Iodine-Triggered Aerobic Oxysulfonylation of Styrenes

Article abstract of DOI:10.1002/adsc.201700772

An iodine-triggered dioxygen activation in oxysulfonylation reactions of unactivated olefins using sulfonyl hydrazides and iodine as catalyst is reported here. In one pot, near quantitative syntheses of β-hydroxysulfones were achieved at 70 °C, within 7 h, in acetonitrile and under aerobic conditions. A plausible mechanism is established by radical trapping and ¹⁸O labelling experiments for the operationally simple, efficient and economically viable transformation. The direct activation of aerial oxygen under metal-free and mild conditions is proposed for the oxysulfonylation of olefins. (Figure presented.).

Full text of DOI:10.1002/adsc.201700772

Title: Iodine Triggered Aerobic Oxysulfonylation of Styrenes
Authors: Khokan Chowdhuri, Tapas Achar, and Prasenjit Mal
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iodine Triggered Aerobic Oxysulfonylation of Styrenes
Khokan Choudhuri,a Tapas Kumar Achara and Prasenjit Mala*
a
School of Chemical Sciences, National Institute of Science Education and Research (NISER), HBNI, Bhubaneswar,
PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India, E-mail: pmal@niser.ac.in
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. An iodine triggered dioxygen activation in
oxysulfonylation reaction of unactivated olefins using
sulfonyl hydrazides and iodine catalyst is reported here. In
one pot, near quantitative synthesis of β-hydroxysulfones
were achieved at 70 ºC, within 7 h, in acetonitrile and under
aerobic condition. A plausible mechanism is established by
radical trapping and 18O labelling experiments for the
operationally simple, efficient and economically viable
transformation. The direct activation of aerial oxygen under
metal free and mild condition is anticipated for the
oxysulfonylation of olefins.
Keywords: Dioxygen Activation; Iodine Triggered; Metal
Free; Oxysulfonylation; Sulfonyl Hydrazides
conditions, among others.[14] In this regard,
developments of efficient, direct and environmentally
benign synthetic methods are highly desirable.[15]
Towards synthesis of organosulfur compounds
oxidative cross-coupling reactions between different
nucleophiles in the presence of appropriate oxidant
have gained popularity.[10a, 16]
Introduction
Activation of aerial dioxygen is a popular research
topic in the areas of bioinorganic chemistry,[1]
synthetic chemistry,[2] enzymology,[3] etc.[4] The
terminal oxidant dioxygen is also considered to be an
ideal oxygen source for the functionalization of
organic molecules towards development of green and
sustainable protocols in organic synthesis. The
dioxygen activation process is mainly explored using
transition metals Pd,[5] Ni,[6] Fe,[7] Cu,[8] etc.[9]
Moreover, transition metal peroxide mediated radical
reactions generally lead to undesired products and
have limited scopes in pharmaceuticals and material
industry.[10] Therefore, under metal-free condition the
use of dioxygen is undoubtedly an encouraging route
Results and Discussion
In continuation of our research interest in iodine
reagent mediated reactions,[17] herein we report a
metal-free approach via iodine triggered[18] and an
expedient dioxygen activation method for an
oxysulfonylation reaction[18a] towards synthesis of β-
hydroxysulfones from styrenes (Figure 1a).[19] The
aerial oxygen was activated for the introduction of -
OH group at benzylic position and near quantitative
synthesis of β-hydroxysulfones was achieved from
styrenes and sulfonyl hydrazides using pyridine
additive (10 mol %) and iodine (10 mol %) as
catalyst.[20] Sulfonyl hydrazides are well known aryl
source through the cleavage of C–S bonds[15c, 18a, 21]
but limited for direct sulfonylation.[7a, 22] Eco-friendly
molecular iodine triggered reactions are popular but
to
widen
the
potential
applicability
in
pharmaceuticals and synthetic laboratories, however,
very few reports are available till date with regard to
such potentiality.[3b]
Sulfonyl group is one of the important precursors
in natural and non-natural products.[11] In particular,
β-hydroxysulfones are present as a basic scaffold in
numerous biologically active molecules, and provide
useful building blocks in organic synthesis.[10a, 12] β-
Hydroxysulfones are prepared via chemical or bio-
reduction of β-keto-sulfones, nucleophilic ring
opening of epoxides with sulfinate, or via
hydroxylation of α,β-unsaturated sulfones.[13] These
efficient and flexible transformations have significant
limitations such as involvement of multistep synthetic
procedure for synthesis of starting materials,
production of unwanted byproducts, harsh reaction
inadequate
examples
are
known
towards
The iodine
23]
functionalization aromatic olefins.[18,
catalyzed example of oxysulfonylation from sulfonyl
hydrazide and olefins is depicted in Figure 1b.[21b] In
Figure 1c, pyridine catalyzed dioxygen activation
from sulfinic acid is presented.[13c]
1
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
Figure 1. β-Hydroxysulfone synthesis by dioxygen
activation. a) Our approach based on iodine as catalyst. b)
Yang et al., described the oxysulfonylation using iodine
catalyst.[21b] c) Lei’s oxysulfonylation method from sulfinic
acid via pyridine catalyzed.[13c]
Table 1. Optimization Methoda
Entry Catalyst
(equiv)
Additive
(equiv)
---
Pyridine (0.1)
Pyridine (0.1)
Pyridine (0.1)
Pyridine (0.1)
Pyridine (0.1)
Solvent
3aa
(%)b
65c
85
1
2
3
4
5
6
I2 (0.2)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
MeCN
EtOH
DCE
DMSO
H2O
82
38
--d
MeCN- 96
H2O
7
8
9
I2 (0.1)
I2 (0.05)
--
Pyridine (0.1)
Pyridine (0.05) MeCN
Pyridine (0.1) MeCN
Pyridine (0.05) MeCN
Pyridine (0.15) MeCN
2,6-Lutidine
2,4,6-Collidine MeCN
Pyrrole (0.1)
Et3N (0.1)
DMAP (0.1)
Na2CO3 (1)
K2CO3 (1)
MeCN
99
40
--d
83
74
30
49
10
19
39
--d
--d
--d
--d
--d
59e
63f
10
11
12
13
14
15
16
17
18
19
20
21
22
23
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
TBAI
Figure 2. Scope of Oxysulfonylation of Olefins.
MeCN
The reaction condition was optimized (Table 1) with
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
the
substrates
styrene
(1a)
and
(2a).
4-
β-
methylbenzenesulfonyl
hydrazide
Hydroxysulfone 3aa was obtained in excellent yield
(> 99%) using iodine catalyst (10 mol %) and
pyridine-additive (10 mol %) in acetonitrile at 70 ºC
under aerobic condition (Table 1, entry 7). No
additional source of oxygen was supplied for this
reaction and sulfonyl radicals were possibly
generated from sulfonyl hydrazides. Besides, when
the reaction was performed under N2 atmosphere no
desired product was detected which indicated that the
source of hydroxyl group possibly from aerial oxygen.
A wide range of solvents were screened and it was
found that acetonitrile works best for this reaction
(Table 1, entries 2-7). The solvent acetonitrile is
known to dissolve ~8.1 mM oxygen at 25 ºC which is
KHPO4 (1)
Pyridine (0.1)
Pyridine (0.1)
Pyridine (0.1)
Pyridine (0.1)
TBAB
I2 (0.1)
I2 (0.1)
aCondition: 1a (0.26 mmol), 2a (0.39 mmol), solvent (1.5
mL), 70 ºC, 7 h. bAfter column chromatography. c24 h. dNo
oxysulfonylation product. e25 ºC, 24 h. f50 ºC.
2
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
significantly higher than commonly used solvents.[24]
The best results were obtained at 70 ºC and at lower
temperature the yield of the product 3aa was
sufficiently lowered (Table 1, entries 22-23).
Compared to pyridine, other bases like 2,6-lutidine,
2,4,6-collidine, pyrrole, Et3N, DMAP, Na2CO3,
K2CO3, KHPO4 were found to be less efficient (Table
1, entries 12-19). Similarly, I2 was the superior as
catalyst (Table 1, entries 20-21) compared to TBAI,
TBAB, etc. Interestingly, when pyridine was solely
used as a catalyst no product formation was detected
(Table 1, entry 9).
hydroxysulfones were obtained for the styrenes with
electron withdrawing groups like cyano (3kc), nitro
(3lc) and methoxy (3na). However, methoxy
substituted styrene (1m) led to the corresponding β-
hydroxysulfone (3mc) in excellent yield (96%) and
no oxysulfonylation product could be isolated from
the reaction with 4-amino styrene. In gram scale
(9.58 mmol) the product 3aa was obtained in 84 %
yield (2.22 g).
Control experiments were performed to
understand the mechanism of the iodine catalyzed[20b,
25]
oxysulfonylation reaction (Figures 3-4). Under
aerobic condition and at 1 atm, near quantitative 3aa
was obtained from styrene 1a and tosyl hydrazide 2a.
In an oxidative environment, formation of sulfonyl
radical from sulfonyl hydrazides via diazene
intermediate is known.[26] Involvement of radical
pathway was confirmed by TEMPO (2,2,6,6-
tetramethyl-1-piperidinyloxy)
radical
trapping
experiment (Figure 3a). Under optimized condition,
also in dry acetonitrile and in absence of olefins,
sulfonyl hydrazides led to sulfonothioic acid in low
yield (14%) (Supporting Information). As shown in
Figure 3c, when 1a was treated with sulfonothioic
acid derivative 4, no 3aa could be obtained which
ruled out the possibility for the formation of sulfonyl
radical via sulfonothioic acid. Furthermore, there was
no deuterium incorporation and a failure of the
reaction under nitrogen atmosphere (Figure 3b) also
supports the hypothesis of aerial dioxygen activation.
The reaction was completely failed in presence of any
aliphatic olefins like allyl benzenes and 1-hexene
(Figures 3e,f). Moreover, under standard condition
and in absence of sulfonyl hydrazide no reaction was
observed with styrene (Figure 3d).
Figure 3. Control Experiments.
Based on our preliminary findings, the substrate
scope for oxysulfonylation between various olefins
and sulfonyl hydrazides was explored (Figure 2).
Using 10 mol % of iodine as catalyst under aerobic
condition, a range of olefins reacted with sulfonyl
hydrazides to afford a variety of β-hydroxysulfones in
good to excellent yields (> 99%). This method was
compatible with aromatic ring having electron-
donating and electron-withdrawing groups. Similarly,
-Cl and -Br substituents on styrene have also worked
well. Bulky substrates, 2-methylstyrene and 2-
chlorostyrene efficiently reacted with sulfonyl
hydrazides and yielded 3ga (72%) and 3ib (61%),
respectively. Notably, α-methylstyrene has also
afforded sterically congested β-hydroxysulfone in
very good yield (3da, 3dc). The reaction was found
to be efficient with both aromatic as well as aliphatic
sulfonyl hydrazides. Relatively poor yields of β-
Figure 4. 18O Isotope Labelling Experiments.
Shown in Figure 4, 18O labelling experiments[13c] also
helped to understand the origin of the hydroxyl
oxygen of β-hydroxysulfone. When 1a and 2a were
treated in the presence of aerobic condition in
MeCN:H2O18 (2:1), the reaction failed to produce any
18O incorporated β-hydroxysulfone, instead 16O
incorporated 3aa was isolated in 96% yield.
Nevertheless, in presence of 18O2, reaction of 1a and
2a afforded 77% of 18O incorporated 3aa (Supporting
Information). So, the role of aerial oxygen was
confirmed for the oxysulfonylation reaction.
3
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
Conclusion
In conclusion, we have developed an operationally
simple and efficient method of aerial dioxygen
activation for oxysulfonylation reaction towards
synthesis of regioselective β-hydroxysulfones from
non-prefunctionalized olefins and sulfonyl hydrazides.
Using a simple and readily available metal-free
reagents like 10 mol % iodine catalyst and pyridine
additive (10 mol %), successful construction of new
C–O and C–S bond in one-pot were achieved via an
intermolecular reaction. We anticipate that this
oxysulfonylation approach via organic pathway and
direct aerial dioxygen activation might offer an
access to several organosulfur compounds in the
synthesis of functionalized materials, complex
molecules and pharmaceuticals.
Figure 5. Plausible Mechanism.
Experimental Section
Instrumentation and Chemicals
A plausible mechanism for oxysulfonylation of
olefins (Figure 5) via radical pathway was
rationalized[27] from control experiments. Sulfonyl
hydrazides reacted with iodine to give diazene I,
which could further be oxidized to sulfonyl radical
III by triplet dioxygen. Following, sulfonyl radical
(III) might reacted with the olefins 1a to produce
stable benzylic radical IV. The stability of radical IV
was important and essential requirement for the
reaction. It has been found that allyl benzene which
generally produce less stable radical could not led to
the formation of any oxysulfonylated product (Figure
3d). Further, the benzylic radical IV possibly trapped
the dioxygen dissolved in acetonitrile to produce
alkylhydroperoxy radical intermediate V.[28] And then,
the intermediate V led to VI by homolytic cleavage
of peroxy linkage by influence of IV.[28a] The
intermediate VI afforded anionic intermediate VII by
single-electron transfer (SET) from iodide and
concomitant proton transfer (PT) from PyH+ and
Styrene were purchased from commercial source used
without further purification. Tosyl hydrazines were
prepared according to the standard procedure.[31] All the
reactions were done under open atmosphere. Column
chromatographic purification of the compounds were done
using silica gel (mess 230-400) and hexane/ethyl acetate as
1
eluent. H and 13C NMR spectra were recorded on a 400
MHz and/or 700 MHz instruments at 25 °C. The chemical
shift (δ, ppm) values were reported with respect to residual
1
chloroform (7.26 for H and 77.16 ppm for 13C). High
resolution mass spectroscopy (HR-ESIMS) was recorded
on ESI-TOF (Time-of-flight) mass spectroscopy. Infrared
spectra were recorded in wave number (cm-1). Melting
points of the compound were determined using digital
melting point apparatus and uncorrected.
Preparation of arylsulfonyl hydrazides.[31] In a round
bottom flask (250 mL) charged with p-tolylsulfonyl
chloride (26.2 mmol) in THF (15 mL). Then hydrazine
mono hydrates (3.37 mL as 80% in water, 55 mmol) were
added drop wise to the solution. Following, the reaction
mixture were stirred at 0 ºC for 30 min. After that the
mixture was concentrated under vacuum and diluted with
ethyl acetate. The solution was washed with water and
dried over anhyd sodium sulphate. Solvents were removed
under reduced pressure and followed by recrystallization
from ethanol to obtain pure sulfonyl hydrazide.
further produced desired β-hydroxysulfone 3ab. In
29]
this reaction amphoteric pyridine[2a,
could play
another important role by stopping the formation of
sulfonothioic acid from sulfonyl hydrazide. This is
because pyridine might have accepted the proton
from hydroiodic acid (HI) and generated iodide anion
which stopped to generate -SPh radical from diazene
(I). It was also confirmed that sulfonothioic acid
derivative 4 with styrene did not results in 3aa. In
parallel, formation of 65% of 3aa (entry 1, Table 1)
in absence of pyridine indicated that the generated
sulfonyl radical might have rapidly reacted with
olefins and led the stable benzyl radical for follow up
reactions. The stability of the benzyl radical was
possibly essential for the reaction because no product
could be detected with aliphatic olefins (Figure 3f).
These aliphatic olefins were expected to create
unstable radicals after reaction with sulfonyl radicals.
Also, no reaction in absence of sulfonyl hydrazide
(Figure 3d) indicated for the involvement of the
sulfonyl radical during the reaction.[7a, 30]
4-Methylbenzenesulfonohydrazide. 1H NMR (400 MHz,
CDCl3) δ 7.79 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H),
5.74 (br s, 1H), 3.38 (br s, 2H), 2.45 (s, 3H).
4-(tButyl)benzenesulfonohydrazide. H NMR (400 MHz,
1
CDCl3) δ 7.85-7.82 (m, 2H), 7.57-7.54 (m, 2H), 5.99 (br s,
1H), 3.63 (br s, 2H), 1.34 (s, 9H).
Benzenesulfonohydrazide. 1H NMR (400 MHz, CDCl3) δ
7.92 (d, J = 7.6 Hz, 2H), 7.65 (t, J = 7.2 Hz, 1H), 7.57 (t, J
= 7.2 Hz, 2H), 5.76 (br s, 1H), 3.62 (br s, 2H).
1
Butane-1-sulfonohydrazide. H NMR (400 MHz, CDCl3)
δ 5.84 (br s, 1H), 3.71 (br s, 2H), 3.12-3.08 (m, 2H), 1.82-
1.74 (m, 2H), 1.46 (dd, J = 14.8, 7.6 Hz, 2H), 0.94 (t, J =
7.2 Hz, 3H).
General procedure for the preparation of Sulfone.
Styrene (60 mg, 0.52 mmol), p-toluenesulfonyl hydrazide
(146 mg, 0.78 mmol) and pyridine (4.5 μL, 0.052 mmol)
were placed in an oven-dried seal tube. Then acetonitrile
4
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
(3.0 mL) and iodine (13.2 mg, 0.052 mmol) were added.
Then the mixture was allowed to stir for 7 h at 70 ºC. After
that the mixture was concentrated under vacuum and
diluted with ethyl acetate. The solution was washed with
water and dried over anhyd sodium sulphate. Resulting
mixtures were purified through column chromatography
using silica gel and n-hexane, ethyl acetate (9:1) solvent
mixture as an eluent to afford the product.
(dd, J = 14.4, 10.0 Hz, 1H), 3.37 (d, J = 14.4 Hz, 1H), 2.47
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 145.4, 141.4, 140.6,
139.8, 136.3, 130.2, 128.9, 128.2, 127.62, 127.60, 127.2,
126.3, 68.4, 64.1, 21.8; IR (KBr) ῡ 3475, 3031, 2995, 2155,
1639, 1598, 1487, 1402, 1288, 1137, 1087, 844; HRMS
(ESI-TOF) calcd for C21H20O3S (M + Na)+ 375.1025,
found 375.1022.
1-(4-Bromophenyl)-2-tosylethanol (3fa).[13c] Rf = 0.35
Gram scale synthesis. Styrene (1.1 mL, 9.58 mmol), p-
toluenesulfonyl hydrazide (2.68 g, 14.37 mmol) and
pyridine (0.077 mL, 0.96 mmol) were placed in two
necked round bottom flask (500 mL). Then acetonitrile (80
mL) and iodine (0.243 mg, 0.96 mmol) were added. Then
the mixture was allowed to stir for 7 h at 70 ºC. After that
the mixture was concentrated under vacuum and diluted
with ethyl acetate. The solution was washed with water
and dried over anhyd sodium sulphate. Resulting mixtures
were purified through column chromatography using silica
gel and n-hexane, ethyl acetate (9:1) solvent mixture as an
eluent to afford 3aa in 84% (2.22 g).
(20% ethyl acetate in hexane); White solid; yield 87% (141
1
mg); mp 109-110 ºC; H NMR (400 MHz, CDCl3) δ 7.81
(d, J = 8.2 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.38 (d, J =
8.2 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 5.22 (d, J = 10.0 Hz,
1H), 3.82 (d, J = 1.6 Hz, 1H), 3.42 (dd, J = 14.4, 10.0 Hz,
1H), 3.28 (dd, J = 14.4, 2.0 Hz, 1H), 2.47 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ 145.6, 139.8, 136.1, 132.0,
130.3, 128.1, 127.5, 122.3, 68.0, 63.9, 21.8; IR (KBr) ν
3484, 3063, 2982, 2924, 2305, 2104, 1916, 1641, 1596,
1487, 1400, 1300, 1288, 1196, 1137, 1102, 1087, 1070,
1010, 913, 863; HRMS (ESI-TOF) calcd for C15H15BrO3S
(M + Na)+ 376.9817, found 376.9827.
̃
1-Phenyl-2-tosylethanol (3aa).[32] Rf = 0.28 (20% ethyl
1-(o-Tolyl)-2-tosylethanol (3ga).[32] Rf = 0.27 (20% ethyl
acetate in hexane); White solid; yield 72% (97 mg); mp
125-126 ºC; 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J =
acetate in hexane); off white solid; yield 99% (142 mg);
1
mp 72-74 ºC (lit.[33] 130 - 131 ºC); H NMR (400 MHz,
CDCl3) δ 7.82 (d, J = 8.2 Hz, 2H), 7.37 (d, J = 8.2 Hz, 2H), 8.2 Hz, 2H), 7.49 (d, J = 7.2 Hz, 1H), 7.40 (d, J = 8.2 Hz,
7.34-7.23 (m, 5H), 5.24 (d, J = 10.0 Hz, 1H), 3.78 (br s,
1H), 3.47 (dd, J = 14.4, 10.0 Hz, 1H), 3.31 (dd, J = 14.4, 2
Hz, 1H), 2.45 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
145.3, 140.8, 136.2, 130.1, 128.8, 128.3, 128.1, 125.7, 68.5,
2H), 7.24-7.12 (m, 2H), 7.08 (d, J = 7.2 Hz, 1H), 5.44 (d, J
= 10.0 Hz, 1H), 3.67 (d, J = 1.6 Hz, 1H), 3.40 (dd, J = 14.4,
10.0 Hz, 1H), 3.24 (d, J = 14.4 Hz, 1H), 2.47 (s, 3H), 2.09
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 145.4, 138.8, 136.2,
64.0, 21.7; IR (KBr) ῡ 3484, 3063, 2924, 1640, 1598, 1494, 133.8, 130.7, 130.3, 128.21, 128.18, 126.7, 125.4, 65.2,
1453, 1401, 1300, 1288, 1137, 1087, 994, 816; HRMS
(ESI-TOF) calcd for C15H16O3S (M + Na)+ 299.0712,
found 299.0713.
63.1, 21.8, 18.7; IR (KBr) ῡ 3420, 3105, 2975, 2115, 1643,
1554, 1264, 1140, 896; HRMS (ESI-TOF) calcd for
C16H18O3S (M + Na)+ 313.0869, found 313.0844.
1-(4-Chlorophenyl)-2-tosylethanol (3ba).[32] Rf = 0.30
1-(Naphthalen-2-yl)-2-tosylethanol (3ha).[13b] Rf = 0.27
(20% ethyl acetate in hexane); White solid; yield 93% (144
(20% ethyl acetate in hexane); off white solid; yield 96%
1
1
mg); mp 94-96 ºC; H NMR (400 MHz, CDCl3) δ 7.82 (d,
(142 mg); mp 102-103 ºC; H NMR (400 MHz, CDCl3) δ
J = 8.2 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 7.31-7.21 (m,
4H), 5.23 (d, J = 10.0 Hz, 1H), 3.82 (d, J = 1.6 Hz, 1H),
7.81 (d, J = 8.2 Hz, 2H), 7.79-7.72 (m, 4H), 7.46 (dd, J =
6.0, 3.2 Hz, 2H), 7.36-7.28 (m,3H), 5.41 (dd, J = 10.0, 2.0
3.44 (dd, J = 14.4, 10.0 Hz, 1H), 3.28 (dd, J = 14.4, 2.0 Hz, Hz, 1H), 3.96 (br s, 1H), 3.57 (dd, J = 14.4, 10.0 Hz, 1H),
1H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 145.6,
139.3, 136.1, 134.2, 130.3, 129.0, 128.1, 127.2, 68.0, 64.0,
21.8; IR (KBr) ῡ 3419, 3055, 2987, 2305, 2125, 1641,
1549, 1493, 1264, 1145, 1088, 896; HRMS (ESI-TOF)
calcd for C15H15ClO3S (M + Na)+ 333.0323, found
333.0332.
3.41 (dd, J = 14.4, 2.0 Hz, 1H), 2.41 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 145.2, 138.1, 136.2, 133.2, 133.1,
130.1, 128.7, 128.0 (x 2), 127.7, 126.4, 126.3, 124.8, 123.4,
68.7, 63.9, 21.7; IR (KBr) ῡ 3420, 2965, 2876, 2376, 2307,
2114, 1641, 1550, 1511, 1264, 1136, 1087, 896, 860;
HRMS (ESI-TOF) calcd for C19H18O3S (M + Na)+
349.0869, found 349.0871.
1-(p-Tolyl)-2-tosylethanol (3ca).[13c] Rf = 0.28 (20% ethyl
1
acetate in hexane); Colourless oil; yield 70% (77 mg); H
1-Phenyl-2-(phenylsulfonyl)ethanol (3ab).[34] Rf = 0.38
NMR (400 MHz, CDCl3) δ 7.83 (d, J = 8.2 Hz, 2H), 7.38
(d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.12 (d, J =
8.0 Hz, 2H), 5.21 (d, J = 10.0 Hz, 1H), 3.65 (d, J = 2.0 Hz,
1H), 3.47 (dd, J = 14.4, 10.0 Hz, 1H), 3.30 (dd, J = 14.4,
2.0 Hz, 1H), 2.47 (s, 3H), 2.31 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 145.3, 138.2, 137.9, 136.3, 130.2, 129.5,
(20% ethyl acetate in hexane); White solid; yield 71% (97
1
mg); mp 91-93 ºC (lit.[35] 92-94 ºC); H NMR (400 MHz,
CDCl3) δ 7.96 (d, J = 7.6 Hz, 2H), 7.73-7.65 (m, 1H),
7.64-7.54 (m, 2H), 7.36-7.27 (m, 5H), 5.28 (d, J = 10.0 Hz,
1H), 3.68 (br s, 1H), 3.51 (dd, J = 14.4, 10.0 Hz, 1H), 3.34
(dd, J = 14.4, 2.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
128.1, 125.7, 68.5, 64.1, 21.8, 21.2; IR (KBr) ῡ 3422, 2963, 140.8, 139.3, 134.2, 129.6, 128.9, 128.5, 128.1, 125.8, 68.6,
2877, 2090, 1640, 1422, 1265, 896; HRMS (ESI-TOF)
64.1; IR (KBr) ῡ 3483, 2927, 2089, 1641, 1494, 1479,
1394, 1303, 1199, 1138, 1085, 1025, 996; HRMS (ESI-
TOF) calcd for C14H14O3S (M + Na)+ 285.0556, found
285.0572.
calcd for C16H18O3S (M + Na)+ 313.0869, found 313.0883.
2-Phenyl-1-tosylpropan-2-ol (3da).[32] Rf = 0.40 (20%
ethyl acetate in hexane); White solid; yield 76% (102 mg);
1
mp 100-102 ºC (lit.[7a] 84-85 ºC) H NMR (400 MHz,
1-(4-Chlorophenyl)-2-(phenylsulfonyl)ethanol (3bb).[13d]
CDCl3) δ 7.48 (d, J = 8.4 Hz, 2H), 7.36-7.26 (m, 2H),
7.26-7.08 (m, 5H), 4.63 (br s, 1H), 3.70 (d, J = 14.4 Hz,
1H), 3.59 (d, J = 14.4 Hz, 1H), 2.38 (s, 3H), 1.70 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 144.7, 144.6, 137.5, 129.8,
128.4, 127.7, 127.3, 124.8, 73.3, 66.8, 30.9, 21.7; IR (KBr)
ῡ 3500, 3062, 2984, 2930, 2101, 1632, 1598, 1494, 1447,
1381, 1268, 1184, 1122, 1083, 1048, 1028, 945, 850;
HRMS (ESI-TOF) calcd for C16H18O3S (M + Na)+
313.0869, found 313.0889.
Rf = 0.32 (20% ethyl acetate in hexane); White solid; yield
1
84% (124 mg); mp 104-105 ºC (lit.[36] 61 ºC); H NMR
(400 MHz, CDCl3) δ 7.95 (d, J = 8.0 Hz, 2H), 7.77-7.65
(m, 1H), 7.65-7.55 (m, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.23
(d, J = 8.4 Hz, 2H), 5.27 (d, J = 10.0 Hz, 1H), 3.75 (br s,
1H), 3.46 (dd, J = 14.4, 10.0 Hz, 1H), 3.31 (dd, J = 14.0,
2.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 139.2, 139.1,
134.4, 134.3, 129.7, 129.1, 128.1, 127.2, 68.0, 63.9; IR
(KBr) ῡ 3443, 3055, 2987, 2305, 1641, 1492, 1447, 1421,
1306, 1265, 1146, 1086, 896; HRMS (ESI-TOF) calcd for
C14H13ClO3S (M + Na)+ 319.0166, found 319.0180.
1-([1,1'-Biphenyl]-4-yl)-2-tosylethanol (3ea). Rf = 0.26
(20% ethyl acetate in hexane); White solid; yield 95% (111
1
mg); mp 105-106 ºC; H NMR (400 MHz, CDCl3) δ 7.85
2-(Phenylsulfonyl)-1-(p-tolyl)ethanol (3cb).[13d] Rf = 0.33
(d, J = 8.2 Hz, 2H), 7.60-760 (m, 4H), 7.48-7.30 (m, 7H),
5.31 (d, J = 10.0 Hz, 1H), 3.78 (d, J = 1.6 Hz, 1H), 3.52
(20% ethyl acetate/hexane); white solid; yield 84% (105
1
mg); mp 82-83 ºC; H NMR (400 MHz, CDCl3) δ 8.07-
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201700772
Advanced Synthesis & Catalysis
7.85 (m, 2H), 7.75-7.65 (m, 1H), 7.64-7.53 (m, 2H), 7.18
(d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 5.24 (d, J =
10.0 Hz, 1H), 3.59 (d, J = 1.6 Hz, 1H), 3.50 (dd, J = 14.4,
10.0 Hz, 1H), 3.33 (dd, J = 14.4, 2.0 Hz, 1H), 2.31 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 139.4, 138.3, 137.8, 134.2,
129.6, 129.5, 128.1, 125.7, 68.4, 64.1, 21.2; IR (KBr) ῡ
3483, 3062, 2923, 1994, 1907, 1641, 1585, 1548, 1514,
1478, 1447, 1304, 1199, 1138, 1086, 1022, 998, 913, 864;
HRMS (ESI-TOF) calcd for C15H16O3S (M + Na)+
299.0712, found 299.0694.
1-((4-tButylphenyl)sulfonyl)-2-phenylpropan-2-ol (3dc).
Rf = 0.40 (20% ethyl acetate in hexane); White solid; yield
85% (130 mg); mp 92-93 ºC; 1H NMR (400 MHz, CDCl3)
δ 7.47 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.27-
7.23 (m, 2H), 7.18-7.08 (m, 3H), 4.69 (br s, 1H), 3.73 (d, J
= 14.4 Hz, 1H), 3.60 (d, J = 14.4 Hz, 1H), 1.68 (s, 3H),
1.31 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 157.4, 144.4,
137.2, 128.3, 127.5, 127.3, 126.2, 124.8, 73.2, 66.6, 35.3,
31.2 (x2C); IR (KBr) ῡ 3450, 2965, 2076, 1640, 1493,
1397, 1307, 1251, 1158, 1082, 850; HRMS (ESI-TOF)
calcd for C19H24O3S (M + Na)+ 355.1338, found 355.1343.
1-(Naphthalen-2-yl)-2-(phenylsulfonyl)ethanol (3hb). Rf
= 0.34 (20% ethyl acetate in hexane); White solid; yield
1-([1,1'-Biphenyl]-4-yl)-2-((4-(tert-
1
91% (110 mg); mp 94-96 ºC; H NMR (400 MHz, CDCl3)
butyl)phenyl)sulfonyl)ethanol (3ec). Rf = 0.35 (20%
ethyl acetate in hexane); White solid; yield 79% (103 mg);
mp 115-116 ºC; 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J =
8.4 Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 7.57-7.52 (m, 4H),
δ 8.00-7.92 (m, 2H), 7.82-7.76 (m, 4H), 7.71-7.64 (m, 1H),
7.61-7.54 (m, 2H), 7.50-7.44 (m, 2H), 7.36 (dd, J = 8.0,
2.0 Hz, 1H), 5.46 (d, J = 10.0 Hz, 1H), 3.81 (br s, 1H),
3.59 (dd, J = 14.4, 10.0 Hz, 1H), 3.43 (dd, J = 14.4, 2.0 Hz, 7.47-7.29 (m, 5H), 5.35 (d, J = 10.0 Hz, 1H), 3.81 (d, J =
1H); 13C NMR (100 MHz, CDCl3) δ 139.3, 138.0 (x2C),
134.3, 133.31, 133.29, 129.6, 128.8, 128.1, 127.8, 126.6,
126.5, 124.9, 123.4, 68.7, 64.0; IR (KBr) ῡ 3455, 3089,
2096, 1632, 1509, 1476, 1446, 1387, 1367, 1266, 1136,
1085,737; HRMS (ESI-TOF) calcd for C18H16O3S (M +
Na)+ 335.0712, found 335.0691.
1.6 Hz, 1H), 3.53 (dd, J = 14.4, 10.0 Hz, 1H), 3.39 (dd, J =
14.4, 2.0 Hz, 1H), 1.35 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 158.4, 141.4, 140.6, 139.8, 136.2, 128.9, 128.0,
127.62, 127.59, 127.2, 126.7, 126.3, 68.3, 64.0 35.5, 31.2;
IR (KBr) ῡ 3443, 2928, 2850, 2358, 2096, 1642, 1275,
1261, 764; HRMS (ESI-TOF) calcd for C24H26O3S (M +
Na)+ 417.1495, found 417.1467.
1-(2-Chlorophenyl)-2-(phenylsulfonyl)ethanol (3ib).[13d]
Rf = 0.34 (20% ethyl acetate in hexane); Colourless liquid;
1-(4-Bromophenyl)-2-((4-(tert-
1
yield 61% (84 mg); H NMR (400 MHz, CDCl3) δ 8.04-
butyl)phenyl)sulfonyl)ethanol (3fc). Rf = 0.33 (20% ethyl
acetate in hexane); White solid; yield 83% (150 mg); mp
7.96 (m, 2H), 7.73-7.57 (m, 4H), 7.33-7.27 (m, 1H), 7.25-
1
7.17 (m, 2H), 5.44 (d, J = 10.0 Hz, 1H), 3.99 (br s, 1H),
134-136 ºC; H NMR (400 MHz, CDCl3) δ 7.92-7.76 (m,
3.52 (dd, J = 14.4, 1.2 Hz, 1H), 3.30 (dd, J = 14.4, 10.0 Hz, 2H), 7.62-7.54 (m, 2H), 7.47-7.38 (m, 2H), 7.18 (d, J = 8.2
1H); 13C NMR (175 MHz, CDCl3) δ 138.6, 137.9, 134.3,
131.0, 129.6, 129.5, 129.4, 128.3, 127.5, 127.3, 65.6, 61.9;
IR (KBr) ῡ 3421, 3056, 2998, 2305, 2114, 1641, 1447,
1421, 1265, 1143, 909, 896; HRMS (ESI-TOF) calcd for
C14H13ClO3S (M + Na)+ 319.0166, found 319.0174.
Hz, 2H), 5.26 (dd, J = 10.0, 2.0 Hz, 1H), 3.84 (br s, 1H),
3.44 (dd, J = 14.4, 10.0 Hz, 1H), 3.31 (dd, J = 14.4, 2.0 Hz,
1H), 1.35 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 158.5,
139.8, 136.0, 131.9, 127.9, 127.6, 126.7 122.3, 68.0, 63.8,
35.5, 31.2; IR (KBr) ῡ 3508, 3055, 2969, 2305, 2099, 1643,
1594, 1421, 1398, 1306, 1291, 1198, 1107, 1085, 1011,
895; HRMS (ESI-TOF) calcd for C18H21BrO3S (M + Na)+
419.0287, found 419.0269.
2-((4-tButylphenyl)sulfonyl)-1-phenylethanol (3ac). Rf =
0.32 (20% ethyl acetate in hexane); white solid; yield 94%
1
(120 mg); mp 113-115 ºC; H NMR (400 MHz, CDCl3) δ
7.83 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.30-
2-((4-tButylphenyl)sulfonyl)-1-(naphthalen-2-yl)ethanol
7.19 (m, 5H), 5.25 (d, J = 10.0 Hz, 1H), 3.77 (d, J = 1.6 Hz, (3hc). Rf = 0.34 (20% ethyl acetate in hexane); White
1
1H), 3.46 (dd, J = 14.4, 10.0 Hz, 1H), 3.30 (dd, J = 14.4,
2.0 Hz, 1H), 1.32 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
158.2, 140.8, 136.2, 128.8, 128.4, 127.9, 126.6, 125.8, 68.5,
solid; yield 95% (136 mg); mp 132-134 ºC; H NMR (400
MHz, CDCl3) δ 7.87 (d, J = 8.4 Hz, 2H), 7.83-7.74 (m,
4H), 7.56 (d, J = 8.4 Hz, 2H), 7.52-7.43 (m, 2H), 7.36 (d, J
64.0, 35.4, 31.1; IR (KBr) ῡ 3444, 2965, 2865, 2100, 1641, = 8.4 Hz, 1H), 5.47 (d, J = 10.0 Hz, 1H), 3.89 (br s, 1H),
1550, 1492, 1451, 1396, 1288, 1197, 1140, 1084, 844;
HRMS (ESI-TOF) calcd for C18H22O3S (M + Na)+
341.1182, found 341.1172.
3.58 (dd, J = 14.4, 10.0 Hz, 1H), 3.44 (dd, J = 14.4, 2.0 Hz,
1H), 1.34 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 158.3,
138.1, 136.2, 133.3, 133.2, 128.8, 128.1, 128.0, 127.8,
126.6, 126.5, 126.4, 125.0, 123.4, 68.7, 63.9, 35.4, 31.1; IR
(KBr) ῡ 3507, 3085, 2970, 2340, 2098, 1642, 1510, 1476,
1399, 1365, 1291, 1265, 1152, 1085, 896, 860; HRMS
(ESI-TOF) calcd for C22H24O3S (M + Na)+ 391.1338,
found 391.1357.
2-((4-tButylphenyl)sulfonyl)-1-(4-chlorophenyl)ethanol
(3bc). Rf = 0.30 (20% ethyl acetate in hexane); White
1
solid; yield 83% (146 mg); mp 120-122 ºC; H NMR (400
MHz, CDCl3) δ 7.84 (d, J = 8.4 Hz, 2H), 7.58 (d, J = 8.4
Hz, 2H), 7.30-7.21 (m, 4H), 5.27 (d, J = 10.0 Hz, 1H), 3.84
(d, J = 1.6 Hz, 1H), 3.45 (dd, J = 14.4, 10.0 Hz, 1H), 3.31
(dd, J = 14.4, 2.0 Hz, 1H), 1.35 (s, 9H); 13C NMR (175
MHz, CDCl3) δ 158.5, 139.3, 136.1, 134.2, 129.0, 127.9,
2-((4-tButylphenyl)sulfonyl)-1-(3-chlorophenyl)ethanol
(3jc). Rf = 0.38 (20% ethyl acetate in hexane); White solid;
1
yield 50% (83 mg); mp 77-79 ºC; H NMR (400 MHz,
127.2, 126.7, 67.9, 63.9, 35.5, 31.2; IR (KBr) ῡ 3422, 3057, CDCl3) δ 7.89-7.81 (m, 2H), 7.64-7.56 (m, 2H), 7.32 (s,
2968, 2377, 2306, 2115, 1785, 1640, 1550, 1493, 1399,
1307, 1263, 1198, 1107, 1085, 1014, 995, 896, 864;
HRMS (ESI-TOF) calcd for C18H21O3SCl (M + Na)+
375.0792, found 375.0782.
1H), 7.25-7.15 (m, 3H), 5.27 (dd, J = 10.0, 2.0 Hz, 1H),
3.85 (br s, 1H), 3.45 (dd, J = 14.4, 10.0 Hz, 1H), 3.32 (dd,
J = 14.0, 2.0 Hz, 1H), 1.36 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 158.5, 142.8, 136.0, 134.8, 130.2, 128.6, 128.0,
126.7, 126.1, 124.0, 68.0, 63.9, 35.5, 31.2; IR (KBr) ῡ
3421, 2956, 2356, 2090, 1640, 1275, 1260, 1055; HRMS
(ESI-TOF) calcd for C18H21ClO3S (M + Na)+ 375.0792,
found 375.0776.
2-((4-tButylphenyl)sulfonyl)-1-(p-tolyl)ethanol (3cc). Rf
= 0.34 (20% ethyl acetate in hexane); White solid; yield
65% (98 mg); mp 97-99 ºC; 1H NMR (400 MHz, CDCl3) δ
7.86 (d, J = 8.4 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.18 (d,
J = 8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.24 (d, J = 10.0
Hz, 1H), 3.70 (d, J = 1.6 Hz, 1H), 3.49 (dd, J = 14.4, 10.0
Hz, 1H), 3.33 (dd, J = 14.4, 2.0 Hz, 1H), 2.31 (s, 3H), 1.36
4-(2-((4-tButylphenyl)sulfonyl)-1-
hydroxyethyl)benzonitrile (3kc): Rf = 0.25 (20% ethyl
acetate in hexane); White solid; yield 44% (69 mg); mp
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 158.2, 138.2, 137.9, 120-124 ºC; 1H NMR (700 MHz, CDCl3) δ 7.85 (d, J = 8.0
136.2, 129.5, 127.9, 126.6, 125.7, 68.4, 64.0, 35.4, 31.1,
21.2; IR (KBr) ῡ 3474, 3060, 2967, 2871, 2307, 2099,
1923,1640, 1514, 1476, 1399, 1306, 1267, 1199, 1107,
1085, 1057, 1014, 864, 840; HRMS (ESI-TOF) calcd for
C19H24O3S (M + Na)+ 355.1338, found 355.1325.
Hz, 2H), 7.57 - 7.63 (m, 4H), 7.45 (d, J = 8.0 Hz, 2H), 5.37
(d, J = 10.0 Hz, 1H), 4.03 (s, 1H), 3.43 (dd, J = 14.4, 10.0
Hz, 1H), 3.32 (d, J = 14.4 Hz, 1H), 1.35 (s, 9H); 13C NMR
(175 MHz, CDCl3) δ 158.7, 145.9, 135.8, 132.6, 127.9,
126.8, 126.6, 118.5, 112.2, 67.9, 63.6, 35.5, 31.1; IR (KBr)
ῡ 3484, 3059, 2966, 2871, 2304, 2229, 2098, 1636, 1463,
6
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10.1002/adsc.201700772
Advanced Synthesis & Catalysis
1397, 1291, 1266, 1198, 1143, 1107; HRMS (ESI-TOF)
calcd for C19H21NO3S (M + Na)+ 366.1146, found
366.1134.
1128, 803; HRMS (ESI-TOF) calcd for C16H20O3S (M +
Na)+ 315.1025, found 315.1014.
2-Tosyl-1-(4-(trifluoromethyl)phenyl)ethanol (3na): Rf
= 0.30 (20% ethyl acetate in hexane); White solid; yield
46% (55 mg); mp 98-100 ºC; 1H NMR (700 MHz, CDCl3)
δ 7.82 (d, J = 8.0 Hz, 2H), 7.57 (d, J = 8.0 Hz, 2H), 7.43 (d,
2-((4-tButylphenyl)sulfonyl)-1-(4-nitrophenyl)ethanol
(3lc): Rf = 0.22 (20% ethyl acetate in hexane); White solid;
1
yield 59% (100 mg); mp 130-132 ºC; H NMR (700 MHz,
CDCl3) δ 8.17 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), J = 8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 5.34 (d, J = 10.0
7.60 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H), 5.43 (d,
J = 10.0 Hz, 1H), 4.08 (brs, 1H), 3.45 (dd, J = 14.4, 10.0
Hz, 1H), 3.34 (dd, J = 14.4, 2.0 Hz, 1H), 1.35 (s, 9H); 13C
NMR (175 MHz, CDCl3) δ 158.8, 147.82, 147.81, 135.8,
128.0, 126.8, 126.7, 124.1, 67.8, 63.6, 35.5, 31.1; IR (KBr)
ῡ 3487, 2964, 2870, 1594, 1521, 1346, 1305, 1198, 1144,
1107, 1084; HRMS (ESI-TOF) calcd for C18H21NO5S (M
+ Na)+ 386.1007, found 386.1033.
Hz, 1H), 3.91 (s, 1H), 3.44 (dd, J = 14.4, 10.0 Hz, 1H),
3.32 (d, J = 14.4 Hz, 1H), 2.47 (s, 3H); 13C NMR (175
MHz, CDCl3) δ 145.7, 144.6, 136.0, 130.4, 128.1, 126.20,
125.84 (q, J = 3.7 Hz), 124.8, 123.3, 68.1, 63.9, 21.8; IR
(KBr) ῡ 3400, 3034, 2986, 2928, 2306, 2106, 1926, 1633,
1494, 1412, 1324, 1162, 1133, 1066, 1016; HRMS (ESI-
TOF) calcd for C16H15F3O3S (M + Na)+ 367.0579, found
367.0586.
2-((4-tButylphenyl)sulfonyl)-1-(4-
Preparation of sulfothionic acid (4). p-Toluenesulfonyl
hydrazide (100 mg, 0.54 mmol) was allowed to stir at
standard condition for 8 h. Then the mixture was
concentrated under vacuum and purified through silica gel
column chromatography to afford the 14% of 4.
methoxyphenyl)ethanol (3mc): Rf = 0.32 (20% ethyl
acetate in hexane); white solid ; yield 96% (125 mg); mp
115-119 ºC; 1H NMR (700 MHz, CDCl3) δ 7.86 (d, J = 8.6
Hz, 2H), 7.58 (d, J = 8.6 Hz, 2H), 7.22 (d, J = 8.6 Hz, 2H),
6.84 (d, J = 8.6 Hz, 2H), 5.23 (d, J = 10.0 Hz, 1H), 3.77 (s,
3H), 3.69 (d, J = 1.2 Hz, 1H), 3.49 (dd, J = 14.4, 10.0 Hz,
1H), 3.31 (dd, J = 14.4, 2.0 Hz, 1H), 1.35 (s, 9H); 13C
NMR (175 MHz, CDCl3) δ 159.7, 158.3, 136.3, 133.0,
128.0, 127.2, 126.6, 114.2, 68.2, 64.0, 55.4, 35.5, 31.2. IR
(KBr) ῡ 3466, 2966, 2084, 1632, 1514, 1397, 1304, 1249,
1141, 1032; HRMS (ESI-TOF) calcd for (M + Na)+
371.1290, found 371.1288.
S-p-Tolyl-4-methylbenzenesulfonothioate. 1H NMR (400
MHz, CDCl3) δ 7.46 (d, J = 8.0 Hz, 2H), 7.25-7.19 (m,
4H), 7.14 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H), 2.38 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 144.7, 142.2, 140.6, 136.6,
130.3, 129.5, 127.8, 124.8, 21.8, 21.62.
H2O18 Labelling experiments. An oven dried schlenk tube
was charged with dry CH3CN (3.0 mL), styrene (60 mg,
0.522 mmol), p-toluenesulfonyl hydrazide (146 mg, 0.784
mmol), iodine (13.2 mg, 0.052 mmol), pyridine (4.5 μL,
0.052 mmol). Then 0.5 mL of H2O18 was added to the
reaction mixture and stirred at 70 ºC for 7 h. After that the
mixture was concentrated under vacuum and diluted with
ethyl acetate. The solution was washed with water and
dried over anhyd sodium sulphate. Silica gel column
chromatographic purification of the crude product afforded
96% of 3aa.
2-(Butylsulfonyl)-1-(4-chlorophenyl)ethanol (3bd). Rf =
0.32 (20% ethyl acetate in hexane); White solid; yield 54%
1
(74 mg); mp 97-99 ºC; H NMR (400 MHz, CDCl3) δ
7.40-7.28 (m, 4H), 5.39-5.34 (m, 1H), 3.36 (dd, J = 14.4,
10.0 Hz, 1H), 3.22 (d, J = 2.0 Hz, 1H), 3.18-3.05 (m, 3H),
1.90-1.80 (m, 2H), 1.53-1.43 (m, 2H), 0.97 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 139.7, 134.5, 129.3,
127.2, 68.4, 60.4, 54.7, 24.0, 21.9, 13.7; IR (KBr) ῡ 3422,
3055, 2987, 2685, 2410, 2305, 2124, 1640, 1551, 1421,
1265, 1127, 895; HRMS (ESI-TOF) calcd for C12H17ClO3S
(M + Na)+ 299.0479, found 299.0501.
O18 Labelling experiments. An oven dried schlenk tube
was charged with dry CH3CN (3.0 mL), styrene (60 mg,
0.52 mmol), p-toluenesulfonyl hydrazide (146 mg, 0.78
mmol), iodine (13.2 mg, 0.052 mmol), pyridine (4.5 μL,
0.052 mmol) in a glove box. After taking out the schlenk
tube from glove box 18O2 gas purged and stirred at 70 ºC
for 7 h. After that the mixture was concentrated under
vacuum and diluted with ethyl acetate. The solution was
washed with water and dried over anhyd sodium sulphate.
Silica gel column chromatographic purification of the
crude product afforded 3aa׳ in 77% yield.
1-([1,1'-biphenyl]-4-yl)-2-(butylsulfonyl)ethanol (3ed).
Rf = 0.30 (20% ethyl acetate in hexane); White solid; yield
85% (90 mg); mp 115-118 ºC; 1H NMR (400 MHz,
CDCl3) δ 7.68-7.54 (m, 4H), 7.53-7.40 (m, 4H), 7.39-7.33
(m, 1H), 5.44 (d, J = 10.0 Hz, 1H), 3.45 (dd, J = 14.4, 10.0
Hz, 1H), 3.23-3.05 (m, 4H), 1.93-1.82 (m, 2H), 1.52-1.46
(m, 2H), 0.98 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 141.7, 140.5, 140.2, 129.0, 127.8, 127.7, 127.2,
126.3, 68.9, 60.5, 54.7, 24.0, 21.9, 13.7; IR (KBr) ῡ 3422,
3056, 2988, 2306, 2115, 1641, 1534, 1421, 1265, 895;
HRMS (ESI-TOF) calcd for C18H22O3S (M + Na)+
341.1182, found 341.1162.
CCDC-1543183 (3da) and CCDC-1543008 (3hd) contains
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
1-(4-Bromophenyl)-2-(butylsulfonyl)ethanol (3fd). Rf =
Cambridge
Crystallographic
Data
Centre
0.31 (20% ethyl acetate in hexane); White solid; yield 42%
via www.ccdc.cam.ac.uk/data_request/cif.
1
(62 mg); mp 94-95 ºC; H NMR (400 MHz, CDCl3) δ
7.56-7.45 (m, 2H), 7.28-7.25 (m, 2H), 5.33 (dd, J = 10.0,
2.0 Hz, 1H), 3.35 (dd, J = 14.4, 10.0 Hz, 1H), 3.30 (d, J =
2.8 Hz, 1H), 3.16-3.04 (m, 3H), 1.90-1.77 (m, 2H), 1.55-
1.40 (m, 2H), 0.96 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 140.2, 132.2, 127.5, 122.6, 68.4, 60.4, 54.7, 24.0,
21.8, 13.7; IR (KBr) ῡ 3442, 2965, 2875, 2115, 1639, 1527,
1489, 1398, 1124, 1069, 1010; HRMS (ESI-TOF) calcd
for C12H17BrO3S (M + Na)+ 342.9974, found 342.9987.
Acknowledgements
We thank DST (New Delhi, India) for support, Tapan K. Paine
(IACS, Kolkata) for laboratory facilities to carry out 18O
experiments and T.K.A. thank UGC (India) for fellowship.
2-(Butylsulfonyl)-1-(naphthalen-2-yl)ethanol (3hd). Rf =
0.33 (20% ethyl acetate in hexane); White solid; yield 58%
References
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1
(66 mg); mp 112-114 C; H NMR (400 MHz, CDCl3) δ
7.94-7.80 (m, 4H), 7.55-7.44 (m, 3H), 5.56 (d, J = 10.0 Hz,
1H), 3.49 (dd, J = 14.4, 10.0 Hz, 1H), 3.37-3.08 (m, 4H),
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Iodine Triggered Aerobic Oxysulfonylation of
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Khokan Choudhuri, Tapas Kumar Achar and
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