Various aryl tosylates were prepared next by using the corresponding 10-arylphenothiabismine
,5-dioxides under optimized conditions and the results are summarized in Table 2. Trivalent bismuth
compounds (1b−1m) were synthesized by way of substitution reaction of aryl Grignard reagents with
0-iodophenothiabismine 5,5-dioxide. Bismuth compounds, 1b−1d, having methylphenyl groups gave
5
1
the corresponding aryl tosylates over 80% yields regardless of the substituents’ position (Entries 1−3). In
the cases of bismuth compounds, 1e−1g, having methoxyphenyl groups, m-methoxyphenyl bismuth (1f)
gave m-methoxyphenyl tosylate in 85% yield (Entry 5). However, those with o- and p-methoxyphenyl
groups (1e and 1g) gave o-methoxyphenyl tosylate in 5% and p-methoxyphenyl tosylate in 32% yields
respectively. It was assumed that the intramolecular coordination of oxygen atom of o-methoxy group in
1
3
3
particular retarded the ligand coupling reaction. When the reaction was tried in refluxing CHCl ,
o-methoxyphenyl tosylate and p-methoxyphenyl tosylate were obtained in 52 and 76% yields,
respectively. These increases in the yields were caused by the reaction temperature in CHCl that was
3
higher than CH
ethoxycarbonyl, trifluoromethyl or halide substituents were tolerated to afford the expected aryl tosylates
2h−2l) in moderate to good yields (Entries 7−11), and 2-naphthyl tosylate (2m) was also obtained in
6% yield (Entry 12). In addition, it was found that the alkylbismuth derivative such as
2 2
Cl (Entries 4 and 6). On the other hand, electron-poor aryl groups having
(
8

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HETEROCYCLES, Vol. 74, 2007
1
0-methylphenothiabismine 5,5-dioxide (1n) gave methyl tosylate in moderate yield under these
conditions (Scheme 3).
Table 2. Synthesis of aryl tosylates by using optimized conditions
O
O
S
m-CPBA (1.1 equiv.)
78 to 0 °C, 10 min,
TsOH•H O
2
ArOTs
(
2.8 equiv.)
−
Bi
then reflux, 4 h, CH Cl
1bꢀ 1m
2
2
2bꢀ 2m
Ar
Entry
1
Ar
Product Yield / %a
Entry
Ar
Product Yield / %a
Me
O
1b
1c
2b
2c
2d
2e
2f
81
88
7
1h
1i
2h
2i
76
79
72
73
53
86
EtO
Me
Me
8b
F3C
2
F
3
1d Me
83
9b
1j
2j
OMe
Cl
4b
1e
5(52c)
85
10b
11b
12
1k
2k
2l
MeO
5
1f
1l Cl
6b
2g
32(76c)
1m
2m
1g MeO
a
b
c
Isolated yield. Reflux for 8
ꢀ
12 h. CHCl was used as a solvent (see experimental
3
section for detailed procedure).
O
O
S
m-CPBA (1.1 equiv.)
78 to 0 °C, 10 min,
TsOH•H O
2
MeOTs
n 66%
(
2.8 equiv.)
−
Bi
2
then reflux, 4 h, CH Cl
2
1n
2
Me
Scheme 3

HETEROCYCLES, Vol. 74, 2007
775
In order to examine the generality of this reaction, various sulfonic acids were employed next by using
0-phenylphenothiabismine 5,5-dioxide (1a) or 10-(2-naphthyl)phenothiabismine 5,5-dioxide (1m) under
optimized conditions (Table 3). Unsubstituted aromatic sulfonic acids such as benzenesulfonic acid or
-naphthalenesulfonic acid and those having electron withdrawing substituents such as 4-nitro or 4-chloro
group are applicable to this reaction to afford the desired phenyl sulfonate esters in good yields (Entries
1
2
1
−4). Moreover, the aromatic sulfonic acid having bulky electron donating substituent such as
2
,4,6-trimethyl group gave the expected sulfonate ester in sufficient yield (Entry 5). Although a phenyl
sulfonate ester having a free phenolic hydroxyl group (8a) is considered to be difficult to synthesize by
the conventional methods, the desired 8a was obtained in moderate yields by this method (Entry 6). With
respect to alkyl sulfonic acids, methane or ethanesulfonic acid gave the corresponding phenyl sulfonate
esters in good yields while trifluoromethanesulfonic acid gave expected 2-naphthyl triflate in moderate
yield due to an undesirable decomposition of bismuth compound by TfOH (Entries 7−9).
Table 3. Synthesis of aryl sulfonate esters
O
O
S
m-CPBA (1.1 equiv.)
78 to 0 °C, 10 min,
RSO H
3
RSO Ar
3
(
2.8 equiv.)
−
Bi
then reflux, 4 h, CH Cl
1a or 1m
2
2
ꢀ
3a 10a or 3m
Ar
Entry
1
RSO H
Product Yield / %a Entry
RSO H
Product Yield / %a
3
3
3a
4a
5a
6a
86
83
79
89
SO H
3
5
SO H
7a
8a
80
48
•
H O
2
3
•
xH O
2
SO H
3
2
3
4
•
H O
2
6b
HO
SO H
3
•
xH O
2
7
8
9
MeSO H
9a
10a
3m
89
84
50
O N
SO H
3
2
3
•
xH O
2
EtSO H
3
Cl
SO H
3
•
CF SO H
3
3
xH O
2
a
b
Isolated yield. Reflux 8 h
ꢀ
3a 10a; Ar = Ph, 3m; Ar = 2-naphthyl
The mechanism of this reaction and the reactivity of bismuth compounds are shown below. The reaction
started with the oxidation of trivalent bismuth by m-CPBA to form the corresponding pentavalent bismuth
dicarboxylate or hydroxy-carboxylate, and then the ligands were exchanged for sulfonic acids to afford

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HETEROCYCLES, Vol. 74, 2007
pentavalent bismuth disulfonate. Finally, aryl sulfonate esters were formed by lingand coupling reaction
of the disulfonates (Scheme 4).
O
O
O
O
O
O
S
S
S
m-CPBA
or
oxidation
Bi
Bi
Bi
ROCO
OCOR
ROCO
OH
Ar
Ar
Ar
Cl
Ligand
TsOH
O
Exchange
R =
O
O
O
S
S
Δ
ArOTs
Ligand
Coupling
Bi
Bi
TsO
OTs
Ar
OTs
Scheme 4. Plausible mechanism for the formation of the aryl sulfonate esters.
In order to clarify this mechanism, isolation of pentavalent bismuth compounds was tried, and the
pentavalent bismuth dicarboxylate (1o) was isolated as 1/4 etherate. Preparation of phenyl tosylate was
2 2 2
additionally demonstrated by using 1o and TsOH·H O in CH Cl , and PhOTs was obtained in 92% yield
(
Scheme 5). Although the trivalent bismuth tosylate was not isolated in this reaction, PhOTs was
apparently formed by the ligand coupling reaction of the pentavalent bismuth ditosylate since the
exchange of ligands from carboxylate to sulfonate would take place easily in the reaction of sulfonic acids
Cl
O
OH
(1 equiv.)
O
O
O
O
S
O
O
•
1/4 Et O
2
S
m-CPBA (1.1 equiv.)
Bi
Cl
Cl
Et O/CH Cl = 10/1
2
2
2
Ph
O
Bi
O
0
°C, 30 min
1a
Ph
1
o (96%, isolated)
O
O
S
TsOH•H O (2.2 equiv.)
2
1o
PhOTs (2a)
Bi
CH Cl reflux, 4 h
2
2
92%
OTs
Scheme 5

HETEROCYCLES, Vol. 74, 2007
777
1
g,14
and pentavalent bismuth dicarboxylate.
Thus, it was almost proved that formation of aryl sulfonate
esters by using cyclic organobismuth compounds proceeded as described in Scheme 4.
Further, it is very interesting to note that the cyclic bismuth compound having sulfone functionality gave
aryl sulfonate esters exclusively (see Table 4). When the reactions were carried out by using other
bismuth compounds such as triphenylbismuthane (1p), phenylbiphenyl-2,2’-ylenebismuthane (1q) or
1
0-phenylphenoxabismine (1r), the expected phenyl tosylate was hardly obtained under in any of the
three cases (Entries 1−3). Concerning these three bismuth compounds, it was therefore assumed that the
key step of the final ligand coupling did not proceed effectively though the oxidation with m-CPBA and
subsequent ligand exchange that formed their disulfonate took place. This unique reactivity of 1a might
be caused by transannular interaction of 1a between bismuth and the sulfonyl oxygen atom as was
6
indicated by Suzuki’s group.
Table 4. Effect of organobismuth reagents
m-CPBA (1.1 equiv.)
BiIII
TsOH•H O
PhOTs
2
−
78 to 0 °C, 10 min,
(2.2 equiv.)
2a
then reflux, 4 h, CH Cl
2
2
Entry
1
2
3
4
O
BiIII
Ph Bi
1a
3
Bi
Bi
1p
Ph 1q
1r
Ph
Yield / %
ND
1
trace
87
In conclusion, a synthesis of aryl sulfonate esters by using a novel ligand coupling between aryl group
and sulfonyloxy group on the pentavalent bismuth reagents was established. It was easy to carry out these
reactions since there was no need to isolate the less stable pentavalent bismuth reagents compared with
trivalent ones which are able to be purified regardless of temperature and moisture. Further, this coupling
reaction is considered as an alternative of the conventional method for preparing aryl sulfonate esters
because no preparations of sulfonyl chlorides and phenols in advance are needed. In regard to
organobismuth chemistry, it is interesting to note that the transannular interaction between bismuth and
the sulfonyl oxygen atom of 10-arylphenothiabismine 5,5-dioxides brought about extremely unique
ligand coupling reaction and that the cyclic pentavalent bismuth dicarboxylate (1o) was isolated in high
yield for the first time.
EXPERIMENTAL
General.
Melting points were measured on a micro melting point apparatus (Yanaco MP-S3) and remain

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HETEROCYCLES, Vol. 74, 2007
uncorrected. IR spectra were recorded on a Shimadzu IR-440 spectrophotometer (KBr or neat) or a
1
Thermo Electron Nicolet Avatar 370 spectrometer (ATR). H NMR spectra were recorded on a JEOL
H 3
JNM-EX270 (270 MHz) spectrometer. Chemical shifts (δ ) in CDCl are reported in parts per million
(
ppm) relative to tetramethylsilane (TMS). Splitting patterns are designated as s, singlet; d, doublet; t,
13
triplet; q, quartet; quin, quintet; m, multiplet; br, broad. C NMR spectra were recorded on a JEOL
JNM-EX270 (68 MHz) spectrometer with complete proton decoupling. Chemical shifts (δ ) in CDCl are
reported in ppm relative to TMS using the solvent resonance (CDCl : δ 77.0 ppm) as an internal standard.
C
3
3
C
HRMS spectra were recorded on a JEOL JMS-700V (EI positive) and Agilent 6890 series GC system.
Analytical TLC was performed on Merck TLC plates coated with silica gel (60 F254, 0.25 mm).
Preparative TLC was carried out on glass plates coated with silica gel (Wakogel B-5F). Anhydrous THF,
Et O, CH Cl , CHCl were purchased from Kanto Chemical Co., Inc.. Other solvents were distilled after
2
2
2
3
dehydrated by using appropriate drying agents. m-CPBA (contents > 65 %, remainder 3-chloro benzoic
acid and water) and Ph Bi were purchased from Tokyo Kasei Kogyo (TCI) and used without further
3
purification. Hydrate formed sulfonic acids were also purchased from TCI, and used without further
purification. Commercially available bismuth (III) chloride was activated by refluxing with thionyl
dichloride before use. All reagents were purchased from Tokyo Kasei Kogyo, Kanto Chemical Co., Inc.,
Wako Pure Chemical Industry or Aldrich.
Preparation of organobismuth(III) reagents.
Organobismuth
reagents
such
(1n),
as
10-arylphenothiabismine
5,5-dioxides
(1q)
(1a−1m),
1
1
0-methylphenothiabismine
phenylbiphenyl-2,2’-ylenebismuthane
and
0-phenylphenoxabismine (1r) were prepared by modified method of the reported procedures, and
described below in detail. All the new organobismuth reagents were identified by elemental analysis.
1
1
1
0-Phenylphenothiabismine 5,5-dioxide (1a)
Dichlorophenylbismuthine (16.1 g, 45 mmol) was prepared as insoluble precipitate by the reaction of
triphenylbismuthine (6.6 g, 15 mmol) and bismuth (III) chloride (9.5 g, 30 mmol) in Et O (50 mL) for 2 h
at rt, and 100 mL of THF was added just before proceeding next step. To a solution of
,2’-dilithiodiphenyl sulfone generated from diphenyl sulfone (9.8 g, 45 mmol) and n-butyllithium (36
mL of 2.6 M in hexane, 95 mmol) in Et O (450 mL) was added dropwise a homogeneous solution of
dichlorophenylbismuthine in Et O/THF (150 mL, 50/100) at −78 °C, and resulting mixture was stirred for
2
2
2
2
overnight, during which time the temperature was gradually raised to rt. The reaction mixture was
quenched with cold water, and AcOEt was added. Upper organic layer was separated, and concentrated
under reduced pressure to leave oily residue, and aqueous layer was extracted with CH Cl (3 times).
2
2
2 2
Combined CH Cl layer was mixed with that oily residue, then washed with water and brine, dried with

HETEROCYCLES, Vol. 74, 2007
779
4
MgSO , and filtered through Celite. The filtrate was concentrated, and purified by column
chromatography (silica gel, hexane/AcOEt = 10/1 to 4/1) to afford almost pure product, and washed with
hot EtOH to afford pure product 1a as white solid (10.5 g, 46%).
-1
1
IR (ATR, cm ) 1297, 1286, 1149, 1087, 1074, 766 ,742, 726, 719, 692; H NMR (270 MHz, CDCl
3
) δ =
1
3
8
.38 (d, J = 7.3 Hz, 2H), 7.86 (d, J = 7.0 Hz, 2H), 7.76 (d, J = 7.6 Hz, 2H), 7.45−7.31 (m, 7H); C NMR
(68 MHz, CDCl
3
) δ = 165.3, 158.3, 141.4, 138.4, 137.3, 133.2, 130.6, 128.3, 127.9, 126.8.
1
1
10-Iodophenothiabismine 5,5-dioxide
To a solution of compound 1a (12.5 g, 25.0 mmol) in Et
120 mL) of I (6.6 g, 26.3 mmol), and resulting mixture stirred for 1 h at rt. Yellow powder was filtered
off, washed with CH Cl and Et O to afford 10-iodophenothiabismine 5,5-dioxide as yellow solid (12.7 g,
2 2
O (100 mL) was added dropwise Et O solution
(
2
2
2
2
9
2%).
IR (ATR, cm ) 1287, 1250, 1136, 1114, 1084, 1086, 1008, 754, 739, 713, 700; H NMR (270 MHz,
CDCl ) δ = 9.22 (d, J = 7.3 Hz, 2H), 8.30 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.6 Hz, 2H), 7.49 (t, J = 7.6 Hz,
-1
1
3
1
3
2
H); C NMR (68 MHz, CDCl
3
) δ = 163.5, 140.2, 139.9, 135.8, 128.6, 127.5.
1
0-(2-Methylphenyl)phenothiabismine 5,5-dioxide (1b)
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 2-methylphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred 3 h, during which time the temperature was gradually raised to rt. The reaction
mixture was quenched with cold water and THF was removed under reduced pressure, and aqueous layer
was extracted with CH
with MgSO and concentrated to leave crude solid, which was recrystallized from AcOEt/hexane to
afford 1b as white solid (990 mg, 77%).
2 2
Cl (3 times). Combined organic layer was washed with water and brine, dried
4
-1
1
mp 239−241 ºC; IR (ATR, cm ) 1300, 1287, 1151, 1134, 1118, 1088, 1074, 767, 739, 713; H NMR (270
MHz, CDCl ) δ = 8.37 (dd, J = 7.6 , 1.1 Hz, 2H), 7.87 (d, J = 7.0 Hz, 2H), 7.57 (d, J = 7.3 Hz, 1H),
3
1
3
7
.45−7.30 (m, 6H), 7.06 (t, J = 7.3 Hz, 1H), 2.55 (s, 3H); C NMR (68 MHz, CDCl
3
) δ = 166.9, 157.6,
S:
1
44.2, 141.5, 140.9, 137.7, 133.2, 130.2, 129.2, 128.7, 128.1, 126.9, 26.5; Anal. Calcd for C19
H
15BiO
2
C, 44.19; H, 2.93%. Found: C, 44.10; H, 2.83%.
0-(3,5-Dimethylphenyl)phenothiabismine 5,5-dioxide (1c)
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 3,5-dimethylphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1c as white solid (745 mg,
5
6%).
-1
1
mp 248−249 ºC; IR (ATR, cm ) 1285, 1249, 1140, 1124, 1086, 1073, 836, 758, 739, 714, 704, 688; H

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HETEROCYCLES, Vol. 74, 2007
NMR (270 MHz, CDCl
3
) δ = 8.38 (dd, J = 7.6, 1.9 Hz, 2H), 7.88 (dd, J = 7.0 , 1.4 Hz, 2H), 7.43−7.31 (m,
1
3
6
1
3
1
H), 7.00 (s, 1H), 2.24 (s, 6H); C NMR (68 MHz, CDCl
3
) δ = 165.0, 158.2, 141.5, 140.0, 137.5, 135.9,
33.2, 130.3, 128.0, 126.9, 21.5; Anal. Calcd for C20
.26%.
H17BiO S: C, 45.29; H, 3.23%. Found: C, 45.19; H,
2
1
1
0-(4-Methylphenyl)phenothiabismine 5,5-dioxide (1d)
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 4-methylphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1d as white solid (798 mg,
6
2%).
IR (ATR, cm ) 1438, 1295, 1284, 1149, 1121, 1105, 1085, 1074, 789, 763, 739, 716; H NMR (270 MHz,
CDCl ) δ = 8.37 (dd, J = 1.6, 7.6 Hz, 2H), 7.87 (dd, J = 1.6, 7.3 Hz, 2H), 7.65 (d, J = 7.8 Hz, 2H), 7.40
-1
1
3
1
3
(
td, J = 7.6, 1.6 Hz, 2H), 7.33 (td, J = 7.6, 1.6 Hz, 2H), 7.23 (d, J = 7.6 Hz, 2H), 2.34 (s, 3H); C NMR
68 MHz, CDCl ) δ = 162.0, 158.1, 141.4, 138.5, 138.3, 137.3, 133.1, 131.5, 127.9, 126.8, 21.6.
0-(2-Methoxyphenyl)phenothiabismine 5,5-dioxide (1e)
(
3
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 2-methoxyphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1e as white solid (870 mg,
6
5%).
mp 173−177 ºC; IR (ATR, cm ) 1567, 1424, 1286, 1233, 1150, 1117, 1048, 1021, 755, 738, 713; H
NMR (270 MHz, CDCl ) δ = 8.35 (dd, J =1.9, 7.3 Hz, 2H), 7.90 (dd, J =1.9, 7.0 Hz, 2H), 7.55 (dd, J =
-1
1
3
1
3
1
.6, 7.3 Hz, 1H), 7.41−7.30 (m, 5H), 7.17 (d, J = 8.1 Hz, 1H), 6.89 (t, J = 7.3 Hz, 1H), 4.00 (s, 3H); C
NMR (68 MHz, CDCl
3
) δ = 162.2, 157.7, 152.6, 141.6, 139.3, 137.5, 132.9, 129.9, 127.7, 126.7, 124.7,
S: C, 42.87; H, 2.84%. Found: C, 42.81; H, 2.77%.
0-(3-Methoxyphenyl)phenothiabismine 5,5-dioxide (1f)
1
09.9, 55.6; Anal. Calcd for C20H17BiO
2
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 3-methoxyphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1f as white solid (702 mg,
5
3%).
-1
mp 180−183 ºC; IR (ATR, cm ) 1579, 1564, 1470, 1298, 1283, 1241, 1226, 1148, 1120, 1087, 1072,
1
1
7
029, 762, 739, 715; H NMR (270 MHz, CDCl ) δ = 8.38 (d, J = 7.3 Hz, 2H), 7.89 (d, J = 6.5 Hz, 2H),
3
1
3
3
.43−7.32 (m, 7H), 6.88 (d, J = 7.9 Hz, 1H), 3.70 (s, 3H); C NMR (68 MHz, CDCl ) δ = 166.2, 161.7,

HETEROCYCLES, Vol. 74, 2007
781
2
158.5, 141.5, 137.4, 133.3, 131.7, 130.5, 128.1, 127.0, 124.1, 113.9, 55.2; Anal. Calcd for C20H17BiO S:
C, 42.87; H, 2.84%. Found: C, 42.97; H, 3.06%.
0-(4-Methoxyphenyl)phenothiabismine 5,5-dioxide (1g)
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 4-methoxyphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from CH
2
Cl
2
/hexane to afford 1g as white solid (989 mg,
7
4%).
-1
1
mp 227−230 ºC; IR (ATR, cm ) 1579, 1564, 1487, 1429, 1283, 1241, 1226, 1148, 808, 764, 739, 716; H
NMR (270 MHz, CDCl ) δ = 8.36 (dd, J =1.6, 7.6 Hz, 2H), 7.86 (dd, J =1.6, 7.0 Hz, 2H), 7.65 (d, J = 8.6
3
1
3
Hz, 2H), 7.42−7.30 (m, 4H), 6.92 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H); C NMR (68 MHz, CDCl
3
) δ = 159.7,
1
4
1
58.2, 156.6, 141.5, 140.1, 137.4, 133.2, 128.0, 126.8, 116.6, 55.1; Anal. Calcd for C20
H17BiO S: C,
2
2.87; H, 2.84%. Found: C, 42.55; H, 2.68%.
0-(4-Ethoxycarbonylphenyl)phenothiabismine 5,5-dioxide (1h)
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 4-ethoxycarbonylphenylmagnesium bromide (prepared by method B).
Resulting mixture was stirred overnight, during which time the temperature was gradually raised to rt.
Usual work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1h as white solid (517
mg, 36%).
-1
mp 183−186 ºC; IR (ATR, cm ) 1171, 1583, 1384, 1305, 1279, 1179, 1151, 1101, 1088, 1050, 1010, 842,
1
7
7
3
1
1
39, 714; H NMR (270 MHz, CDCl
3
) δ = 8.39 (d, J = 7.6 Hz, 2H), 8.04 (d, J = 8.1 Hz, 2H), 7.84 (t, J =
.3 Hz, 4H), 7.42 (t, J = 7.6 Hz, 2H), 7.35 (t, J = 7.0 Hz, 2H), 4.37 (q, J = 7.3 Hz, 2H), 1.38 (t, J = 7.3 Hz,
1
3
H); C NMR (68 MHz, CDCl
27.0, 61.0, 14.3; Anal. Calcd for C21
0-(4-Trifluoromethylphenyl)phenothiabismine 5,5-dioxide (1i)
3
) δ = 171.3, 166.4, 158.6, 141.4, 138.5, 137.2, 133.4, 131.1, 130.3, 128.1,
H17BiO
4
S: C, 43.91; H, 2.98%. Found: C, 43.88; H, 3.12%.
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 4-trifluoromethylphenylmagnesium bromide (prepared by method A).
Resulting mixture was stirred for 3 h, during which time the temperature was gradually raised to rt. Usual
2
work-up, and crude solid was recrystallized from Et O/hexane to afford 1i as white solid (751 mg, 53%).
-1
mp 187−190 ºC; IR (ATR, cm ) 1592, 1387, 1322, 1304, 1283, 1152, 1114, 1073, 1040, 1008, 823, 760,
1
7
7
39, 715, 673; H NMR (270 MHz, CDCl
3
) δ = 8.40 (dd J = 7.6, 1.6 Hz, 2H), 7.89 (d, J = 8.1 Hz, 2H),
1
3
.83 (dd, J = 7.6, 1.6 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 7.47−7.34 (m, 4H); C NMR (68 MHz, CDCl
169.7, 158.7, 141.4, 138.9, 137.2, 133.5, 130.3 (q, JC-C-F = 39 Hz), 128.2, 127.1, 127.0 (q, JC-C-C-F = 4
Hz), 124.0 (q, JC-F = 271 Hz); Anal. Calcd for C19 S: C, 40.01; H, 2.12%. Found: C, 39.8; H,
3
) δ
=
3 2
H12BiF O

782
HETEROCYCLES, Vol. 74, 2007
2
.18%.
0-(3-Fluorophenyl)phenothiabismine 5,5-dioxide (1j)
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 3-fluorophenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1j as white solid (911 mg,
7
0%).
mp 193−195 ºC; IR (ATR, cm ) 1573, 1409, 1297, 1254, 1198, 1151, 1086, 785, 768, 741, 717, 681; H
NMR (270 MHz, CDCl ) δ = 8.39 (dd, J = 7.6, 2.2 Hz, 2H), 7.86 (dd, J = 6.8, 1.4 Hz, 2H), 7.56 (d, J =
.3 Hz, 1H), 7.51−7.34 (m, 6H), 7.02 (td, J = 8.1 Hz, 1H); C NMR (68 MHz, CDCl ) δ = 166.8, 165.2
-1
1
3
13
7
3
(
d, JC-F = 252 Hz), 158.6, 141.3, 137.2, 133.7 (d, JC-C-C-C-F = 3 Hz), 133.4, 131.9 (d, JC-C-C-F = 6 Hz), 128.1,
1
2
1
27.0, 125.1 (d, JC-C-F = 19 Hz), 115.6 (d, JC-C-F = 20 Hz); Anal. Calcd for C18
.32%. Found: C, 41.48; H, 2.24%.
2
H12BiFO S: C, 41.55; H,
0-(3-Chlorophenyl)phenothiabismine 5,5-dioxide (1k)
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0°C was
added dropwise a solution of 3-chlorophenylmagnesium bromide (prepared by method B). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1k as white solid (577 mg,
4
3%).
-1
mp 212−215 ºC; IR (ATR, cm ) 1564, 1426, 1285, 1249, 1149, 1086, 1073, 1014, 836, 758, 739, 714,
1
6
88; H NMR (270 MHz, CDCl
3
) δ = 8.39 (dd, J = 7.3, 1.6 Hz, 2H), 7.86 (dd, J = 6.8, 1.1 Hz, 2H), 7.77
1
3
(
s, 1H), 7.61 (d, J = 7.3 Hz, 1H), 7.46−7.30 (m, 6H); C NMR (68 MHz, CDCl
3
) δ = 166.6, 158.8, 141.4,
1
38.0, 137.4, 137.3, 136.4, 133.5, 132.0, 128.7, 128.3, 127.2; Anal. Calcd for C H BiClO S: C, 40.28;
1
9
12
2
H, 2.25%. Found: C, 40.10; H, 2.08%.
0-(4-Chlorophenyl)phenothiabismine 5,5-dioxide (1l)
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 4-chlorophenylmagnesium bromide (prepared by method B). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1l as white solid (638 mg,
4
8%).
mp 209−211 ºC; IR (ATR, cm ) 1557, 1470, 1429, 1377, 1299, 1287, 1151, 1087, 766, 740, 715; H
NMR (270 MHz, CDCl ) δ = 8.38 (d, J = 7.0 Hz, 2H), 7.85 (d, J = 7.0 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H),
-1
1
3
1
3
7
1
.44−7.34 (m, 6H); C NMR (68 MHz, CDCl ) δ = 163.4, 158.6, 141.5, 140.1, 137.3, 134.7, 133.4,
3
2
30.9, 128.2, 127.1; Anal. Calcd for C19H12BiClO S: C, 40.28; H, 2.25%. Found: C, 40.15; H, 2.41%.

HETEROCYCLES, Vol. 74, 2007
783
1
0-(2-Naphthyl)phenothiabismine 5,5-dioxide (1m)
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of 2-naphtylphenylmagnesium bromide (prepared by method A). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
2 2
work-up, and crude solid was recrystallized from CH Cl /hexane to afford 1m as white solid (785 mg,
5
7%).
-1
mp 230−233 ºC; IR (ATR, cm ) 1564, 1284, 1250, 1149, 1107, 1087, 1072, 1013, 860, 814, 762, 742,
1
7
3
15; H NMR (270 MHz, CDCl
3
) δ = 8.43−8.39 (m, 3H), 7.86 (dd, J = 7.3, 1.1 Hz, 2H), 7.82−7.77 (m,
H), 7.62 (dd, J = 8.1, 1.1 Hz, 1H), 7.57−7.47 (m, 2H), 7.41 (td, J = 7.3, 1.1 Hz, 2H) 7.31 (td, J = 7.6, 1.6
1
3
Hz, 2H); C NMR (68 MHz, CDCl
30.5, 128.1, 127.9, 127.6, 127.0, 126.4, 126.3; Anal. Calcd for C22
Found: C, 47.51; H, 2.85%.
0-Methylphenothiabismine 5,5-dioxide (1n)
3
) δ = 162.8, 158.3, 141.6, 138.3, 137.5, 135.6, 134.8, 133.3, 133.0,
1
H15BiO
2
S: C, 47.83; H, 2.74%.
11
1
To a suspension of 10-iodophenothiabismine 5,5-dioxide (1.38 g, 2.5 mmol) in THF (7.5 mL) at 0 °C was
added dropwise a solution of methylmagnesium bromide (3 mL, ca. 1 mol/l in THF solution). Resulting
mixture was stirred overnight, during which time the temperature was gradually raised to rt. Usual
work-up, and crude solid was recrystallized from AcOEt/hexane to afford 1n as white solid (610 mg,
5
5%).
-1
1
IR (ATR, cm ) 1560, 1428, 1290, 1144, 1072, 1014, 764, 717; H NMR (270 MHz, CDCl
3
) δ = 8.30
1
3
(
dd, J = 7.0, 1.6 Hz, 2H), 8.04 (dd, J = 7.0, 1.6 Hz, 2H), 7.45−7.34 (m, 4H), 1.41 (s, 3H); C NMR (68
MHz, CDCl ) δ = 150.6, 141.4, 136.2, 132.9, 128.0, 126.7, 19.7.
3
Preparation of Grignard reagent.
Method A: To a solution of Mg turnings (73 mg, 0.3 mmol) in THF (2.5 mL) was added ArBr (2. 75
mmol). When the reaction started, the temperature was raised and the color of solution was changed to
black, and the mixture was stirred until the solution was cooled to rt.
Method B: To a solution of ArI (2. 75 mmol) in THF (7.5 mL) was added isopropyl magnesium bromide
(
3.3 mL, ca. 1 mol/l in THF solution) at −45 to −35 ºC, and stirred at −45 to −35 ºC for 1 h.
1
5
Phenylbiphenyl-2,2’-ylenebismuthane (1q)
To a solution of 2,2’-dilithiodiphenyl−TMEDA (TMEDA = N,N,N,N-tetramethylethylenediamine)
generated from biphenyl (6.17 g, 40 mmol), TMEDA (13.3 ml, 88 mmol) and n-butyllithium (34 mL of
2
.6 M in hexane, 88 mmol) was added dropwise a solution of dichlorophenylbismuthine (16.1 g, 45 mmol,
as described above) at −78 °C, and resulting mixture was stirred for overnight, during which time the

784
HETEROCYCLES, Vol. 74, 2007
temperature was gradually raised to rt. The reaction mixture was quenched with cold water, and AcOEt
was added. Upper organic layer was separated, and concentrated under reduced pressure to leave oily
residue. Aqueous layer was extracted with CH
that oily residue, then washed with water and brine, dried with MgSO
filtrate was concentrated, and purified by column chromatography (silica gel, hexane/CH
/1) to afford almost pure product. The crude solid was washed with hot EtOH, and recrystallized from
AcOEt/hexane to afford 1q as white solid (5.34 g, 30%).
2
Cl
2
(3 times). Combined CH
, and filtered through Celite. The
Cl = 10/1 to
2 2
Cl layer was mixed with
4
2
2
4
-1
1
3
IR (ATR, cm ) 3049, 1564, 1425, 742, 726; H NMR (270 MHz, CDCl ) δ = 7.90 (d, J = 7.6 Hz, 2H),
1
3
7
1
1
3
.75−7.67 (m, 4H), 7.43−7.36 (m, 4H), 7.19−7.15 (m, 3H); C NMR (68 MHz, CDCl ) δ = 163.6, 157.8,
52.0, 137.1, 136.8, 130.0, 128.2, 127.6, 127.2, 126.3.
1
1
0-Phenylphenoxabismine (1r)
To a solution of 2,2’-dilithiodiphenylether generated from diphenyl ether (3.57 g, 21 mmol) and
n-butyllithium (17.8 mL of 2.6 M in hexane, 46 mmol) in Et O/THF (200 mL, 110/90) was added
2
dropwise a solution of dichlorophenylbismuthine (7.5 g, 21 mmol, as described above) at −78 °C, and
resulting mixture was stirred for overnight, during which time the temperature was gradually raised to rt.
The reaction mixture was quenched with cold water, and AcOEt was added. Upper organic layer was
separated, and aqueous layer was extracted with AcOEt (2 times). Combined AcOEt layer was washed
4
with water and brine, dried with MgSO , and filtered through Celite. The filtrate was concentrated, and
purified by column chromatography (silica gel, hexane/AcOEt = 10/1) to afford almost pure product. The
crude solid was recrystallized from AcOEt-hexane to afford 1r as white solid (1.5 g, 16%).
-
1
1
IR (ATR, cm ) 3051, 1568, 1421, 1259, 1207, 1108, 872, 792, 754, 694; H NMR (270 MHz, CDCl
3
) δ =
.81−7.74 (m, 4H), 7.63 (d, J = 8.1 Hz, 2H), 7.31−7.22 (m, 5H), 7.07 (t, J = 7.0 Hz, 2H); C NMR (68
MHz, CDCl ) δ = 156.9, 152.3, 137.5, 137.1, 134.2, 130.2, 130.1, 127.7, 125.4, 119.4; Anal. Calcd for
C H BiO: C, 47.59; H, 2.88%. Found: C, 47.44; H, 2.89%.
13
7
3
1
8
13
Typical procedure for the formation of phenyl tosylate (2a)
To a solution of m-CPBA (65% content, 87.6 mg, 0.33 mmol) and TsOH·H
2
O (159.8 mg, 0.84 mmol) in
, initial bath
temperature was maintained at −55 to −60 °C). The resulting mixture was stirred in an ice-water bath for
0 min. The color of the solution changed to yellow during this time. Following that, reaction mixture
was stirred under reflux for 4 h. After CH Cl was removed from the reaction mixture under reduced
2 2 3
CH Cl (2 mL) was added 1a at −78 °C (when the reaction was carried out in CHCl
1
2
2
pressure, then Et
filtered and concentrated. The resulting residue was purified by preparative TLC (silica gel,
hexane/CH Cl = 1/1) to afford the desired phenyl tosylate 2a as white solid.
2 4
O was added, and the precipitate was filtered off. The filtrate was dried with MgSO ,
2
2

HETEROCYCLES, Vol. 74, 2007
785
4
b
-1
Phenyl tosylate (2a) : White solid; IR (ATR, cm ) 1486, 1373, 1195, 1171, 1147, 1091, 855, 815, 804,
1
7
75, 724, 687, 657; H NMR (270 MHz, CDCl
3
) δ = 7.69 (d, J = 8.1 Hz, 2H), 7.31−7.20 (m, 5H), 6.98
) δ = 149.5, 145.2, 132.2, 129.6, 129.5,
1
3
(
dd, J = 8.1, 1.4 Hz, 2H), 2.44 (s, 3H); C NMR (68 MHz, CDCl
3
1
2
7
2
1
3
1
28.4, 126.9, 122.3, 21.8.
4
b
-1
-Methylphenyl tosylate (2b) : White solid; IR (ATR, cm ) 1371, 1193, 1179, 1153, 1088, 871, 786,
1
77, 731, 710, 699, 659; H NMR (270 MHz, CDCl
3
) δ = 7.73 (d, J = 8.1 Hz, 2H), 7.31 (d, J = 7.8 Hz,
13
3
H), 7.15−7.08 (m, 3H), 7.00−6.97 (m, 1H), 2.45 (s, 3H), 2.07 (s, 3H); C NMR (68 MHz, CDCl ) δ =
48.2, 145.1, 133.0, 131.4(131.44), 131.4(131.41), 129.6, 128.2, 126.8, 126.7, 122.2, 21.8, 16.3.
1
6
-1
,5-Dimethylphenyl tosylate (2c) : White solid; IR (ATR, cm ) 1593, 1368, 1188, 1176, 1123, 1093,
1
018, 942, 854, 806, 770, 668; H NMR (270 MHz, CDCl ) δ = 7.72 (d, J = 8.1 Hz, 2H), 7.31 (d, J = 8.6
3
1
3
Hz, 2H), 6.86 (s, 1H), 6.60 (s, 2H), 2.45 (s, 3H), 2.23 (s, 6H); C NMR (68 MHz, CDCl
3
) δ = 149.3,
S:
1
45.0, 139.3, 132.6, 129.5, 128.6, 128.4, 119.7, 21.7, 21.2; HRMS (EI positive) Calcd. for C15H O
16 3
+
[
M+·] 276.0820, Found: m/z 276.0815.
4
b
-1
4
1
-Methylphenyl tosylate (2d) : White solid; IR (ATR, cm ) 1596, 1503, 1372, 1198, 11174, 1155,
1
093, 859, 829, 818, 786, 724, 693, 653; H NMR (270 MHz, CDCl
3
) δ = 7.69 (d, J = 8.1 Hz, 2H), 7.29
13
(
d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 2.43 (s, 3H), 2.29 (s, 3H); C
NMR (68 MHz, CDCl ) δ = 147.3, 145.1, 136.8, 132.3, 129.9, 129.6, 128.4, 121.9, 21.7, 20.9;
3
1
7
-1
2
1
7
1
-Methoxylphenyl tosylate (2e) : Colorless oil; IR (ATR, cm ) 1600, 1498, 1368, 1258, 1179, 1157,
1
090, 866, 758, 659; H NMR (270 MHz, CDCl
3
) δ = 7.74 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H),
13
.22−7.12 (m, 2H), 6.90−6.82 (m, 2H), 3.55 (s, 3H), 2.44 (s, 3H); C NMR (68 MHz, CDCl
3
) δ = 151.6,
44.8, 138.3, 133.1, 129.2, 128.4, 127.9, 123.9, 120.5, 112.6, 55.5, 21.7; HRMS (EI positive) Calcd. for
+
C
14
H
14
O
4
S: [M+·] 278.0613, Found: m/z 278.0613.
1
8
-1
3
1
2
-Methoxylphenyl tosylate (2f) : Colorless oil; IR (ATR, cm ) 1606, 1588, 1485, 1369, 1191, 1177,
1
121, 1090, 1039, 939, 926, 803, 786, 718, 684, 661; H NMR (270 MHz, CDCl
3
) δ = 7.72 (d, J = 8.4 Hz,
H), 7.31 (d, J = 8.6 Hz, 2H), 7.16 (td, J = 7.3, 1.4 Hz, 1H), 6.80−6.76 (m, 1H), 6.56−6.52 (m, 2H), 3.72
1
3
(
s, 3H), 2.45 (s, 3H); C NMR (68 MHz, CDCl
3
) δ = 160.2, 150.3, 145.2, 132.3, 129.7, 129.6, 128.4,
+
1
2
4
8
14.2, 112.9, 108.1, 55.4, 21.7; HRMS (EI positive) Calcd. for C14
78.0610.
H
14
O
4
S: [M+·] 278.0613, Found: m/z
19
-1
-Methoxylphenyl tosylate (2g) : Colorless oil; IR (ATR, cm ) 1596, 1500, 1368, 1250, 1168, 1092,
1
37, 786, 695; H NMR (270 MHz, CDCl
3
) δ = 7.68 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 6.87 (td,
1
3
3
J = 2.2, 9.2 Hz, 2H), 6.76 (td, J = 2.2, 8.9 Hz, 2H), 3.76 (s, 3H), 2.45 (s, 3H); C NMR (68 MHz, CDCl )
δ = 158, 145.1, 142.9, 132.2, 129.6, 128.4, 123.2, 114.4, 55.6, 21.8; HRMS (EI positive) Calcd. for
+
C
14
H
14
O
4
S: [M+·] 278.0613, Found: m/z 278.0615.
20
-1
Ethyl (4-tosyloxy)benzoate (2h) : Colorless oil; IR (ATR, cm ) 1719, 1371, 1287, 1175, 1154, 1119,

786
HETEROCYCLES, Vol. 74, 2007
1
1
090, 1021, 866, 839, 814, 774, 731, 692, 667; H NMR (270 MHz, CDCl
3
) δ = 7.98 (d, J = 8.6 Hz, 2H),
7
.70 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.6 Hz, 2H), 4.36 (q, J = 7.0 Hz, 2H), 2.45
13
(
s, 3H), 1.38 (t, J = 7.0 Hz, 3H); C NMR (68 MHz, CDCl
3
) δ = 165.2, 152.6, 145.5, 131.9, 131.0, 129.7,
+
1
29.1, 128.3, 122.1, 61.2, 21.7, 14.3; HRMS (EI positive) Calcd. for C16
H
16
O
5
S: [M+·] 320.0718,
Found: m/z 320.0710.
3
d
-1
4
-Trifluoromethylphenyl tosylate (2i) : White solid; IR (ATR, cm ) 1378, 1322, 1202, 1175, 1159,
1
1
124, 1102, 1065, 1017, 859, 853, 815, 776, 716, 664; H NMR (270 MHz, CDCl
3
) δ = 7.72 (d, J = 8.4
1
3
Hz, 2H), 7.57 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.6 Hz, 2H), 2.45 (s, 3H); C
NMR (68 MHz, CDCl
3
) δ = 151.7, 145.8, 131.8, 129.8, 129.2 (q, JC-C-F = 33 Hz), 128.3, 126.9 (q, JC-C-C-F
+
=
4 Hz) 123.4 (q, JC-F = 272 Hz), 122.8, 21.7; HRMS (EI positive) Calcd. for C H O F S: [M+·]
14 11 3 3
3
3
9
16.0381, Found: m/z 316.0380.
2
1
-1
-Fluorophenyl tosylate (2j) : Colorless oil; IR (ATR, cm ) 1600, 1482, 1373, 1901, 1178, 1111, 1091,
1
48, 803, 789, 719, 679, 660; H NMR (270 MHz, CDCl
3
) δ = 7.71 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4
1
3
Hz, 2H), 7.27−7.21 (m, 1H), 6.97 (td, J = 8.1, 2.4 Hz, 1H), 6.82−6.72 (m, 2H), 2.46 (s, 3H); C NMR
68 MHz, CDCl ) δ = 162.4 (d, JC-F = 248 Hz), 150.0 (d, JC-C-C-F = 11 Hz) , 145.5, 131.9, 130.2 (d, JC-C-C-F
9 Hz), 129.8, 128.4, 118.1 (d, JC-C-C-C-F = 3 Hz), 114.2 (d, JC-C-F = 20 Hz), 110.4 (d, JC-C-F = 24 Hz),
(
3
=
+
2
3
8
2
1.8; HRMS (EI positive) Calcd. for C13
H
11
O
3
FS: [M+·] 266.0413, Found: m/z 266.0409.
3
c
-1
-Chlorophenyl tosylate (2k) : Pale yellow solid; IR (ATR, cm ) 1585, 1468, 1373, 1197, 1170, 1087,
1
93, 786, 751, 676, 659; H NMR (270 MHz, CDCl
3
) δ = 7.71 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.4 Hz,
13
H), 7.27−7.21 (m, 2H), 7.04−7.02 (m, 1H), 6.91−6.86 (m, 1H), 2.46 (s, 3H); C NMR (68 MHz,
CDCl
3
) δ = 149.7, 145.6, 134.7, 131.9, 130.2, 129.8, 128.4, 127.3, 122.9, 120.6, 21.8; HRMS (EI
+
positive) Calcd. for C13
H
11
O
3
ClS: [M+·] 282.0117, Found: m/z 282.0113.
1
c
-1
4
-Chlorophenyl tosylate (2l) : White solid; IR (ATR, cm ) 1596, 1484, 1373, 1201, 1171, 1089, 863,
1
8
3
40, 748, 671; H NMR (270 MHz, CDCl ) δ = 7.69 (d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 7.24 (d,
1
3
J = 8.6 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 2.45 (s, 3H); C NMR (68 MHz, CDCl
3
) δ = 147.9, 145.5,
+
1
2
2
8
7
1
1
32.6, 131.9, 129.7, 129.6, 128.4, 128.7, 21.8; HRMS (EI positive) Calcd. for C13
11 3
H O ClS: [M+·]
82.0117, Found: m/z 282.0122.
1
c
-1
-Naphthyl tosylate (2m) : White solid; IR (ATR, cm ) 1596, 1374, 1190, 1175, 1145, 1090, 958, 906,
1
63, 818, 785, 750, 707, 660; H NMR (270 MHz, CDCl
3
) δ = 7.82−7,70 (m, 5H), 7.51−7.44 (m, 3H),
1
3
3
.28 (d, J = 8.1 Hz, 2H), 7.09 (dd, J = 8.9, 2.4 Hz, 1H), 2.43 (s, 3H); C NMR (68 MHz, CDCl ) δ =
47.0, 145.2, 133.3, 132.3, 131.7, 129.6(129.64), 129.6(129.61), 128.4, 127.7, 127.6, 126.7, 126.2, 121.0,
+
19.8, 21.8; HRMS (EI positive) Calcd. for C17
H
14
O
3
S: [M+·] 298.0664, Found: m/z 298.0667.
2
2
-1
Methyl tosylate (2n) : Colorless oil; IR (ATR, cm ) 1598, 1453, 1356, 1173, 1096, 986, 813, 759, 658;
1
3
H NMR (270 MHz, CDCl ) δ = 7.78 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 3.74 (s, 3H), 2.45 (s,

HETEROCYCLES, Vol. 74, 2007
787
1
3
3
H); C NMR (68 MHz, CDCl
3
) δ = 144.7, 132.1, 129.7, 127.9, 56.1, 21.6.
2
3
-1
Phenyl benzenesulfonate (3a) : Colorless oil; IR (ATR, cm ) 1589, 1485, 1372, 1198, 1172, 1091, 857,
1
7
40, 685; H NMR (270 MHz, CDCl
3
) δ = 7.82 (dd, J = 8.4, 1.1 Hz, 2H), 7.66 (t, J = 7.0 Hz, 1H), 7.51 (t,
1
3
J = 7.6 Hz, 2H), 7.31−7.21 (m, 3H), 6.97 (dd, J = 7.6, 1.4 Hz, 2H); C NMR (68 MHz, CDCl
3
) δ = 149.4,
1
35.2, 134.1, 129.5, 129.0, 128.3, 127.0, 122.2.
2
4
-1
Phenyl naphthalene-2-sulfonate (4a) : White solid; IR (ATR, cm ) 1585, 1486, 1372, 1189, 1145,
1
1
2
1
074, 915, 862, 780, 726; H NMR (270 MHz, CDCl
3
) δ = 8.34 (s, 1H), 7.97−7.80 (m, 4H), 7.69−7.56 (m,
13
3
H), 7.27−7.16 (m, 3H), 6.98 (dd, J = 8.1, 2.2 Hz, 2H); C NMR (68 MHz, CDCl ) δ = 149.4, 135.2,
32.0, 131.6, 130.3, 129.5, 129.4, 129.3, 129.2, 127.8, 127.7, 127.0, 122.7, 122.2; HRMS (EI positive)
+
Calcd. for C16
H
12
O
3
S: [M+·] 284.0507, Found: m/z 284.0500.
2
3
-1
Phenyl 4-nitrobenzenesulfonate (5a) : Pale yellow solid; IR (ATR, cm ) 3108, 1524, 1485, 1372, 1349,
1
1
8
1
2
194, 1141, 1090, 854, 780, 684; H NMR (270 MHz, CDCl
3
) δ = 8.37 (d, J = 8.9 Hz, 2H), 8.03 (d, J =
1
3
.9 Hz, 2H), 7.37−7.29 (m, 3H), 6.99 (dd, J = 8.1, 2.2 Hz, 2H); C NMR (68 MHz, CDCl
3
) δ = 150.8,
+
49.1, 140.9, 129.9, 129.8, 127.6, 124.2, 122.0; HRMS (EI positive) Calcd. for C12
79.0201, Found: m/z 279.0199.
9 5
H O NS: [M+·]
2
3
-1
Phenyl 4-chlorobenzenesulfonate (6a) : White solid; IR (ATR, cm ) 1585, 1477, 1377, 1283, 1172,
1
1
146, 1087, 855, 823, 780, 759, 687; H NMR (270 MHz, CDCl
3
) δ = 7.76 (d, J = 8.6 Hz, 2H), 7.49 (d, J
13
=
8.6 Hz, 2H), 7.34−7.23 (m, 3H), 6.98 (dd, J = 8.6, 1.9 Hz, 2H); C NMR (68 MHz, CDCl
3
) δ = 149.3,
+
1
2
40.8, 133.7, 129.8, 129.6, 129.4, 127.2, 122.2; HRMS (EI positive) Calcd. for C12
67.9961, Found: m/z 267.9962.
9 3
H O ClS: [M+·]
2
5
-1
Phenyl 2,4,6-trimethylbenzenesulfonate (7a) : White solid; IR (ATR, cm ) 1485, 1455, 1362, 1195,
1
1
6
2
145, 851, 785, 731, 691; H NMR (270 MHz, CDCl
3
) δ = 7.29−7.21 (m, 3H), 6.97−6.94 (m, 4H), 2.54 (s,
1
3
H), 2.31 (s, 3H); C NMR (68 MHz, CDCl ) δ = 149.3, 143.7, 140.3, 131.6, 130.4, 129.4, 126.8, 122.1,
3
+
2.8, 21.2; HRMS (EI positive) Calcd. for C15
H
16
O
3
S: [M+·] 276.0820, Found: m/z 276.0823.
2
6
-1
Phenyl 4-hydroxybenzenesulfonate (8a) : Pale yellow solid; IR (ATR, cm ) 3432, 1585, 1486, 1357,
1
1
7
194, 1149, 1091, 860, 837, 786, 733; H NMR (270 MHz, CDCl
3
) δ = 7.69 (d, J = 8.6 Hz, 2H),
13
.31−7.21 (m, 3H), 6.98 (dd, J = 7.6, 1.9 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 6.17 (br s, 1H); C NMR (68
MHz, CDCl
3
) δ = 160.9, 149.4, 130.9, 129.5, 127.1, 126.3, 122.3, 115.9; HRMS (EI positive) Calcd. for
+
C
12
H
10
O
4
S: [M+·] 250.0300, Found: m/z 250.0296.
5b
-1
Phenyl mesylate (9a) : White solid; IR (ATR, cm ) 1588, 1485, 1353, 1168, 1139, 967, 858, 793, 767,
1
13
6
1
88; H NMR (270 MHz, CDCl
3
) δ = 7.46−7.26 (m, 5H), 3.13 (s, 3H); C NMR (68 MHz, CDCl
3
) δ =
49.1, 129.9, 127.3, 121.9, 37.4.
27
-1
Phenyl ethanesulfonate (10a) : Colorless oil; IR (ATR, cm ) 1588, 1487, 1360, 1141, 858, 779, 749,
1
6
88; H NMR (270 MHz, CDCl
3
) δ = 7.44−7.26 (m, 5H), 3.27 (q, J = 7.6 Hz, 2H), 1.53 (t, J = 7.6 Hz,

788
HETEROCYCLES, Vol. 74, 2007
1
3
3
H); C NMR (68 MHz, CDCl
3
) δ = 149.0, 129.8, 127.1, 121.9, 45.0, 8.3; HRMS (EI positive) Calcd. for
+
C
8 10 3
H O S: [M+·] 186.0351, Found: m/z 186.0347.
2
8
-1
2
-Naphthyl triflate (3m) : Colorless oil; IR (ATR, cm ) 1511, 1420, 1202, 1136, 1106, 955, 912, 832;
1
3
H NMR (270 MHz, CDCl ) δ = 7.91−7.83 (m, 3H), 7.74 (d, J = 2.2 Hz, 1H), 7.59−7.52 (m, 2H), 7.36
1
3
(
dd, J = 9.2, 2.4 Hz, 1H); C NMR (68 MHz, CDCl
27.1, 119.4, 119.1, 118.8 (q, JC-F = 320 Hz).
3
) δ = 147.0, 133.2, 132.3, 130.5, 127.9, 127.8, 127.5,
1
Preparation of pentavalent bismuth(V) dicarboxylate;
0,10-Di(3-chlorobenzenecarboxy)-10-(4-methylphenyl)phenothia-10 5-bismine 5,5-dioxide 1/4
etherate (1o)
To a suspension of 1a (1.51 g, 3 mmol) in Et O (6 mL) at 0 °C was added dropwise a solution of
λ
1
2
3
-chlorobenzoic acid (0.47 g, 3 mmol) in Et
g, 3.3 mmol) in Et O (7 mL) was added dropwise. CH
was stirred at 0 °C for 30 min. Yellow precipitate was filtered off and washed with CH
afford 1o as yellow solid (2.35 g, 96%).
2
O (7 mL) and then a solution of m-CPBA (65% content, 0.88
Cl (2 mL) was added and the reaction mixture
Cl /Et O = 1/10 to
2
2
2
2
2
2
-1
1
mp 129−132 ºC; IR (ATR, cm ) 1597, 1545, 1467, 1426, 1321, 1152, 981, 743; H NMR (270 MHz,
CDCl ) δ = 8.50 (dd, J = 7.6, 1.1 Hz, 2H), 8.40 (d, J = 7.6 Hz, 2H), 8.17 (d, J = 7.8 Hz, 2H), 7.97 (s, 2H),
.87 (d, J = 7.8 Hz, 2H), 7.73 (td, J = 7.6, 1.4 Hz, 2H), 7.64−7.42 (m, 7H), 7.30 (d, J = 7.8 Hz, 2H), 3.48
3
7
1
3
(
q, J = 7.0 Hz, 1H), 1.21 (t, J = 7.0 Hz, 1.5H); C NMR (68 MHz, CDCl
35.1, 134.9, 134.1, 133.0, 132.4, 132.1, 131.6, 131.4, 130.9, 130.3, 129.3, 128.4, 127.9, 65.8, 15.3; Anal.
Calcd for C32 S.1/4Et O: C, 47.64; H, 2.85%. Found: C, 47.46; H, 2.90%.
3
) δ = 172.7, 168.1, 163.4, 147.9,
1
H21BiCl
2
O
6
2
ACKNOWLEDGEMENTS
This study was supported in part by the Grant of the 21st Century COE Program from Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan. The authors wish to thank Ms.
Tomoko Shinohara (Otsuka Pharmaceutical Co., Ltd.) for her support in elemental analysis and Dr.
Hirokazu Ohsawa (Analytical group in Banyu pharmaceutical Co., Ltd.) for his support in high resolution
mass spectrometry analysis.
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