Sulfonylative alkoxyhydroxylation of 2-arylpropenes

Article abstract of DOI:10.1016/j.tet.2017.09.047

One-pot three-step sulfonylative alkoxyhydroxylation of 2-arylpropenes 1 affords oxygenated sulfonylcumenes 4 in moderate yields via a sequential route: (i) NBS-mediated allylic bromination of 2-arylpropenes 1 in CH₂Cl₂, (ii) sodium sulfinates 2-promoted nucleophilic substitution of the resulting styryl bromides in a co-solvent of alcohol and water, and (iii) V₂O₅/H₂O₂ mediated alkoxyhydroxylation of corresponding styryl sulfones 3 in alcohol. The synthetic route provides a highly effective protocol for the 1,2,3-tricarbofunctionalization of 2-arylpropenes 1 via two carbon-oxygen and one carbon-sulfur bond formations.

Full text of DOI:10.1016/j.tet.2017.09.047

Tetrahedron xxx (2017) 1e6
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Sulfonylative alkoxyhydroxylation of 2-arylpropenes
Huei-Sin Wang, Yan-Shin Wu, Meng-Yang Chang*
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University Hostiptal, Kaohsiung Medical University, Kaohsiung, 807, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
One-pot three-step sulfonylative alkoxyhydroxylation of 2-arylpropenes 1 affords oxygenated sulfo-
nylcumenes 4 in moderate yields via a sequential route: (i) NBS-mediated allylic bromination of 2-
arylpropenes 1 in CH2Cl2, (ii) sodium sulfinates 2-promoted nucleophilic substitution of the resulting
styryl bromides in a co-solvent of alcohol and water, and (iii) V2O5/H2O2 mediated alkoxyhydroxylation
of corresponding styryl sulfones 3 in alcohol. The synthetic route provides a highly effective protocol for
the 1,2,3-tricarbofunctionalization of 2-arylpropenes 1 via two carbon-oxygen and one carbon-sulfur
bond formations.
Received 15 August 2017
Received in revised form
18 September 2017
Accepted 26 September 2017
Available online xxx
Keywords:
Sulfonylative alkoxyhydroxylation
2-Arylpropenes
© 2017 Elsevier Ltd. All rights reserved.
1,2,3-Tricarbofunctionalization
1. Introduction
applications of sodium sulfinates,6 we turn the synthetic aim to the
1,2,3-tricarbofunctionalization from 2-arylpropenes to oxygenated
During the past decade, much attention has been paid to the
vicinal difunctionalization of olefinic arms on styrene (vinylarene)
via transition-metal,1 non-metallic peroxide2 or iodoarene-
containing oxidant,3 and organocatalyst4 promoted carbon-
heteroatom or carbon-carbon formations. Based on recent re-
ports, transition-metal ions such as Ni(II),1a Pd(II)/Cu(II),1b or
Pd(II)1c promoting one-step 1,2-dicarbofunctionalization of
substituted styrenes with substituted stannanes, boronic acids, or
triflates, have been major pathways (Scheme 1). Among these
routes, we find that selenium-based compounds (selenocycteine2a
or SeO22b-c) containing H2O2 mediated direct dihydroxylation or
alkoxyhydroxylation of double bonds on styrene synthons provide
some facile accesses to substituted vicinal diols or alkoxyalcohols.
Oxidative functionalization of styrene derivatives has great
relevance in organic fields. Despite remarkable advances in the
functionalization of alkenes, new transition metal promoted syn-
thetic designs of sulfone-based building blocks still represent a
continuing demand in the organic field, especially those that allow
one-pot regioselective well-defined operations. Compared with
commercially available substituted styrenes, few reports have been
sulfonylcumenes via three regioselective bond formations of 2
carbon-oxygen (C-O) and 1 carbon-sulfur (C-S).
In Scheme 2, we describe a facile one-pot synthetic route of
oxygenated sulfonylcumenes 4, including (i) NBS-mediated allylic
bromination of 2-arylpropenes 1 in CH2Cl2, (ii) sodium sulfinates (2,
YSO2Na)-promoted nucleophilic substitution of the resulting styryl
bromides in a co-solvent of alcohol and water, and (iii) V2O5/H2O2
mediated alkoxyhydroxylation of the corresponding styryl sulfones
3 in alcohol.7 According to a report from Desbordes and Euvrard
(Rhone-Poulenc Agrochimie company),8 a series of dihydroxyl
sulfonylcumenes performed highly effective herbicidal activity.
2. Results and discussion
To initiate our work, allylic bromination of model substrate 1a
(1.0 mmol) with NBS (1.05 equiv) in CH2Cl2 (5 mL) at reflux for 2 h
followed by nucleophilic substitution of the resulting allylic bro-
mide with TolSO2Na (2a, 1.07 equiv) in MeOH (10 mL) at reflux for
2 h provided 3a in a nearly quantitative yield. By the one-pot two-
step transformation from 1a to 3a, the sulfonyl group was effi-
documented for synthetic application of
a-methylstyrene (2-
ciently installed into the a-methyl position of 1a via a C-S bond
arylpropene, cumene).5 Notably, no reports for one-pot 1,2,3-
tricarbofunctionalization of the propenyl group on 2-
arylpropenes have been presented. In our ongoing research in the
formation. Without further purification, 4a produced an 82% yield
with the addition of V2O5 (0.3 equiv) and H2O2 (35%, 0.5 mL) to the
resulting reaction mixture at reflux for 2 h via two C-C bond for-
mations.9 The one-pot three-step regioselective process showed
sulfonylative methoxyhydroxylation (Table 1, entry 1). With the
results in mind, different metal oxides (e.g. MeReO3, MoO5)10,11 and
* Corresponding author. Tel.: þ886 7 3121101x2220; fax: þ886 7 3125339.
E-mail address: mychang@kmu.edu.tw (M.-Y. Chang).
https://doi.org/10.1016/j.tet.2017.09.047
0040-4020/© 2017 Elsevier Ltd. All rights reserved.
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10.1016/j.tet.2017.09.047

2
H.-S. Wang et al. / Tetrahedron xxx (2017) 1e6
coupling constant of 12.0 Hz at
4.29 ppm, which indicates that one methylene group (for the
sulfonyl arm) and the other methylene group (for the hydroxyl
arm) is doublet with a coupling constant 15.2 Hz at 3.75 ppm and
15.2 Hz at 3.73 ppm. The structure of 4a with three arms (one
d 4.36 ppm and 12.0 Hz at
transition-metal
selenium-based
d
selenocysteine
H O
Ni(II)
R
OH
OH
Ar-I, R-I
2
2
Ph
Ph
Ph
Ph
Nevado (ref 1a)
Pd(II)/Cu(II)
Santi (ref 2a)
d
Ar
d
Ar
OH
OH
HO
SeO /H O
2 2 2
2 Ar-SnBu
3
hydroxyl, one methoxy, and one sulfonyl group) was determined by
single-crystal X-ray analysis (see Fig. 1).13 To our best knowledge,
there is currently no experimental report on V2O5/H2O2-mediated
methoxyhydroxylation. On the basis of experimental results, a
possible reaction mechanism is shown in Scheme 3. The mecha-
nism should be initiated to form NBS-mediated bromination of 1a.
By the involvement of 2a, 3a is yielded. In the presence of MeOH (2
equiv), V2O5 forms methyl peroxyvanadate (2 equiv) under the
H2O2 mediated oxidation condition. After the coordination of 3a
with the corresponding peroxy species, intermediate A with a six-
membered ring conformation is provided. Then, by the removal of
in situ generated VO2, 3a is produced. Finally, V2O5 is recovered via
the complexation of VO2 and H2O2.
Ph
Ph
Ph
Ph
Sigman (ref 1b)
Konwar (ref 2b)
Ar
Pd(II)
R
SeO /H O /ROH
2 2 2
Ar-B(OH) , R-OTf
2
Ph
Ph
Ph
Ph
RO
Nevado (ref 1c)
Chang (ref 2c)
Ar
Scheme 1. Difunctionalization of olefin motif on styrenes.
OH
NBS, CH Cl
2
2
V O
2
5
2
Ar
OR
O
Ar
Ar
O
then
H O
2
S
S
YSO Na 2
Y
2
O
O
Y
ROH, H O
1
2
3
4
According to the above reaction conditions, we explored the
substrate scope, and the results are shown in Table 2. To adjust the
Ar group of 2a-f, a Y group of 3a-m and an R group of alcohols, 4a-v
(Ar ¼ Ph, 4-NO2C6H4, 3-FC6H4, 4-CF3C6H4, 4-ClC6H4, 3,4-Cl2C6H3;
Y ¼ Tol, Ph, Me, nBu, 4-FC6H4, 4-MeOC6H4, 3-MeC6H4, 4-EtC6H4, 4-
iPrC6H4, 4-nBuC6H4, 4-tBuC6H4, 4-BrC6H4, 4-ClC6H4,; R ¼ Me, Et,
nBu, iPr, tBu) were provided in a range of 5%e86% yields, as shown
in entries 1e22. For the uses of Ar and Y substituents, the phenyl
ring with an electron-donating group, electron-neutral group, and
electron-withdrawing group (besides entry 14, Ar ¼ 4-nitrophenyl
group) were well tolerated. For the R group, the primary and sec-
ondary alphabetic substituents performed well.
Scheme 2. Trifunctionalization of olefin motif on styrenes.
Table 1
Reaction Conditions.a
OH
oxides
H O
NBS, CH Cl
2
2
Ph
Ph
Ph
OMe
O
S
O
then
TolSO Na 2a
2
2
S
Tol
2
O
O
Tol
MeOH, H O
2
1a
3a
4a
Especially, when reaction of 2b (Ar ¼ 4-NO2C6H4) and 3a was
treated with the optimal combination, only trace amounts of 4n
(5%) was observed and 4n-1 was isolated in a 34% yield (entry 14).
From the results, we believed that the key nitro group promoted
the removal of methoxy group of 4n to generate the stable tertiary
carbocation such that the epoxide ring was formed by an intra-
molecular annulation of primary hydroxyl group. However, with
the use of tBuOH as the solvent (entry 22), only diol 4v-1 was
isolated in a 74% yield via the introduction of H2O. During the
process, only water was involved into tertiary carbon center and no
t-butyl substituent was installed due to the bulky steric hindrance
of t-Bu group. When the reaction of 2a (Ar ¼ Ph) was treated with
3n (Y ¼ CF3) in MeOH, complex products was detected under the
optimal condition (entry 23). Furthermore, when Ar was a 2-furyl
Entry
Oxides (equiv)
Temp (ꢀC)
Time (h)
4a (%)b
1
2
3
4
5
6
7
8
9
V2O5 (0.3)
MeReO3 (0.3)
TeO2 (0.3)
MoO5 (0.3)
SeO2 (0.3)
V2O5 (0)
V2O5 (0.1)
V2O5 (1.0)
V2O5 (0.3)
V2O5 (0.3)
65
65
65
65
65
65
65
65
25
65
2
2
2
2
2
2
2
2
2
10
82
c-d
-
-
c-d
10d
61
c-d
-
48
81
<10d
75
10
a
Reactions were run on a 1.0 mmol scale with 1a, NBS (187 mg, 1.05 equiv),
CH2Cl2 (5 mL), reflux, 2 h; TolSO2Na (2a, 190 mg, 1.07 equiv), MeOH (10 mL), reflux,
2 h; oxides, H2O2 (35% in H2O, 0.5 mL).
b
Isolated yields.
No reaction.
3a was recovered as the major product.
c
d
non-metal oxides (e.g. SeO2, TeO2)2b-c,e12 were also examined for
the one-pot process. When the resulting 3a was treated with
MeReO3, TeO2, MoO5, or SeO2 or at a reflux for 2 h, no isolation of 3a
was observed (for entries 2e3); and 4a was isolated in low (for
entry 4, 10%) and moderate yields (for entry 5, 61%), respectively. By
increasing or decreasing the amounts of V2O5 (0, 0.1 or 1.0 equiv),
the yield of 4a was poorer than for the 1.1 equiv (entries 6e8, 0%,
48% or 81%). Therefore, V2O5 (0.3 equiv) was chosen as the oxidant
for scanning the reaction conditions. When the reaction tempera-
ture was decreased (65 / 25, entry 9), only <10% yield of 4a was
obtained. Next, by elongating the reaction time (2 / 10 h), the yield
of 4a was slightly decreased to 75% (entry 10). On the basis of a
higher yield and activity, we believe that V2O5 could be an optimal
oxidant for the formation of 4a.
The structural framework and relative regiochemistry of 4a
were determined from 1H NMR and J coupling analysis. In the 1H
NMR spectrum, the equatorial proton showed a doublet with a
Fig. 1. X-ray structure of 4a.
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H.-S. Wang et al. / Tetrahedron xxx (2017) 1e6
3
O
V
3. Conclusion
HO-OH
2
+
H O
2
V O
2
+ 2 MeOH
5
MeO
O
OH
In summary, we have developed a one-pot three-step synthesis
of oxygenated 4 via a sequential route: (i) NBS-mediated allylic
bromination of 1 in CH2Cl2, (ii) sodium sulfinate-promoted nucle-
ophilic substitution of the resulting styryl bromides in a co-solvent
of alcohol and water, and (iii) V2O5/H2O2 mediated alkoxyhydrox-
ylation of 3 in alcohol. The synthetic route provides a highly
effective protocol for the 1,2,3-tricarbofunctionalization of 2-
arylpropenes 1 via two carbon-oxygen and one carbon-sulfur
bond formations. The plausible mechanism has been discussed
and proposed.
H O
2
O
S
Ph
2
Tol
H O
2
3a
2
O
2 VO
2
O
OH
HO
TolSO Na 2a
2
O
V
O
S
MeO
Ph
2
2
MeO
Ph
O
NBS
2
2
Ph
1a
Ph
Tol
S
Tol
Br
O
O
A
4a
Scheme 3. Possible Mechanism.
4. Experimental section
Table 2
Synthesis of 4.a
4.1. General
OH
OH
OH
NBS, CH Cl
2
V O
2
2
5
All reagents and solvents were obtained from commercial
sources and used without further purification. Reactions were
routinely carried out under an atmosphere of dry air with magnetic
stirring. Products in organic solvents were dried with anhydrous
magnesium sulfate before concentration in vacuo. Melting points
were determined with a SMP3 melting apparatus. Infrared spectra
were recorded with a PerkineElmer 100 series FTIR spectrometer.
1H and 13C NMR spectra were recorded on a Varian INOVA-400
spectrometer operating at 400 and at 100 MHz, respectively.
O
Ar
OR
O
Ar
Ph
Ar
1
O
then
O
O
S
Tol
H O
2
2
S
S
S
YSO Na 2
Y
2
O
O
Y
O
Tol
O
ROH, H O
2
3
4
4n-1
(Ar = 4-NO C H )
4v-1
2
6 4
Entry
1, Ar ]
2, Y ]
ROH
4 (%)b
1
2
3
4
5
6
7
8
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2a, Ph
2b, 4-NO2C6H4
2c, 3-FC6H4
2d, 4-CF3C6H4
2e, 4-ClC6H4
2f, 3,4-Cl2C6H3
2a, Ph
2a, Ph
3a, Tol
3b, Ph
3c, Me
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
4a, 82
4b, 80
4c, 70
4d, 70
4e, 83
4f, 80
4g, 82
4h, 78
4i, 80
4j, 84
4k, 86
4l, 80
4m, 81
4n, 5c
4o, 62
4p, 60
4q, 78
4r, 72
4s, 80
4t, 72
4u, 58
4v, -d
4w, -e
4x, -e
Chemical shifts (d) are reported in parts per million (ppm) and the
3d, nBu
3e, 4-FC6H4
coupling constants (J) are given in Hertz. High resolution mass
spectra (HRMS) were measured with a mass spectrometer Fin-
nigan/Thermo Quest MAT 95XL. X-ray crystal structures were ob-
tained with an Enraf-Nonius FR-590 diffractometer (CAD4, Kappa
CCD).
3f, 4-MeOC6H4
3g, 3-MeC6H4
3h, 4-EtC6H4
3i, 4-iPrC6H4
3j, 4-nBuC6H4
3k, 4-tBuC6H4
3l, 4-BrC6H4
3m, 4-ClC6H4
3a, Tol
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
4.1.1. 1-Methyl-4-(2-phenylallylsulfonyl)benzene (3a)
NBS (N-bromosuccinimide, 187 mg, 1.05 mmol) was added to a
solution of 2-phenylpropene (1a, 118 mg, 1.0 mmol) in CH2Cl2
(5 mL) at rt. The reaction mixture was stirred at reflux for 2 h. The
reaction mixture was cooled to 25 ꢀC and a solution of sodium
toluenesulfinates 2 (2a, TolSO2Na, 190 mg, 1.07 mmol) in MeOH
(10 mL) at rt. Then, the reaction mixture was stirred at reflux for 2 h.
The reaction mixture was cooled to 25 ꢀC and the solvent was
concentrated. The residue was diluted with water (10 mL) and the
mixture was extracted with CH2Cl2 (3 ꢁ 20 mL). The combined
organic layers were washed with brine, dried, filtered and evapo-
rated to afford crude product under reduced pressure. Purification
on silica gel (hexanes/EtOAc ¼ 8/1e4/1) afforded 3a. Yield ¼ ~100%
(270 mg); Colorless solid; mp ¼ 96e97 ꢀC (recrystallized from
hexanes and EtOAc); IR (CHCl3): 3102, 3023, 2985, 1503, 1123, 956,
783 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C16H17O2S 273.0949, found
3a, Tol
3a, Tol
3a, Tol
3a, Tol
3a, Tol
3a, Ph
3a, Ph
3a, Ph
3n, CF3
3a, Tol
3a, Tol
3a, Tol
nBuOH
iPrOH
tBuOH
MeOH
MeOH
MeOH
MeOH
2a, Ph
2a, Ph
2a, Ph
2g, 2-furyl
2h, 4-MeOC6H4
2i, 4-MeC6H4
4y, -e
4z, -e
a
Reactions were run on a 1.0 mmol scale with 1a, NBS (187 mg, 1.05 equiv),
CH2Cl2 (5 mL), reflux, 2 h; YSO2Na (2, 1.07 equiv), ROH (10 mL), reflux, 2 h; V2O5
(60 mg, 0.3 equiv), H2O2 (35% in H2O, 0.5 mL).
b
Isolated yields.
34% of 4n-1 was isolated.
74% of 4v-1 was isolated.
Complex products were isolated.
273.0948; 1H NMR (400 MHz, CDCl3):
7.28e7.20 (m, 7H), 5.59 (s, 1H), 5.21 (s, 1H), 4.25 (s, 2H), 2.39 (s, 3H);
13C NMR (100 MHz, CDCl3):
144.56, 138.84, 136.57, 135.42, 129.46
d
7.66 (d, J ¼ 8.4 Hz, 2H),
c
d
e
d
(2x), 128.64 (2x), 128.32 (2x), 127.89, 126.20 (2x), 121.70, 62.12,
21.54.
(for 2g, a heterocyclic ring), 4-methoxyphenyl (for 2h, an electron-
donating group) or 4-methylphenyl substituent (for 2i, a benzylic
position), complex mixture were still observed in entries 24e26.
From the results, we found that 2-furyl, 4-MeOC6H4 and 4-MeC6H4
groups could be affected in the first bromination step. The
reasonable explanation should be NBS triggered 2g-i to produce
inseparated bromoarenes (e.g., bromofurans, oxygenated bromo-
benzenes, or benzylic bromides) in converting into complex
mixture. Moreover, when 1.18 g of 1a (10.0 mmol) was treated with
the combination, 2.33 g of 4a was isolated in a 73% yield. This route
can be enlarged to gram scale.
A representative synthetic procedure of skeleton 4 is as follows:
NBS (N-bromosuccinimide, 187 mg, 1.05 mmol) was added to a
solution of 2-phenylpropene (1a, 118 mg, 1.0 mmol) in CH2Cl2
(5 mL) at rt. The reaction mixture was stirred at reflux for 2 h. The
reaction mixture was cooled to 25 ꢀC and a solution of sodium
toluenesulfinates (2a, TolSO2Na, 190 mg, 1.07 mmol) in alcohols
(10 mL) at rt. The reaction mixture was stirred at reflux for 2 h. The
reaction mixture was cooled to 25 ꢀC. Without further purification,
V2O5 (60 mg, 0.3 mmol) and H2O2 (35% in H2O, 0.5 mL) were added
to the resulting mixture at rt. Then, the reaction mixture was stirred
at reflux for 2 h. The residue was diluted with water (10 mL) and the
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4
H.-S. Wang et al. / Tetrahedron xxx (2017) 1e6
mixture was extracted with CH2Cl2 (3 ꢁ 20 mL). The combined
organic layers were washed with brine, dried, filtered and evapo-
rated to afford crude product under reduced pressure. Purification
on silica gel (hexanes/EtOAc ¼ 8/1e4/1) afforded 4.
4.1.7. 2-Methoxy-3-(4-methoxybenzenesulfonyl)-2-phenylpropan-
1-ol (4f)
Yield ¼ 80% (269 mg); Colorless oil; IR (CHCl3): 3608, 2980,
1522, 1151 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C17H21O5S 337.1110,
found 337.1108; 1H NMR (400 MHz, CDCl3):
d
7.73 (d, J ¼ 9.2 Hz, 2H),
7.33e7.24 (m, 5H), 6.91 (d, J ¼ 9.2 Hz, 2H), 4.35 (d, J ¼ 12.0 Hz, 1H),
4.1.2. 2-Methoxy-2-phenyl-3-(toluene-4-sulfonyl)propan-1-ol (4a)
Yield ¼ 82% (262 mg); Colorless solid; mp ¼ 107e109 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3606, 2985,
1521, 1145 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C17H21O4S 321.1161,
4.30 (d, J ¼ 12.0 Hz, 1H), 3.85 (s, 3H), 3.73 (d, J ¼ 2.0 Hz, 2H), 2.98 (s,
3H), 2.82 (br s, 1H); 13C NMR (100 MHz, CDCl3):
d 163.52, 139.48,
132.08, 130.04 (2x), 128.56 (2x), 128.13, 126.39 (2x), 114.14 (2x),
80.15, 64.43, 61.49, 55.62, 50.47.
found 321.1162; 1H NMR (400 MHz, CDCl3):
d
7.69 (d, J ¼ 8.4 Hz, 2H),
7.33e7.24 (m, 7H), 4.36 (d, J ¼ 12.0 Hz, 1H), 4.29 (d, J ¼ 12.0 Hz, 1H),
4.1.8. 2-Methoxy-2-phenyl-3-(toluene-3-sulfonyl)propan-1-ol (4g)
Yield ¼ 82% (262 mg); Colorless solid; mp ¼ 106e108 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3611, 2984,
1525, 1149 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C17H21O4S 321.1161,
3.74 (d, J ¼ 1.6 Hz, 2H), 2.98 (s, 3H), 2.91 (br s, 1H), 2.40 (s, 3H); 13
C
NMR (100 MHz, CDCl3): d 144.40, 139.43, 137.64, 129.53 (2x), 128.51
(2x), 128.06, 127.80 (2x), 126.39 (2x), 80.16, 64.39, 61.26, 50.45,
21.48. Single-crystal X-Ray diagram: crystal of compound 4a was
grown by slow diffusion of EtOAc into a solution of compound 4a in
CH2Cl2 to yield colorless prisms. The compound crystallizes in the
monoclinic crystal system, space group C 2/c, a ¼ 32.603(4) Å,
found 321.1162; 1H NMR (400 MHz, CDCl3):
d 7.62e7.60 (m, 1H),
7.56 (s, 1H), 7.36 (s, 1H), 7.34e7.24 (m, 6H), 4.37 (d, J ¼ 12.0 Hz, 1H),
4.33 (d, J ¼ 11.8 Hz, 1H), 3.78 (d, J ¼ 14.4 Hz, 1H), 3.72 (d, J ¼ 14.4 Hz,
1H), 3.00 (s, 3H), 2.61 (br s, 1H), 2.37 (s, 3H); 13C NMR (100 MHz,
b ¼ 5.7618(6) Å, c ¼ 16.0111(16) Å, V ¼ 3005.1(6) Å3, Z ¼ 8, dcalcd
¼
CDCl3):
d 140.36, 139.24, 139.18, 134.21, 128.84, 128.49 (2x), 128.17,
1.354 g/cm3, F(000) ¼ 1296, 2
q
range 1.250e26.398ꢀ, R indices (all
128.08, 126.44 (2x), 124.85, 80.15, 64.20, 61.25, 50.46, 21.17.
data) R1 ¼ 0.0948, wR2 ¼ 0.2174.
4.1.9. 3-(4-Ethylbenzenesulfonyl)-2-methoxy-2-phenylpropan-1-ol
(4h)
4.1.3. 3-Benzenesulfonyl-2-methoxy-2-phenylpropan-1-ol (4b)
Yield ¼ 80% (245 mg); Colorless solid; mp ¼ 93e95 ꢀC (recrys-
tallized from hexanes and EtOAc); IR (CHCl3): 3611, 2987, 1525,
1144 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C16H19O4S 307.1004, found
Yield ¼ 78% (261 mg); Colorless solid; mp ¼ 100e102 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3612, 2984,
1524, 1143 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C18H23O4S 335.1317,
307.1008; 1H NMR (400 MHz, CDCl3):
d 7.82e7.79 (m, 2H),
found 335.1321; 1H NMR (400 MHz, CDCl3):
d
7.69 (d, J ¼ 8.4 Hz,
7.59e7.55 (m, 1H), 7.48e7.44 (m, 2H), 7.33e7.23 (m, 5H), 4.37 (d,
J ¼ 11.6 Hz, 1H), 4.32 (d, J ¼ 12.0 Hz, 1H), 3.80 (d, J ¼ 14.4 Hz, 1H),
3.75 (d, J ¼ 14.4 Hz, 1H), 3.10 (br s, 1H), 2.97 (s, 3H); 13C NMR
2H), 7.31e7.22 (m, 7H), 4.34 (d, J ¼ 11.6 Hz, 1H), 4.30 (d, J ¼ 12.0 Hz,
1H), 3.78 (d, J ¼ 14.4 Hz, 1H), 3.73 (d, J ¼ 14.8 Hz, 1H), 2.97 (s, 3H),
2.82 (br s, 1H), 2.68 (q, J ¼ 7.6 Hz, 2H), 1.23 (t, J ¼ 8.0 Hz, 3H); 13C
(100 MHz, CDCl3): d 140.54, 139.22, 133.39, 128.93 (2x), 128.55 (2x),
NMR (100 MHz, CDCl3): d 150.42, 139.24, 137.70, 128.43 (2x), 128.35
128.18, 127.77 (2x), 126.40 (2x), 80.12, 64.26, 61.20, 50.43.
(2x), 128.02, 127.83 (2x), 126.37 (2x), 80.06, 64.17, 61.06, 50.36,
28.70, 15.02.
4.1.4. 3-Methanesulfonyl-2-methoxy-2-phenylpropan-1-ol (4c)
Yield ¼ 70% (172 mg); Colorless oil; IR (CHCl3): 3613, 2982,1522,
1141 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C11H17O4S 245.0848, found
4.1.10. 3-(4-Isopropylbenzenesulfonyl)-2-methoxy-2-
phenylpropan-1-ol (4i)
Yield ¼ 80% (278 mg); Colorless solid; mp ¼ 107e109 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3608, 2984,
1523, 1147 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C19H25O4S 349.1474,
245.0845; 1H NMR (400 MHz, CDCl3):
d 7.45e7.31 (m, 5H), 4.38 (d,
J ¼ 12.0 Hz, 1H), 4.28 (d, J ¼ 12.4 Hz, 1H), 3.58 (d, J ¼ 15.2 Hz, 1H),
3.51 (d, J ¼ 15.2 Hz, 1H), 3.16 (s, 3H), 2.91 (s, 3H); 13C NMR
found 349.1480; 1H NMR (400 MHz, CDCl3):
d
7.69 (d, J ¼ 8.4 Hz,
(100 MHz, CDCl3):
d 139.56, 128.90 (2x), 128.44, 126.25 (2x), 79.40,
2H), 7.31e7.20 (m, 7H), 4.35 (d, J ¼ 12.0 Hz, 1H), 4.32 (d, J ¼ 12.0 Hz,
1H), 3.79 (d, J ¼ 14.4 Hz, 1H), 3.73 (d, J ¼ 14.4 Hz, 1H), 2.99e2.90 (m,
1H), 2.98 (s, 3H), 2.62 (br s, 1H), 1.23 (d, J ¼ 7.2 Hz, 6H); 13C NMR
63.61, 62.41, 50.87, 43.38.
4.1.5. 3-(Butane-1-sulfonyl)-2-methoxy-2-phenylpropan-1-ol (4d)
Yield ¼ 70% (200 mg); Colorless oil; IR (CHCl3): 3605, 2982,
1522, 1144 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C14H23O4S 287.1317,
(100 MHz, CDCl3):
d 154.96, 139.18, 137.71, 128.44 (2x), 128.05,
127.85 (2x), 126.99 (2x), 126.39 (2x), 80.04, 64.09, 61.06, 50.36,
34.06, 23.49, 23.46.
found 287.1312; 1H NMR (400 MHz, CDCl3):
d 7.45e7.30 (m, 5H),
4.40 (d, J ¼ 12.4 Hz,1H), 4.27 (d, J ¼ 12.0 Hz,1H), 3.60 (br s, 1H), 3.54
(d, J ¼ 15.2 Hz, 1H), 3.42 (d, J ¼ 15.2 Hz, 1H), 3.15 (s, 3H), 3.07e2.90
(m, 2H), 1.81e1.73 (m, 2H), 1.45e1.35 (m, 2H), 0.92 (t, J ¼ 7.2 Hz,
4.1.11. 3-(4-Butylbenzenesulfonyl)-2-methoxy-2-phenylpropan-1-
ol (4j)
Yield ¼ 84% (304 mg); Colorless solid; mp ¼ 90e92 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3611, 2988,
1526, 1139 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C20H27O4S 363.1630,
3H); 13C NMR (100 MHz, CDCl3):
d 139.80, 128.82 (2x), 128.35,
126.21 (2x), 79.48, 63.55, 60.48, 54.92, 50.82, 23.77, 21.53, 13.40.
found 363.1633; 1H NMR (400 MHz, CDCl3):
d
7.65 (d, J ¼ 8.4 Hz,
4.1.6. 3-(4-Fluorobenzenesulfonyl)-2-methoxy-2-phenylpropan-1-
ol (4e)
2H), 7.28e7.19 (m, 7H), 4.31 (d, J ¼ 12.0 Hz, 1H), 4.29 (d, J ¼ 12.0 Hz,
1H), 3.74 (d, J ¼ 14.4 Hz, 1H), 3.69 (d, J ¼ 14.4 Hz, 1H), 2.93 (s, 3H),
2.82 (br s, 1H), 2.61 (t, J ¼ 8.0 Hz, 2H), 1.58e1.50 (m, 2H), 1.33e1.26
Yield ¼ 83% (269 mg); Colorless solid; mp ¼ 125e127 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3606, 2979,
1521, 1143 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C16H18FO4S 325.0910,
(m, 2H), 0.88 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d 149.19,
139.30, 137.70, 128.89 (2x), 128.45 (2x), 128.04, 127.77 (2x), 126.39
(2x), 80.09, 64.24, 61.10, 50.37, 35.40, 33.01, 22.06, 13.70.
found 325.0911; 1H NMR (400 MHz, CDCl3):
d 7.80e7.76 (m, 2H),
7.29e7.24 (m, 5H), 7.13e7.08 (m, 2H), 4.32 (s, 2H), 3.81 (d,
J ¼ 14.4 Hz, 1H), 3.75 (d, J ¼ 14.8 Hz, 1H), 2.97 (s, 3H), 2.63 (br s, 1H);
4.1.12. 3-(4-tert-Butylbenzenesulfonyl)-2-methoxy-2-
phenylpropan-1-ol (4k)
13C NMR (100 MHz, CDCl3):
d
165.47 (d, J ¼ 254.7 Hz),138.95,136.60
(d, J ¼ 3.0 Hz), 130.73 (d, J ¼ 9.1 Hz, 2x), 128.58 (2x), 128.24, 126.42
Yield ¼ 86% (311 mg); Colorless solid; mp ¼ 115e117 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3615, 2985,
(2x), 116.12 (d, J ¼ 22.8 Hz, 2x), 79.90, 63.88, 61.43, 50.36.
Please cite this article in press as: Wang H-S, et al., Sulfonylative alkoxyhydroxylation of 2-arylpropenes, Tetrahedron (2017), https://doi.org/
10.1016/j.tet.2017.09.047

H.-S. Wang et al. / Tetrahedron xxx (2017) 1e6
5
1529, 1143 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C20H27O4S 363.1630,
389.1034, found 389.1035; 1H NMR (400 MHz, CDCl3):
d
7.62 (d,
found 363.1635; 1H NMR (400 MHz, CDCl3):
d
7.70 (d, J ¼ 8.8 Hz,
J ¼ 8.4 Hz, 2H), 7.52 (d, J ¼ 8.4 Hz, 2H), 7.44 (d, J ¼ 8.4 Hz, 2H), 7.24
(d, J ¼ 8.0 Hz, 2H), 4.36 (s, 2H), 3.77 (d, J ¼ 14.8 Hz, 1H), 3.70 (d,
J ¼ 14.4 Hz, 1H), 3.03 (s, 3H), 2.84 (br s, 1H), 2.41 (s, 3H); 13C NMR
2H), 7.45 (d, J ¼ 8.4 Hz, 2H), 7.32e7.23 (m, 5H), 4.37 (d, J ¼ 12.4 Hz,
1H), 4.34 (d, J ¼ 12.0 Hz, 1H), 3.78 (d, J ¼ 14.8 Hz, 1H), 3.72 (d,
J ¼ 14.8 Hz, 1H), 2.99 (s, 3H), 2.61 (br s, 1H), 1.32 (s, 9H); 13C NMR
(100 MHz, CDCl3):
d
144.76, 143.49, 137.25, 130.34 (d, J ¼ 31.9 Hz),
(100 MHz, CDCl3):
d
157.32, 139.29, 137.42, 128.52 (2x), 128.14,
129.68 (2x), 127.80 (2x), 127.08 (d, J ¼ 262.3 Hz), 127.05 (2x), 125.47
127.62 (2x), 126.46 (2x), 125.96 (2x), 80.15, 64.20, 61.27, 50.44,
35.12, 30.96 (3x).
(q, J ¼ 3.8 Hz, 2x), 79.84, 63.86, 61.21, 50.64, 21.50.
4.1.18. 2-(4-Chlorophenyl)-2-methoxy-3-(toluene-4-sulfonyl)
propan-1-ol (4q)
4.1.13. 3-(4-Bromobenzenesulfonyl)-2-methoxy-2-phenylpropan-
1-ol (4l)
Yield ¼ 78% (276 mg); Colorless solid; mp ¼ 103e105 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3612, 2989,
Yield ¼ 80% (307 mg); Colorless solid; mp ¼ 126e128 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3610, 2985,
1535, 1151 cmꢂ1
;
HRMS (ESI, Mþþ1) calcd for C17H20ClO4S
1530, 1148 cmꢂ1
;
HRMS (ESI, Mþþ1) calcd for C16H18BrO4S
355.0771, found 355.0776; 1H NMR (400 MHz, CDCl3):
d 7.62 (d,
385.0109, found 385.0115; 1H NMR (400 MHz, CDCl3):
d
7.61 (d,
J ¼ 8.4 Hz, 2H), 7.24 (d, J ¼ 8.0 Hz, 2H), 7.22 (br s, 4H), 4.29 (s, 2H),
J ¼ 8.8 Hz, 2H), 7.56 (d, J ¼ 8.8 Hz, 2H), 7.30e7.25 (m, 5H), 4.32 (br s,
3.75 (d, J ¼ 14.8 Hz, 1H), 3.67 (d, J ¼ 14.4 Hz, 1H), 2.97 (s, 3H), 2.91
2H), 3.80 (d, J ¼ 14.8 Hz, 1H), 3.74 (d, J ¼ 14.4 Hz, 1H), 2.97 (s, 3H),
(br s, 1H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3):
d 144.57, 137.71,
2.86 (br s, 1H); 13C NMR (100 MHz, CDCl3):
d
139.46, 138.80, 132.12
137.30, 134.10, 129.56 (2x), 128.60 (2x), 128.00 (2x), 127.73 (2x),
79.61, 63.67, 61.03, 50.35, 21.50.
(2x), 132.10, 129.38 (2x), 128.59 (2x), 128.24, 126.42 (2x), 79.84,
63.76, 61.36, 50.38.
4.1.19. 2-(3,4-Dichlorophenyl)-2-methoxy-3-(toluene-4-sulfonyl)
propan-1-ol (4r)
4.1.14. 3-(4-Chlorobenzenesulfonyl)-2-methoxy-2-phenylpropan-1-
ol (4m)
Yield ¼ 72% (279 mg); Colorless solid; mp ¼ 128e130 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3612, 2985,
1532, 1151 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C17H19Cl2O4S
Yield ¼ 81% (275 mg); Colorless solid; mp ¼ 122e124 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3605, 2983,
1528, 1152 cmꢂ1
;
HRMS (ESI, Mþþ1) calcd for C16H18ClO4S
389.0381, found 389.0383; 1H NMR (400 MHz, CDCl3):
d 7.58 (d,
341.0614, found 341.0618; 1H NMR (400 MHz, CDCl3):
d
7.70 (d,
J ¼ 8.0 Hz, 2H), 7.33e7.31 (m, 2H), 7.23 (d, J ¼ 8.4 Hz, 2H), 7.18e7.11
(m, 2H), 4.28 (d, J ¼ 12.0 Hz, 1H), 4.26 (d, J ¼ 12.0 Hz, 1H), 3.75 (d,
J ¼ 14.8 Hz, 1H), 3.65 (d, J ¼ 14.8 Hz, 1H), 3.02 (s, 3H), 2.42 (s, 3H);
J ¼ 8.8 Hz, 2H), 7.41 (d, J ¼ 8.8 Hz, 2H), 7.28 (br s, 5H), 4.33 (s, 2H),
3.80 (d, J ¼ 14.8 Hz, 1H), 3.74 (d, J ¼ 14.8 Hz, 1H), 2.98 (s, 3H), 2.80
(br s, 1H); 13C NMR (100 MHz, CDCl3):
d
140.08, 139.01, 138.92,
13C NMR (100 MHz, CDCl3):
d 144.81, 139.50, 136.98, 132.76, 132.41,
129.37 (2x), 129.18 (2x), 128.65 (2x), 128.30, 126.44 (2x), 79.92,
63.91, 61.56, 50.43.
130.40, 129.59 (2x), 128.87, 127.69 (2x), 126.02, 79.21, 63.30, 60.91,
50.49, 21.54.
4.1.15. 2-(4-Nitrophenyl)-2-(toluene-4-sulfonylmethyl)oxirane (4n-
1)
4.1.20. 2-Ethoxy-2-phenyl-3-(toluene-4-sulfonyl)propan-1-ol (4s)
Yield ¼ 80% (267 mg); Colorless oil; IR (CHCl3): 3603, 2982,
1525, 1147 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C18H23O4S 335.1317,
Yield ¼ 34% (113 mg); Colorless solid; mp ¼ 114e116 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3113, 3092,
2933, 1512, 1315, 1023, 892 cmꢂ1; HRMS (ESI, Mþþ1) calcd for
found 335.1318; 1H NMR (400 MHz, CDCl3):
d
7.71 (d, J ¼ 8.4 Hz,
2H), 7.35e7.25 (m, 7H), 4.35 (d, J ¼ 12.0 Hz, 1H), 4.31 (d, J ¼ 12.0 Hz,
1H), 3.77 (d, J ¼ 14.8 Hz, 1H), 3.73 (d, J ¼ 14.8 Hz, 1H), 3.24e3.17 (m,
1H), 3.10e3.02 (m, 1H), 2.98 (br s, 1H), 2.42 (s, 3H), 0.94 (t,
C
16H16NO5S 334.0749, found 334.0752; 1H NMR (400 MHz, CDCl3):
d
8.15 (d, J ¼ 8.8 Hz, 2H), 7.67 (d, J ¼ 8.4 Hz, 2H), 7.56 (d, J ¼ 8.8 Hz,
2H), 7.29 (d, J ¼ 8.4 Hz, 2H), 3.90 (d, J ¼ 14.8 Hz, 1H), 3.68 (d,
J ¼ 14.8 Hz, 1H), 3.28 (d, J ¼ 4.8 Hz, 1H), 2.82 (d, J ¼ 4.8 Hz, 1H), 2.43
J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d 144.35, 140.27, 137.80,
129.49 (2x), 128.53 (2x), 128.02, 127.95 (2x), 126.22 (2x), 79.76,
64.80, 62.10, 57.99, 21.52, 15.08.
(s, 3H); 13C NMR (100 MHz, CDCl3):
d 147.61, 145.37, 144.41, 136.67,
129.88 (2x), 128.09 (2x),127.19 (2x), 123.57 (2x), 61.90, 54.93, 54.79,
21.60.
4.1.21. 2-n-Butoxy-2-phenyl-3-(toluene-4-sulfonyl)propan-1-ol
(4t)
4.1.16. 2-(3-Fluorophenyl)-2-methoxy-3-(toluene-4-sulfonyl)
propan-1-ol (4o)
Yield ¼ 72% (261 mg); Colorless oil; IR (CHCl3): 3619, 2993,1530,
1149 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C20H27O4S 363.1630, found
Yield ¼ 62% (210 mg); Colorless solid; mp ¼ 90e92 ꢀC (recrys-
tallized from hexanes and EtOAc); IR (CHCl3): 3628, 2986, 1530,
1149 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C17H20FO4S 339.1066,
363.1634; 1H NMR (400 MHz, CDCl3):
d
7.67 (d, J ¼ 8.4 Hz, 2H),
7.31e7.20 (m, 7H), 4.32 (d, J ¼ 12.0 Hz, 1H), 4.28 (d, J ¼ 12.4 Hz, 1H),
3.73 (d, J ¼ 14.4 Hz, 1H), 3.68 (d, J ¼ 14.8 Hz, 1H), 3.10e3.05 (m, 1H),
3.00 (br s, 1H), 2.95e2.90 (m, 1H), 2.38 (s, 3H), 1.26e1.18 (m, 2H),
1.17e1.04 (m, 2H), 0.75 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz,
found 339.1068; 1H NMR (400 MHz, CDCl3):
d
7.69 (d, J ¼ 8.0 Hz,
2H), 7.29e7.24 (m, 3H), 7.14e7.10 (m, 1H), 7.03 (dt, J ¼ 2.4, 10.4 Hz,
1H), 6.94 (dt, J ¼ 2.4, 8.0 Hz, 1H), 4.34 (d, J ¼ 12.0 Hz, 1H), 4.26 (d,
J ¼ 12.0 Hz, 1H), 3.70 (d, J ¼ 1.6 Hz, 2H), 3.00 (s, 3H), 2.70 (br s, 1H),
CDCl3):
d 144.29, 140.19, 137.84, 129.49 (2x), 128.49 (2x), 128.01,
127.90 (2x), 126.33 (2x), 79.48, 64.60, 62.31, 62.14, 31.84, 21.50,
19.04, 13.84.
2.41 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
162.90 (d, J ¼ 244.9 Hz),
144.66, 142.41 (d, J ¼ 6.8 Hz), 137.42, 130.12 (d, J ¼ 7.6 Hz), 129.62
(2x),127.83 (2x), 122.08 (d, J ¼ 2.3 Hz),115.08 (d, J ¼ 20.5 Hz),113.73
(d, J ¼ 22.7 Hz), 79.88, 64.24, 61.18, 50.60, 21.51.
4.1.22. 2-Isopropoxy-2-phenyl-3-(toluene-4-sulfonyl)propan-1-ol
(4u)
Yield ¼ 58% (202 mg); Colorless solid; mp ¼ 110e112 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3608, 2988,
1528, 1143 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C19H25O4S 349.1474,
4.1.17. 2-Methoxy-3-(toluene-4-sulfonyl)-2-(4-
trifluoromethylphenyl)propan-1-ol (4p)
Yield ¼ 60% (233 mg); Colorless solid; mp ¼ 131e133 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3621, 2994,
found 349.1478; 1H NMR (400 MHz, CDCl3):
2H), 7.40e7.38 (m, 2H), 7.27e7.23 (m, 5H), 4.51e4.47 (m, 1H), 4.36
(d, J ¼ 12.0 Hz, 1H), 3.84 (d, J ¼ 14.8 Hz, 1H), 3.65 (d, J ¼ 14.8 Hz, 1H),
d
7.65 (d, J ¼ 8.4 Hz,
1537, 1155 cmꢂ1
;
HRMS (ESI, Mþþ1) calcd for C18H20F3O4S
Please cite this article in press as: Wang H-S, et al., Sulfonylative alkoxyhydroxylation of 2-arylpropenes, Tetrahedron (2017), https://doi.org/
10.1016/j.tet.2017.09.047

6
H.-S. Wang et al. / Tetrahedron xxx (2017) 1e6
(c) Chang M-Y, Lin C-H, Chen Y-L. Tetrahedron Lett. 2010;51:1430.
3. Aertker K, Rama RJ, Opalach J, Muniz K. PhI(OAc)2-mediated vicinal difunc-
tionalizations. see Adv Synth Catal. 2017;359:1290.
4. Li J, Li Z, Zhang X, Xu B, Shi Y. (DHQD)2PHAL-mediated vicinal bromohydrox-
ylation. see Org Chem Front. 2017;4:1084.
5. For vicinal difunctionalization of 2-arylpropenes, for t-BuO2H, see: (a) Li X,
Xu X, Zhou C. Chem Commun. 2012;48:12240. For I2, see;
(b) Sawangphon T, Katrun P, Chaisiwamongkhol K, et al. Synth Commun.
2013;43:1642. For NaBO3, see;
(c) Gupton JT, Duranceau SJ, Miller JF, Kosiba ML. Synth Commun. 1988;18:937.
For mCPBA, see;
3.40e3.34 (m, 1H), 3.00 (br s, 1H), 2.41 (s, 3H), 0.97 (d, J ¼ 6.4 Hz,
3H), 0.78 (d, J ¼ 6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d 144.20,
139.96, 137.81, 129.43 (2x), 128.21 (2x), 128.18, 127.92 (2x), 127.03
(2x), 80.16, 65.99, 63.71, 63.38, 24.45, 24.12, 21.52.
4.1.23. 2-Phenyl-3-(toluene-4-sulfonyl)propane-1,2-diol (4v-1)
Yield ¼ 74% (226 mg); Colorless solid; mp ¼ 138e140 ꢀC
(recrystallized from hexanes and EtOAc); IR (CHCl3): 3612, 3498,
2976, 1523, 1138, 978 cmꢂ1; HRMS (ESI, Mþþ1) calcd for C16H19O4S
(d) Monk KA, Duncan NC, Bauch EA, Garner CM. Tetrahedron. 2008;64:8605. For
other, see;
307.1004, found 307.1007; 1H NMR (400 MHz, CDCl3):
d 7.42 (d,
(e) O'Neill PM, Mukhtar A, Ward SA, et al. Org Lett. 2004;6:3035.
6. For recent synthetic applications of sodium sulfinates by the authors, see: (a)
Chang M-Y, Chen Y-C, Chan C-K. Tetrahedron. 2014;70:8908;
(b) Chang M-Y, Cheng Y-J, Lu Y-J. Org Lett. 2014;16:6252;
(c) Chang M-Y, Lu Y-J, Cheng Y-C. Tetrahedron. 2015;71:1192;
(d) Chang M-Y, Cheng Y-J. Org Lett. 2016;18:608.
J ¼ 8.0 Hz, 2H), 7.25e7.23 (m, 2H), 7.18e7.14 (m, 3H), 7.11 (d,
J ¼ 8.4 Hz, 2H), 4.91 (s, 1H), 3.95 (d, J ¼ 14.8 Hz, 1H), 3.73 (d,
J ¼ 14.8 Hz, 1H), 3.64 (s, 2H), 2.64 (br s, 1H), 2.37 (s, 3H); 13C NMR
(100 MHz, CDCl3):
d 144.58, 140.34, 136.92, 129.62, 128.27 (2x),
127.55 (4x), 125.14 (2x), 75.73, 70.40, 61.76, 21.52.
7. For synthesis of allylic sulfones, see: (a) Jiang L, Lei Q, Huang X, Cui H-L, Zhou X,
Chen Y-C. Chem Eur J. 2011;17:9489;
(b) Gembus V, Postikova S, Levacher V, Briere J-F. J Org Chem. 2011;76:4194;
(c) Diez D, Garcia P, Marcos IS, et al. Org Lett. 2003;5:3687;
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Acknowledgments
The authors would like to thank the Ministry of Science and
Technology of the Republic of China for its financial support (MOST
106-2628-M-037-001-MY3).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.tet.2017.09.047.
(c) Espenson JH. Chem Commun. 1999:479.
11. For MoO5, see Bonchio M, Carofiglio T, Di Furia F, Fornasier R. J Org Chem.
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Please cite this article in press as: Wang H-S, et al., Sulfonylative alkoxyhydroxylation of 2-arylpropenes, Tetrahedron (2017), https://doi.org/
10.1016/j.tet.2017.09.047