An Efficient Organic Electrosynthesis of β-Hydroxysulfones

Article abstract of DOI:10.1055/s-0036-1589051

An efficient organic electrosynthesis of tertiary β-hydroxysulfones from functionalized α-methylstyrenes with substituted sodium sulfinates has been established. The novel electrosynthetic method provided the desired products in excellent yields, and the key structure was confirmed by X-ray single-crystal diffraction analysis.

Full text of DOI:10.1055/s-0036-1589051

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2017, 49, A–I
paper
A
en
C.-K. Chan et al.
Paper
Synthesis
An Efficient Organic Electrosynthesis of β-Hydroxysulfones
Chieh-Kai Chan
Nai-Chang Lo
Po-Yu Chen*
Meng-Yang Chang*
Department of Medicinal and Applied Chemistry,
General Research Centers of R & D Office, Kaohsiung
Medical University Hospital, Kaohsiung Medical
University, Kaohsiung 807, Taiwan, Republic of
China
pyc@kmu.edu.tw
mychang@kmu.edu.tw
Received: 07.04.2017
Accepted after revision: 19.05.2017
Published online: 25.07.2017
DOI: 10.1055/s-0036-1589051; Art ID: ss-2017-h0231-op
HO
HO
O
O
O
O
N
N
S
Me
N
N
S
Me
N
N
F
Abstract An efficient organic electrosynthesis of tertiary β-hydroxy-
sulfones from functionalized α-methylstyrenes with substituted sodium
sulfinates has been established. The novel electrosynthetic method pro-
vided the desired products in excellent yields, and the key structure was
confirmed by X-ray single-crystal diffraction analysis.
F
CF3
Sch42427 (1)
SSY726 (2)
NC
F
O
O
S
Key words electrosynthesis, α-methylstyrene, β-hydroxysulfone, sul-
fone radical, sulfone
F3C
N
H
O
OH
bicalutamide (3)
Figure 1 Bioactive compounds possessing a sulfone group
Sulfone compounds are crucial materials owing to their
valuable bioactivities and use as versatile building blocks in
organic synthesis.1 In regard to their derivatives, β-hydrox-
ysulfones are not only basic skeletons in a number of phar-
maceutically important compounds and synthetically use-
ful molecules, such as Sch42427 (1) and SSY726 (2) that
show antifungal activities and the efficacious bicalutamide
(3),2 but also crucial precursors in the synthesis of many bi-
ological compounds3 and reaction intermediates in organic
synthesis (Figure 1).4 Therefore, the development of various
approaches for the synthesis of β-hydroxysulfones is of
great interest. In general, the construction of β-hydroxysul-
fones includes the biological5a–c or chemical5d–h reduction of
β-ketosulfones, the nucleophilic opening addition of epox-
ides with sulfinate salts,6 the catalytic conjugate boration of
α,β-unsaturated sulfones,7 and the visible light-induced
photocatalytic8 or acid-catalyzed9 synthesis of sulfonyl
chlorides with alkenes. Therefore, the development of the
direct hydroxysulfonylation of in situ generated sulfonyl
radicals with alkenes is of great interest.
bon radical to sulfur dioxide.15 Some approaches for the
preparation of β-hydroxysulfones by the addition of sulfo-
nyl radicals to styrene have been reported. As shown in
Scheme 1, Taniguchi and co-workers reported Fe(III)16a or
Ni(II)16b metal-catalyzed sulfonyl radical formation from
sulfonyl hydrazide or sulfinate, and the oxidative addition
of the radical to alkenes toward β-hydroxysulfones. In 2013,
the Lei group developed an aerobic O2-activated sulfinic
acid generating sulfonyl radical and reacted it with alkenes
under basic conditions.17 Very recently, Reiser and col-
leagues described a visible light-mediated sulfonyl radical
preparation from sulfonyl chloride and its addition to
alkenes in the presence of an Ir(III) photocatalyst.8 From our
recent work, we were interested in the synthetic applica-
tions of β-ketosulfone.18 A literature survey revealed that
the reactions of olefin compounds with sodium sulfinates
under electrochemical conditions were much less devel-
oped.19 Recently, electrochemical methods have been wide-
ly used in the field of organic synthesis to develop environ-
mentally compatible methodologies and processes.20 To the
best of our knowledge, the use of an electrochemical route
Sulfonyl radicals can be effectively produced from vari-
ous sulfonic acid derivatives, such as sulfonyl halides,9,10
sulfonyl azides,11 sulfonyl selenides,12 sulfonyl cyanides13
and sulfonyl hydrazides,14 or through the addition of a car-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

B
C.-K. Chan et al.
Paper
Synthesis
to synthesize β-hydroxysulfones has not been reported
thus far. Herein, we have developed an efficient electro-
chemical protocol to synthesize β-hydroxysulfones.
Table 1 Reaction Conditions of 4aa
O
HO
Ph
electrosynthesis
Tol
O
TolSO2Na
S
+
Ph
O
HO
Ph
4a
5a
conditions
6a
Tol
O
S
TolSO2 source
+
Ph
Entry
Anode-
Cathode
Supporting
electrolyte
Solvent
6a Yield
(%)b
metal-promoted (Taniguchi's work): Fe(III),16a TolSO2NHNH2; Ni(II),16b TolSO2Na
O2-activated (Lei's work):17 TolSO2H
1
2
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Pt
GCE-Cu
GCE-Ni
GCE-Pd
GCE-Pt
GCE-Pt
GCE-Pt
NaI
NaCl
NaBr
NH4I
NH4Cl
NH4Br
LiI
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
1,4-dioxane
THF
90
c
photo-catalyzed (Reiser's work):8 visible light, TolSO2Cl
electro-mediated (our work): Pt-GC electrodes, TolSO2Na
–
c
3
–
4
85
Scheme 1 Synthetic approaches for the conversion of α-methylsty-
rene to β-hydroxysulfone
c
5
–
c
6
–
7
91
93
82
20
40
86
87
89
65
62
We began our studies with the reaction of α-methylsty-
rene (4a) with sodium p-toluenesulfinate (5a) as model
substrates to validate the electrochemical conditions. Ini-
tially, we examined some reaction conditions, such as elec-
trode materials, supporting electrolytes, and solvents. The
effect of the supporting electrolyte was first investigated. As
shown in Table 1, when NaI was used as the supporting
electrolyte, the desired product was isolated in 90% (Table 1,
entry 1). The desired product was not obtained with other
sodium salts, such as NaCl and NaBr (entries 2, 3). A similar
trend was observed when employing ammonium salts as
supporting electrolytes, where only NH4I was reactive in
this transformation (entries 4–6). Furthermore, other alkali
metal iodide salts, LiI and KI, were efficient in this transfor-
mation with similar isolated yields (entries 7, 8). Neverthe-
less, transition metal iodide salts were tested in this reac-
tion, but the isolated yields decreased (entries 9, 10). Tetra-
n-butylammonium iodide (n-Bu4NI) was also examined in
this reaction, but the yield obtained showed that it was not
appropriate (entry 11). Observable but insignificant de-
crease of yield was detected for the use of other cathodes
(Cu, Ni, or Pd), as shown in entries 12–14. It is possible that
the poor radical stability in 1,4-dioxane and THF resulted in
lower yields of 6a (entries 15, 16). Accordingly, no reaction
occurred without potential, all starting materials were re-
covered (entry 17).
With the optimal conditions in hand (Table 1, entry 8),
the substrate scope of the reaction between α-methylsty-
renes 4 and sodium sulfinates 5 was further explored. The
corresponding structures and related yields are shown in
Scheme 2. Various sodium sulfinates 5, including the neu-
tral benzene containing 5b, electron-withdrawing group
containing 5c, and electron-donating group containing 5d,
were satisfactorily shown to react with 4a under identical
conditions to give the desired β-hydroxysulfones 6b–d in
90–94% yields. Subsequently, a variety of functionalized α-
methylstyrenes 4 (4b, 4-PhC6H4; 4c, 2-naphthyl; 4d, 4-
OCH2OC6H3; 4e, 4-NO2C6H4; 4f, 4-FC6H4; 4g, 4-MeC6H4; 4h,
4-MeOC6H4) also reacted with 5 under the optimized condi-
8
KI
9
CuI
AgI
n-Bu4NI
KI
10
11
12
13
14
15
16
17d
KI
KI
KI
KI
c
KI
MeCN
–
a Reaction conditions: 4 (1.0 mmol), 5a (1.05 mmol), supporting electrolyte
(0.01 M; 10 mL, solvent/H2O: 9:1), electrochemical cell, constant potential
of 1.8 V vs. Ag/AgCl, 5 h, r.t.
b Isolated yield.
c No detection.
d Without potential.
tions to give the β-hydroxysulfones 6e–p in good to excel-
lent yields. It is worth noting that a nitro substituent on the
aromatic ring, which is usually unfavorable for reactions
with radical participation, also worked well (6q–t, 89–
96%).21 The electron-withdrawing-group-containing 4f and
the electron-donating-group-substituted styrene 4g and 4h
reacted with 5 satisfactorily to give the corresponding
products 6u–z in high yields. The product 6aa was also pre-
pared from 4a and 5e under the optimized conditions in
94% yield. The reaction demonstrated a broad tolerance for
the synthesis of substituted β-hydroxysulfones 6a–aa in a
range of 85–96% yields. The structure of 6v was also con-
firmed by single-crystal X-ray crystallography.22
Furthermore, this reaction was also suitable for cyclic
styrene derivatives 7a–c reacting with 5a under the opti-
mized conditions for the formation of 8a–c in high yields.
The corresponding results and related yields are shown in
Scheme 3.
Based on the results, a possible reaction mechanism is
shown in Scheme 4. The α-methylstyrene 4a and sodium p-
toluenesulfinate 5a were selected as model substrates. First,
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

C
C.-K. Chan et al.
Paper
Synthesis
O
S
electrosynthesis
Ar1
O
HO
Ar
+
Ar1SO2Na
Ar
4
5
6
F
OMe
O
S
O
O
S
O
S
HO
HO
HO
HO
S
O
O
O
O
6a, 93%
6b, 92%
6c, 94%
6d, 90%
F
OMe
O
O
S
O
S
O
HO
HO
HO
HO
S
S
O
O
O
O
6e, 95%
6f, 88%
6g, 94%
6h, 87%
OMe
F
O
S
O
O
O
S
HO
HO
HO
HO
S
S
O
O
O
O
6i, 90%
6j, 91%
6k, 95%
6l, 94%
F
OMe
OMe
O
S
O
S
O
S
O
S
HO
HO
HO
HO
HO
O
O
O
O
O
O
O
O
O
O
O
O
6m, 86%
6n, 89%
6o, 85%
6p, 90%
F
O
O
S
O
S
O
S
HO
HO
HO
S
O
O
O
O
O2N
O2N
O2N
O2N
6q, 96%
6r, 94%
6s, 96%
6t, 89%
OMe
F
O
S
O
S
O
O
S
HO
HO
HO
HO
S
O
O
O
O
F
F
F
F
6u, 90%
6v, 95%
6w, 93%
6x, 91%
O
S
O
S
O
S
HO
HO
HO
O
O
O
MeO
6y, 95%
6z, 95%
6aa, 94%
Scheme 2 Synthesis of 6. Reagents and conditions: 4 (1.0 mmol), 5 (1.05 mmol), KI (0.1 mmol), MeCN (9 mL), H2O (1 mL), electrochemical cell, with
constant potential of 1.8 V vs. Ag/AgCl, 5 h, and r.t.; isolated yields are shown.
O
HO
S
R1
R1
O
electrosynthesis
+
TolSO2Na
( )n
( )n
5a
7
8
O
O
S
O
HO
S
HO
HO
S
MeO
O
O
O
8a, 91%
8b, 92%
8c, 95%
Scheme 3 Synthesis of 8. Reagents and conditions: 7 (1.0 mmol), 5a (1.05 mmol), KI (0.1 mmol), MeCN (9 mL), H2O (1 mL), electrochemical cell,
constant potential of 1.8 V vs. Ag/AgCl, 5 h, and r.t.; isolated yields are shown.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

D
C.-K. Chan et al.
Paper
Synthesis
KI dissociated in water to form iodine ions. At the glassy
carbon electrode, iodine ions were oxidized to iodine (I– →
1/2I2 + e–).19 The salt 5a reacted with I2 to produce p-tolu-
enesulfonyl iodide intermediate I,8 and this intermediate de-
composed to form a p-toluenesulfonyl radical and an iodine
radical, which regenerated iodine. Through the addition of
the sulfonyl radical to 4a, the intermediate II was pro-
duced,16,17 followed by the loss of one electron to form the
stable tertiary carbocation III.23 Finally, with the hydration
of III, the desired product 6a was isolated.
method. Various substituted α-methylstyrenes were also
suitable in this procedure. The key structure was confirmed
by X-ray single-crystal diffraction analysis.
All reagents and solvents were obtained from commercial sources
and used without further purification. Reactions were routinely car-
ried out under an atmosphere of dry N2 with magnetic stirring. Prod-
ucts in organic solvents were dried with anhyd MgSO4 before concen-
tration in vacuo. All electrochemical reactions were performed with a
CHI 621A electrochemical analyzer using a three electrode system.
Purity was determined by NMR and melting point. Melting points
were determined with a SMP3 melting apparatus. 1H and 13C NMR
spectra were recorded on a Varian spectrometer operating at 400 and
at 100 MHz, respectively. Chemical shifts (δ) are reported in parts per
million (ppm) and the coupling constants (J) are given in hertz. High-
resolution mass spectra (HRMS) were recorded on a microTOF-Q
mass spectrometer by ESI using a hybrid ion-trap. X-ray crystal struc-
tures were obtained with a diffractometer (CAD4, Kappa CCD).
H2O
O
HO
Tol
S
Ph
O
I–
6a
O
S
Tol
O
O
Ph
I
+
S
Tol
III
O
I
1/2 I2
– e
β-Hydroxysulfones 6 and 8 and Sulfone 9; General Procedure
TolSO2I
α-Methylstyrene 4 or 7 (1 mmol), sodium sulfinate 5 (1.05 mmol), KI
(0.1 mmol), H2O (1 mL), and MeCN (9 mL) were added to the electro-
chemical cell at r.t. The electrosynthesis was performed at a constant
potential (V) at r.t. in the electrochemical cell with a Pt coil as the
cathode and a glassy-carbon electrode (GCE) as the anode. The elec-
trolysis was conducted in stirred solutions at r.t. for 5 h, then the reac-
tion mixture were transferred to a flask and the solvent was concen-
trated. The residue was diluted with H2O (10 mL) and the mixture was
extracted with EtOAc (3 × 10 mL). The combined organic layers were
washed with brine, dried, filtered and evaporated to afford the crude
product. Purification on silica gel (hexanes/EtOAc 10:1 → 6:1) afford-
ed the desired product 6, 8, or 9.
O
S
Tol
TolSO2
5a
Ph
Ph
O
4a
II
Scheme 4 Possible mechanism
In addition, 7d contains two electron-donating methoxy
groups on the 3 and 4 positions, which were able to tolerate
the dehydration, and the allyl sulfone 9 was isolated in a
91% yield (Scheme 5). The simple styrene 10 was also ex-
amined with 5a under the optimal conditions, and the de-
sired β-hydroxysulfone 11 was obtained in good yield
(Scheme 6).
2-Phenyl-1-tosylpropan-2-ol (6a)8
Yield: 270 mg (93%); colorless solid; mp 87–88 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.47 (d, J = 8.0 Hz, 2 H), 7.30–7.27 (m, 2
H), 7.20–7.14 (m, 5 H), 4.65 (br s, 1 H), 3.71 (d, J = 14.4 Hz, 1 H), 3.59
(d, J = 14.4 Hz, 1 H), 3.37 (s, 3 H), 1.69 (s, 3 H).
O
S
O
electrosynthesis
13C NMR (100 MHz, CDCl3): δ = 144.41, 144.40, 137.2, 129.6 (2 ×),
128.1 (2 ×), 127.4 (2 ×), 127.0, 124.5 (2 ×), 73.0, 66.5, 30.7, 21.5.
HRMS (ESI): m/z (M+ + Na) calcd for C16H18O3SNa: 313.0874; found:
313.0866.
MeO
MeO
MeO
MeO
TolSO2Na
+
7d
5a
9 (91%)
Scheme 5 Synthesis of 9
2-Phenyl-1-(phenylsulfonyl)propan-2-ol (6b)8
Yield: 254 mg (92%); colorless solid; mp 102–103 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.59 (d, J = 8.0 Hz, 2 H), 7.52 (t, J = 7.2
Hz, 1 H), 7.37 (t, J = 8.0 Hz, 2 H), 7.29–7.27 (m, 2 H), 7.20–7.14 (m, 3
H), 4.22 (br s, 1 H), 3.74 (d, J = 14.8 Hz, 1 H), 3.62 (d, J = 14.8 Hz, 1 H),
1.70 (s, 3 H).
OH
O
S
electrosynthesis
O
+
TolSO2Na
10
5a
11 (90%)
13C NMR (100 MHz, CDCl3): δ = 144.2, 140.2, 133.4, 129.0 (2 ×), 128.2
Scheme 6 Synthesis of 11
(2 ×), 127.4 (2 ×), 127.2, 126.1, 124.6, 73.1, 66.6, 30.7.
HRMS (ESI): m/z (M+ + Na) calcd for C15H16O3SNa: 299.0718; found:
299.0710.
In summary, a facile electrosynthesis for the prepara-
tion of β-hydroxysulfones in good to excellent yields is re-
ported. This strategy provides an efficient, non-metal
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

E
C.-K. Chan et al.
Paper
Synthesis
1-[(4-Fluorophenyl)sulfonyl]-2-phenylpropan-2-ol (6c)8
13C NMR (100 MHz, CDCl3): δ = 165.3 (d, J = 254.7 Hz), 142.8, 140.21,
140.18, 135.9 (d, J = 3.0 Hz), 130.4 (d, J = 9.8 Hz, 2 ×), 128.8 (2 ×),
127.4, 126.9 (2 ×), 126.8 (2 ×), 125.2 (2 ×), 116.2 (d, J = 22.8 Hz, 2 ×),
72.8, 66.7, 31.0.
HRMS (ESI): m/z (M+ + Na) calcd for C21H19FO3SNa: 393.0937: found:
393.0933.
Yield: 276 mg (94%); colorless solid; mp 109–110 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 8.8 Hz, 1 H), 7.52 (d, J = 8.8
Hz, 1 H), 7.25–7.22 (m, 2 H), 7.20–7.15 (m, 3 H), 7.00 (t, J = 8.4 Hz, 2
H), 4.57 (br s, 1 H), 3.76 (d, J = 14.8 Hz, 1 H), 3.63 (d, J = 14.8 Hz, 1 H),
1.67 (s, 3 H).
2-([1,1′-Biphenyl]-4-yl)-1-[(4-methoxyphenyl)sulfonyl]propan-2-
ol (6h)
13C NMR (100 MHz, CDCl3): δ = 165.4 (d, J = 254.7 Hz), 144.0, 136.1 (d,
J = 3.0 Hz), 130.4 (d, J = 9.9 Hz, 2 ×), 128.3 (2 ×), 127.3, 124.6 (2 ×),
116.3 (d, J = 22.7 Hz, 2 ×), 73.0, 66.7, 31.0.
HRMS (ESI): m/z (M+ + Na) calcd for C15H15FO3SNa: 317.0624; found:
317.0617.
Yield: 332 mg (87%); colorless solid; mp 106–107 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 8.0 Hz, 2 H), 7.45 (d, J = 8.0
Hz, 2 H), 7.42–7.41 (m, 2 H), 7.38–7.33 (m, 3 H), 7.28 (d, J = 8.8 Hz, 2
H), 6.72 (d, J = 8.8 Hz, 2 H), 4.78 (br s, 1 H), 3.80 (d, J = 15.2 Hz, 1 H),
3.65 (s, 3 H), 3.64 (d, J = 14.8 Hz, 1 H), 1.68 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 163.4, 143.2, 140.4, 139.9, 131.5,
129.7 (2 ×), 128.8 (2 ×), 127.4, 126.9 (2 ×), 126.7 (2 ×), 125.2 (2 ×),
114.1 (2 ×), 72.9, 66.7, 55.5, 31.1.
1-[(4-Methoxyphenyl)sulfonyl]-2-phenylpropan-2-ol (6d)8
Yield: 275 mg (90%); colorless solid; mp 86–87 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 9.2 Hz, 2 H), 7.29 (dd, J = 1.6,
8.0 Hz, 2 H), 7.22–7.14 (m, 3 H), 6.81 (d, J = 8.8 Hz, 2 H), 4.67 (br s, 1
H), 3.84 (s, 3 H), 3.69 (d, J = 14.8 Hz, 1 H), 3.59 (d, J = 14.4 Hz, 1 H),
1.69 (s, 3 H).
HRMS (ESI): m/z (M+ + Na) calcd for C22H22O4SNa: 405.1137; found:
405.1133.
13C NMR (100 MHz, CDCl3): δ = 163.5, 144.5, 131.8, 129.7 (2 ×), 128.3
(2 ×), 127.1, 124.6 (2 ×), 114.3 (2 ×), 73.1, 66.8, 55.7, 30.8.
2-(Naphthalen-2-yl)-1-tosylpropan-2-ol (6i)17
Yield: 306 mg (90%); colorless solid; mp 118–119 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.58–7.70 (m, 3 H), 7.54 (d, J = 8.8 Hz, 1
H), 7.47–7.44 (m, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.21 (dd, J = 2.0, 8.8 Hz,
1 H), 6.84 (d, J = 8.0 Hz, 2 H), 4.80 (br s, 1 H), 3.85 (d, J = 14.4 Hz, 1 H),
3.68 (d, J = 14.8 Hz, 1 H), 2.18 (s, 3 H), 1.74 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.3, 141.2, 136.7, 132.9, 132.4,
129.3 (2 ×), 128.1, 127.9, 127.4 (2 ×), 127.2, 126.1, 126.0, 123.7, 122.7,
73.1, 66.3, 31.0, 21.3.
HRMS (ESI): m/z (M+ + Na) calcd for C16H18O4SNa: 329.0824; found:
329.0819.
2-([1,1′-Biphenyl]-4-yl)-1-tosylpropan-2-ol (6e)
Yield: 348 mg (95%); colorless solid; mp 95–96 °C (hexanes and EtO-
Ac).
1H NMR (400 MHz, CDCl3): δ = 7.52 (d, J = 8.0 Hz, 2 H), 7.46–7.42 (m, 4
H), 7.39–7.35 (m, 3 H), 7.31 (d, J = 8.8 Hz, 2 H), 7.11 (d, J = 8.0 Hz, 2 H),
4.74 (br s, 1 H), 3.80 (d, J = 14.8 Hz, 1 H), 3.65 (d, J = 14.4 Hz, 1 H), 2.30
(s, 3 H), 1.72 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.3, 143.2, 140.4, 139.9, 137.1,
129.6 (2 ×), 128.7 (2 ×), 127.5 (2 ×), 127.4, 126.9 (2 ×), 126.7 (2 ×),
125.1 (2 ×), 72.9, 66.6, 30.9, 21.4.
HRMS (ESI): m/z (M+ + Na) calcd for C20H20O3SNa: 363.1031; found:
363.1026.
2-(Naphthalen-2-yl)-1-(phenylsulfonyl)propan-2-ol (6j)
Yield: 297 mg (91%); colorless solid; mp 112–113 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J = 2.0 Hz, 1 H), 7.76–7.71 (m, 2
H), 7.53 (d, J = 8.8 Hz, 2 H), 7.48–7.44 (m, 3 H), 7.33 (t, J = 7.6 Hz, 1 H),
7.19 (dd, J = 2.0, 8.8 Hz, 1 H), 7.12 (t, J = 7.6 Hz, 2 H), 4.80 (br s, 1 H),
3.86 (d, J = 14.8 Hz, 1 H), 3.71 (d, J = 14.8 Hz, 1 H), 1.77 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 141.3, 139.8, 133.2, 132.9, 132.4,
128.8 (2 ×), 128.2, 127.9, 127.4 (2 ×), 127.3, 126.2, 126.1, 123.7, 122.6,
73.2, 66.5, 30.0.
HRMS (ESI): m/z (M+ + Na) calcd for C22H22O3SNa: 389.1187; found:
389.1181.
2-([1,1′-Biphenyl]-4-yl)-1-(phenylsulfonyl)propan-2-ol (6f)
Yield: 310 mg (88%); colorless solid; mp 112–113 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.57–7.42 (m, 7 H), 7.38–7.29 (m, 7 H),
4.70 (br s, 1 H), 3.82 (d, J = 14.8 Hz, 1 H), 3.67 (d, J = 14.8 Hz, 1 H), 1.72
(s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 143.1, 140.5, 140.10, 140.08, 133.3,
129.0 (2 ×), 128.8 (2 ×), 127.5 (2 ×), 127.4, 127.0 (2 ×), 126.9 (2 ×),
125.2 (2 ×), 73.0, 66.7, 30.9.
HRMS (ESI): m/z (M+ + Na) calcd for C19H18O3SNa: 349.0874; found:
349.0867.
1-[(4-Fluorophenyl)sulfonyl]-2-(naphthalen-2-yl)propan-2-ol
(6k)
HRMS (ESI): m/z (M+ + Na) calcd for C21H20O3SNa: 375.1031; found:
375.1025.
Yield: 327 mg (95%); colorless solid; mp 116–117 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 1.6 Hz, 1 H), 7.76–7.72 (m, 2
H), 7.54 (d, J = 8.8 Hz, 1 H), 7.50–7.46 (m, 2 H), 7.42–7.37 (m, 2 H),
7.14 (dd, J = 1.6, 8.4 Hz, 1 H), 6.71–6.66 (m, 2 H), 4.71 (br s, 1 H), 3.88
(d, J = 14.8 Hz, 1 H), 3.72 (d, J = 14.8 Hz, 1 H), 1.74 (s, 3 H).
2-([1,1′-Biphenyl]-4-yl)-1-[(4-fluorophenyl)sulfonyl]propan-2-ol
(6g)
Yield: 348 mg (94%); colorless solid; mp 117–118 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.55–7.44 (m, 6 H), 7.39–7.35 (m, 3 H),
7.29 (d, J = 8.4 Hz, 2 H), 6.99–6.94 (m, 2 H), 4.23 (br s, 1 H), 3.84 (d, J =
14.8 Hz, 1 H), 3.69 (d, J = 14.8 Hz, 1 H), 1.70 (s, 3 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

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13C NMR (100 MHz, CDCl3): δ = 165.2 (d, J = 254.7 Hz), 141.0, 135.6 (d,
J = 3.0 Hz), 132.8, 132.3, 130.3 (d, J = 9.9 Hz, 2 ×), 128.0, 127.9, 127.3,
126.4, 126.3, 123.8, 122.6, 115.9 (d, J = 22.8 Hz, 2 ×), 73.1, 66.5, 31.0.
13C NMR (100 MHz, CDCl3): δ = 165.5 (d, J = 254.7 Hz), 147.6, 146.8,
138.1, 136.1 (d, J = 3.0 Hz), 130.5 (d, J = 9.9 Hz, 2 ×), 118.0, 116.2 (d, J =
22.7 Hz, 2 ×), 107.8, 105.6, 101.2, 72.9, 66.8, 31.1.
HRMS (ESI): m/z (M+ + Na) calcd for C19H17FO3SNa: 367.0780; found:
HRMS (ESI): m/z (M+ + Na) calcd for C16H15FO5SNa: 361.0522; found:
367.0775.
361.0518.
1-[(4-Methoxyphenyl)sulfonyl]-2-(naphthalen-2-yl)propan-2-ol
(6l)
2-(Benzo[d][1,3]dioxol-5-yl)-1-[(4-methoxyphenyl)sulfonyl]pro-
pan-2-ol (6p)
Yield: 335 mg (94%); colorless solid; mp 97–98 °C (hexanes and
EtOAc).
Yield: 315 mg (90%); colorless solid; mp 93–94 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 2.0 Hz, 1 H), 7.75–7.71 (m, 2
H), 7.54 (d, J = 8.8 Hz, 1 H), 7.48–7.44 (m, 2 H), 7.31 (d, J = 8.8 Hz, 2 H),
7.18 (dd, J = 2.0, 8.8 Hz, 1 H), 6.45 (d, J = 8.8 Hz, 2 H), 4.88 (br s, 1 H),
3.86 (d, J = 14.8 Hz, 1 H), 3.69 (d, J = 14.8 Hz, 1 H), 3.61 (s, 3 H), 1.72 (s,
3 H).
1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 8.8 Hz, 2 H), 6.83 (d, J = 8.8
Hz, 2 H), 6.81 (dd, J = 2.0, 8.4 Hz, 1 H), 6.63 (d, J = 8.0 Hz, 1 H), 6.58 (d,
J = 1.6 Hz, 1 H), 5.89 (d, J = 1.6 Hz, 1 H), 5.84 (d, J = 1.6 Hz, 1 H), 4.62
(br s, 1 H), 3.85 (s, 3 H), 3.66 (d, J = 14.8 Hz, 1 H), 3.54 (d, J = 14.8 Hz, 1
H), 1.61 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 163.2, 141.3, 133.0, 132.3, 131.0,
129.6 (2 ×), 128.1, 127.8, 127.2, 126.2, 126.0, 123.7, 122.8, 113.8 (2 ×),
73.1, 66.4, 55.4, 31.2.
13C NMR (100 MHz, CDCl3): δ = 163.5, 147.5, 146.6, 138.4, 131.6,
129.8 (2 ×), 118.0, 114.1 (2 ×), 107.8, 105.6, 101.1, 72.9, 66.7, 55.6,
31.1.
HRMS (ESI): m/z (M+ + Na) calcd for C20H20O4SNa: 379.0980; found:
HRMS (ESI): m/z (M+ + Na) calcd for C17H18O6SNa: 373.0722; found:
379.0975.
373.0718.
2-(Benzo[d][1,3]dioxol-5-yl)-1-tosylpropan-2-ol (6m)
2-(4-Nitrophenyl)-1-tosylpropan-2-ol (6q)17
Yield: 287 mg (86%); colorless solid; mp 116–117 °C (from hexanes
and EtOAc).
Yield: 322 mg (96%); colorless solid; mp 138–139 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.49 (d, J = 8.4 Hz, 2 H), 7.20 (d, J = 8.0
Hz, 2 H), 6.79 (dd, J = 2.0, 8.4 Hz, 1 H), 6.65 (d, J = 2.0 Hz, 1 H), 6.62 (d,
J = 8.0 Hz, 1 H), 5.89 (d, J = 1.6 Hz, 1 H), 5.86 (d, J = 1.6 Hz, 1 H), 4.61
(br s, 1 H), 3.66 (d, J = 14.8 Hz, 1 H), 3.54 (d, J = 14.8 Hz, 1 H), 2.40 (s, 3
H), 1.64 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 147.5, 146.6, 144.5, 138.6, 137.2,
129.6 (2 ×), 127.6 (2 ×), 118.0, 107.8, 105.6, 101.0, 72.9, 66.7, 30.9,
21.5.
1H NMR (400 MHz, CDCl3): δ = 7.99 (d, J = 9.2 Hz, 2 H), 7.46 (d, J = 8.0
Hz, 2 H), 7.45 (d, J = 9.2 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 2 H), 4.83 (br s, 1
H), 3.75 (d, J = 14.8 Hz, 1 H), 3.62 (d, J = 14.8 Hz, 1 H), 2.37 (s, 3 H),
1.67 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.4, 146.9, 145.3, 136.7, 129.8 (2 ×),
127.5 (2 ×), 125.9 (2 ×), 123.3 (2 ×), 73.0, 65.7, 31.0, 21.5.
HRMS (ESI): m/z (M+ + Na) calcd for C16H17NO5SNa: 358.0725; found:
358.0721.
HRMS (ESI): m/z (M+ + Na) calcd for C17H18O5SNa: 357.0773; found:
357.0767.
2-(4-Nitrophenyl)-1-(phenylsulfonyl)propan-2-ol (6r)
Yield: 302 mg (94%); colorless solid; mp 150–151 °C (hexanes and
EtOAc).
2-(Benzo[d][1,3]dioxol-5-yl)-1-(phenylsulfonyl)propan-2-ol (6n)
Yield: 285 mg (89%); colorless solid; mp 109–110 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 8.02 (d, J = 8.8 Hz, 2 H), 7.64–7.54 (m, 3
H), 7.48 (d, J = 8.8 Hz, 2 H), 7.41–7.37 (m, 2 H), 4.81 (br s, 1 H), 3.77 (d,
J = 14.8 Hz, 1 H), 3.65 (d, J = 14.8 Hz, 1 H), 1.69 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.4, 147.0, 139.8, 133.9, 129.2 (2 ×),
127.5 (2 ×), 125.9 (2 ×), 123.4 (2 ×), 73.1, 65.8, 30.9.
1H NMR (400 MHz, CDCl3): δ = 7.62 (d, J = 8.4 Hz, 2 H), 7.55 (t, J = 7.6
Hz, 1 H), 7.41 (t, J = 7.6 Hz, 2 H), 6.77 (dd, J = 2.0, 8.4 Hz, 1 H), 6.67 (d,
J = 2.0 Hz, 1 H), 6.60 (d, J = 8.0 Hz, 1 H), 5.89 (d, J = 1.6 Hz, 1 H), 5.86 (d,
J = 1.6 Hz, 1 H), 4.57 (br s, 1 H), 3.70 (d, J = 14.8 Hz, 1 H), 3.57 (d, J =
14.8 Hz, 1 H), 1.65 (s, 3 H).
HRMS (ESI): m/z (M+ + Na) calcd for C15H15NO5SNa: 344.0569; found:
344.0566.
13C NMR (100 MHz, CDCl3): δ = 147.5, 146.7, 140.2, 138.4, 133.4,
129.0 (2 ×), 127.5 (2 ×), 118.0, 107.8, 105.6, 101.0, 72.9, 66.6, 30.9.
HRMS (ESI): m/z (M+ + Na) calcd for C16H16O5SNa: 343.0616; found:
343.0612.
1-[(4-Fluorophenyl)sulfonyl]-2-(4-nitrophenyl)propan-2-ol (6s)
Yield: 325 mg (96%); colorless solid; mp 118–119 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 8.08 (d, J = 9.2 Hz, 2 H), 7.69 (dd, J = 5.2,
9.2 Hz, 2 H), 7.52 (d, J = 8.8 Hz, 2 H), 7.10 (t, J = 8.8 Hz, 2 H), 4.71 (br s,
1 H), 3.73 (d, J = 14.8 Hz, 1 H), 3.63 (d, J = 14.8 Hz, 1 H), 1.72 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 165.9 (d, J = 257.0 Hz), 151.5, 147.1,
135.9 (d, J = 3.1 Hz), 130.5 (d, J = 9.9 Hz, 2 ×), 125.0 (2 ×), 123.4 (2 ×),
116.6 (d, J = 22.7 Hz, 2 ×), 73.2, 66.0, 30.8.
2-(Benzo[d][1,3]dioxol-5-yl)-1-[(4-fluorophenyl)sulfonyl]propan-
2-ol (6o)
Yield: 287 mg (85%); colorless solid; mp 127–128 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.59 (d, J = 8.8 Hz, 1 H), 7.58 (d, J = 8.8
Hz, 1 H), 7.08–7.04 (m, 2 H), 6.81 (dd, J = 1.6, 8.0 Hz, 1 H), 6.64 (d, J =
8.0 Hz, 1 H), 6.55 (d, J = 1.6 Hz, 1 H), 5.91 (d, J = 1.6 Hz, 1 H), 5.87 (d, J =
1.6 Hz, 1 H), 4.51 (br s, 1 H), 3.71 (d, J = 14.8 Hz, 1 H), 3.58 (d, J = 14.8
Hz, 1 H), 1.62 (s, 3 H).
HRMS (ESI): m/z (M+ + Na) calcd for C15H14FNO5SNa: 362.0474;
found: 362.0471.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

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Synthesis
1-[(4-Methoxyphenyl)sulfonyl]-2-(4-nitrophenyl)propan-2-ol (6t)
HRMS (ESI): m/z (M+ + Na) calcd for C15H14F2O3SNa: 335.0529; found:
335.0523.
Yield: 312 mg (89%); colorless solid; mp 125–126 °C (hexanes and
EtOAc).
2-(4-Fluorophenyl)-1-[(4-methoxyphenyl)sulfonyl]propan-2-ol
(6x)
1H NMR (400 MHz, CDCl3): δ = 8.02 (d, J = 8.8 Hz, 2 H), 7.49 (d, J = 8.8
Hz, 2 H), 7.46 (d, J = 8.8 Hz, 2 H), 6.81 (d, J = 8.8 Hz, 2 H), 4.83 (br s, 1
H), 3.81 (s, 3 H), 3.74 (d, J = 14.8 Hz, 1 H), 3.62 (d, J = 14.8 Hz, 1 H),
1.67 (s, 3 H).
Yield: 295 mg (91%); colorless solid; mp 112–113 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.49 (d, J = 8.8 Hz, 2 H), 7.23 (d, J = 8.8
Hz, 2 H), 6.88–6.81 (m, 4 H), 4.61 (br s, 1 H), 3.84 (s, 3 H), 3.67 (d, J =
14.8 Hz, 1 H), 3.57 (d, J = 14.8 Hz, 1 H), 1.65 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 163.6, 161.8 (d, J = 244.1 Hz), 140.2 (d,
J = 3.0 Hz), 133.8, 129.7 (2 ×), 126.5 (d, J = 8.3 Hz, 2 ×), 114.9 (d, J =
21.2 Hz, 2 ×), 114.3 (2 ×), 72.8, 66.6, 55.7, 31.1.
13C NMR (100 MHz, CDCl3): δ = 163.9, 151.6, 147.0, 131.1, 129.7 (2 ×),
125.9 (2 ×), 123.3 (2 ×), 114.4 (2 ×), 73.1, 65.9, 55.7, 31.0.
HRMS (ESI): m/z (M+ + Na) calcd for C16H17NO6SNa: 374.0674; found:
374.0668.
2-(4-Fluorophenyl)-1-tosylpropan-2-ol (6u)
HRMS (ESI): m/z (M+ + Na) calcd for C16H17FO4SNa: 347.0729; found:
347.0723.
Yield: 277 mg (90%); colorless solid; mp 128–129 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.48 (d, J = 8.4 Hz, 2 H), 7.24 (d, J = 8.8
Hz, 1 H), 7.23 (d, J = 8.8 Hz, 1 H), 7.19 (d, J = 8.4 Hz, 2 H), 6.87–6.81 (m,
2 H), 4.62 (br s, 1 H), 3.68 (d, J = 14.8 Hz, 1 H), 3.57 (d, J = 14.8 Hz, 1 H),
2.40 (s, 3 H), 1.67 (s, 3 H).
2-(p-Tolyl)-1-tosylpropan-2-ol (6y)17
Yield: 289 mg (95%); colorless solid; mp 105–106 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.4 Hz, 2 H), 7.16 (d, J = 8.0
Hz, 2 H), 7.15 (d, J = 8.4 Hz, 2 H), 6.97 (d, J = 8.0 Hz, 2 H), 4.24 (br s, 1
H), 3.69 (d, J = 14.8 Hz, 1 H), 3.57 (d, J = 14.8 Hz, 1 H), 2.39 (s, 3 H),
2.28 (s, 3 H), 1.68 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 161.9 (d, J = 244.8 Hz), 144.7, 140.2 (d,
J = 3.0 Hz), 137.2, 129.7 (2 ×), 127.5 (2 ×), 126.4 (d, J = 7.6 Hz, 2 ×),
114.9 (d, J = 20.4 Hz, 2 ×), 72.8, 66.5, 30.9, 21.5.
HRMS (ESI): m/z (M+ + Na) calcd for C16H17FO3SNa: 331.0780; found:
331.0774.
13C NMR (100 MHz, CDCl3): δ = 144.3, 141.5, 137.4, 136.8, 129.5 (2 ×),
128.8 (2 ×), 127.5 (2 ×), 124.5 (2 ×), 73.0, 66.7, 30.7, 21.5, 20.9.
2-(4-Fluorophenyl)-1-(phenylsulfonyl)propan-2-ol (6v)
HRMS (ESI): m/z (M+ + Na) calcd for C17H20O3SNa: 327.1031; found:
327.1027.
Yield: 279 mg (95%); colorless solid; mp 131–132 °C (hexanes and
EtOAc).
2-(4-Methoxyphenyl)-1-tosylpropan-2-ol (6z)14c
1H NMR (400 MHz, CDCl3): δ = 7.58 (d, J = 8.8 Hz, 2 H), 7.54 (d, J = 7.6
Hz, 1 H), 7.39 (t, J = 8.4 Hz, 2 H), 7.24 (d, J = 8.8 Hz, 1 H), 7.22 (d, J = 8.8
Hz, 1 H), 6.83 (t, J = 8.8 Hz, 2 H), 4.61 (br s, 1 H), 3.72 (d, J = 14.4 Hz, 1
H), 3.60 (d, J = 14.4 Hz, 1 H), 1.66 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 161.8 (d, J = 244.8 Hz), 140.06 (d, J =
3.1 Hz), 140.05, 133.5, 129.1 (2 ×), 127.4 (2 ×), 126.4 (d, J = 8.3 Hz, 2 ×),
114.9 (d, J = 21.2 Hz, 2 ×), 72.8, 66.5, 30.9.
Yield: 307 mg (95%); colorless solid; mp 78–79 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.47 (d, J = 8.4 Hz, 2 H), 7.19–7.15 (m, 4
H), 6.68 (d, J = 9.2 Hz, 2 H), 4.58 (br s, 1 H), 3.75 (s, 3 H), 3.68 (d, J =
14.8 Hz, 1 H), 3.55 (d, J = 14.8 Hz, 1 H), 2.38 (s, 3 H), 1.67 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 158.6, 144.3, 137.3, 136.6, 129.6 (2 ×),
127.5 (2 ×), 125.8 (2 ×), 113.4 (2 ×), 72.8, 66.8, 55.1, 30.7, 21.5.
HRMS (ESI): m/z (M+ + Na) calcd for C15H15FO3SNa: 317.0624; found:
HRMS (ESI): m/z (M+ + Na) calcd for C17H20O4SNa: 343.0980; found:
317.0617.
343.0974.
X-ray Crystal Data
Single crystal of 6v was grown by slow diffusion of EtOAc into a solu-
tion of 6v in CH2Cl2 to yield a colorless prism. The compound crystal-
lized in the monoclinic crystal system, space group P 21/c, a =
11.8458(16) Å, b = 5.8269(9) Å, c = 20.094(3) Å, V = 1386.9(3) Å3, Z = 4,
dcalcd = 1.410 g/cm3, F(000) = 616, 2θ range 1.72–26.31°, R indices (all
data) R1 = 0.0587, wR2 = 0.1547.
1-[(4-Ethylphenyl)sulfonyl]-2-phenylpropan-2-ol (6aa)
Yield: 289 mg (95%); colorless solid; mp 77–78 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.4 Hz, 2 H), 7.27–7.23 (m, 2
H), 7.17–7.11 (m, 5 H), 4.23 (br s, 1 H), 3.73 (d, J = 14.8 Hz, 1 H), 3.59
(d, J = 14.8 Hz, 1 H), 2.64 (q, J = 7.2 Hz, 2 H), 1.67 (s, 3 H), 1.20 (t, J = 7.2
Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 150.4, 144.1, 137.1, 128.4 (2 ×), 128.0
(2 ×), 127.4 (2 ×), 126.9, 124.5 (2 ×), 72.9, 66.3, 30.7, 28.7, 15.1.
HRMS (ESI): m/z (M+ + Na) calcd for C17H20O3SNa: 327.1031; found:
327.1030.
2-(4-Fluorophenyl)-1-[(4-fluorophenyl)sulfonyl]propan-2-ol (6w)
Yield: 290 mg (93%); colorless solid; mp 130–131 °C (hexanes and
EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 8.8 Hz, 1 H), 7.58 (d, J = 9.2
Hz, 1 H), 7.24 (d, J = 8.8 Hz, 1 H), 7.23 (d, J = 9.2 Hz, 1 H), 7.10–7.04 (m,
2 H), 6.90–6.85 (m, 2 H), 4.56 (br s, 1 H), 3.71 (d, J = 14.8 Hz, 1 H), 3.60
(d, J = 14.8 Hz, 1 H), 1.67 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 165.6 (d, J = 255.5 Hz), 161.9 (d, J =
244.9 Hz), 140.0 (d, J = 3.0 Hz), 136.1 (d, J = 3.0 Hz), 130.4 (d, J = 9.8
Hz, 2 ×), 126.5 (d, J = 7.6 Hz, 2 ×), 116.4 (d, J = 22.7 Hz, 2 ×), 115.0 (d,
J = 21.2 Hz, 2 ×), 72.8, 66.7, 31.0.
1-(Tosylmethyl)-2,3-dihydro-1H-inden-1-ol (8a)
Yield: 275 mg (91%); colorless gum.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

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C.-K. Chan et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 7.83 (d, J = 8.0 Hz, 2 H), 7.37 (d, J = 8.0
Hz, 2 H), 7.29 (d, J = 7.6 Hz, 1 H), 7.25–7.18 (m, 3 H), 4.18 (br s, 1 H),
3.74 (d, J = 14.0 Hz, 1 H), 3.42 (d, J = 14.0 Hz, 1 H), 3.14–3.07 (m, 1 H),
2.90–2.82 (m, 1 H), 2.79–2.72 (m, 1 H), 2.46 (s, 3 H), 2.43–2.34 (m, 1
H).
13C NMR (100 MHz, CDCl3): δ = 145.1, 145.1, 142.7, 138.0, 130.0 (2 ×),
129.0, 127.7 (2 ×), 127.0, 125.1, 122.8, 81.4, 63.9, 39.2, 29.8, 21.7.
HRMS (ESI): m/z (M+ + Na) calcd for C15H16O3SNa: 299.0718; found:
299.0716.
Funding Information
We thank the Ministry of Science and Technology of the Republic of
China for financial support (MOST 105-2113-M-037-001). This study
was supported partially by Kaohsiung Medical University ‘Aim for the
HRMS (ESI): (M+ + Na) calcd for C17H18O3SNa: 325.0874; found:
325.0867.
Top Universities Grant’ No. KMU-TP105PR02.
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Supporting Information
Yield: 291 mg (92%); colorless gum.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.4 Hz, 2 H), 7.52–7.47 (m, 1
H), 7.35 (dd, J = 0.8, 8.4 Hz, 2 H), 7.18–7.13 (m, 2 H), 7.08–7.04 (m, 1
H), 4.22 (br s, 1 H), 3.57 (d, J = 14.4 Hz, 1 H), 3.51 (d, J = 14.4 Hz, 1 H),
2.89–2.71 (m, 3 H), 2.45 (s, 3 H), 2.19–2.12 (m, 1 H), 2.02–1.94 (m, 1
H), 1.87–1.77 (m, 1 H).
Supporting information for this article is available online at
https://doi.org /10.1055/s-0036-1589051.
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References
13C NMR (100 MHz, CDCl3): δ = 144.9, 139.8, 138.2, 136.2, 130.0 (2 ×),
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129.1, 127.9, 127.6 (2 ×), 126.4, 126.1, 72.6, 65.1, 35.5, 29.0, 21.6, 19.9.
HRMS (ESI): m/z (M+ + Na) calcd for C18H20O3SNa: 339.1031; found:
339.1024.
7-Methoxy-1-(tosylmethyl)-1,2,3,4-tetrahydronaphthalen-1-ol
(8c)
Yield: 325 mg (94%); colorless gum.
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz, 2 H), 7.35 (dd, J = 0.8,
8.4 Hz, 2 H), 7.02 (d, J = 2.8 Hz, 1 H), 6.96 (d, J = 8.4 Hz, 1 H), 6.73 (dd,
J = 2.8, 8.4 Hz, 1 H), 4.23 (br s, 1 H), 3.75 (s, 3 H), 3.58 (d, J = 14.4 Hz, 1
H), 3.48 (d, J = 14.4 Hz, 1 H), 2.81–2.66 (m, 3 H), 2.45 (s, 3 H), 2.12–
2.05 (m, 1 H), 2.00–1.91 (m, 1 H), 1.84–1.73 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 158.1, 144.9, 140.8, 138.2, 130.1, 130.0
(2 ×), 128.2, 127.6 (2 ×), 114.6, 110.5, 72.8, 64.9, 55.3, 35.4, 28.1, 21.6,
20.1.
HRMS (ESI): m/z (M+ + Na) calcd for C19H22O4SNa: 369.1137; found:
369.1131.
6,7-Dimethoxy-4-(tosylmethyl)-1,2-dihydronaphthalene (9)
Yield: 326 mg (91%); colorless gum.
1H NMR (400 MHz, CDCl3): δ = 7.66 (d, J = 8.4 Hz, 2 H), 7.23 (d, J = 0.4
Hz, 1 H), 7.21 (d, J = 0.4 Hz, 1 H), 6.75 (s, 1 H), 6.62 (s, 1 H), 5.74 (t, J =
4.8 Hz, 1 H), 4.18 (s, 2 H), 3.86 (s, 3 H), 3.81 (s, 3 H), 2.61 (t, J = 8.4 Hz,
2 H), 2.39 (s, 3 H), 2.20–2.15 (m, 2 H).
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1-Phenyl-2-tosylethan-1-ol (11)8
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1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.0 Hz, 2 H), 7.37 (d, J = 8.4
Hz, 2 H), 7.36–7.24 (m, 5 H), 5.23 (d, J = 10.0 Hz, 1 H), 3.47 (dd, J =
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(2 ×), 128.2, 127.9 (2 ×), 125.6 (2 ×), 68.4, 63.9, 21.6.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I

I
C.-K. Chan et al.
Paper
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I