FeBr3-catalyzed regioselective hydroxysulfenylation of N-allylsulfonamides with sulfonyl hydrazides

Article abstract of DOI:10.1016/j.tet.2018.12.044

Regioselective hydroxysulfenylation of unactivated C[dbnd]C double bonds was reported. Using FeBr₃-bpy as the catalyst, Na₂S₂O₈ as the oxidant, and sulfonyl hydrazides as the sulfenyl sources, hydroxysulfenylation of unfunctionalized olefins proceeded readily, giving a variety of β-hydroxysulfides in moderate to good isolated yields.

Full text of DOI:10.1016/j.tet.2018.12.044

Tetrahedron 75 (2019) 643e651
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FeBr3-catalyzed regioselective hydroxysulfenylation of
N-allylsulfonamides with sulfonyl hydrazides
,
, b, *
Zhong-Qi Xu a, Lin-Chuang Zheng a, Lin Li a, Lili Duan a **, Yue-Ming Li a
a State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Research, Nankai University,
Tianjin, People's Republic of China
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032,
People's Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Regioselective hydroxysulfenylation of unactivated C]C double bonds was reported. Using FeBr3-bpy as
Received 24 October 2018
Received in revised form
13 December 2018
Accepted 21 December 2018
Available online 23 December 2018
the catalyst, Na2S2O8 as the oxidant, and sulfonyl hydrazides as the sulfenyl sources, hydrox-
ysulfenylation of unfunctionalized olefins proceeded readily, giving a variety of
b-hydroxysulfides in
moderate to good isolated yields.
© 2018 Elsevier Ltd. All rights reserved.
Keywords:
Unfunctionalized olefins
Regioselective hydroxysulfenylation
FeBr3 sulfonyl hydrazides
b
-hydroxysulfides
1. Introduction
Other methods for the formation of b-hydroxysulfides include the
thiol-oxygen co-oxidation (TOCO) of alkenes with thiols [11]. Using
1,2-Difunctionalization of C]C double bonds constitutes one of
the most powerful methods for the introduction of functional
groups into the olefinic substrates, and significant efforts have been
made as a result [1]. Among the reactions studied, direct hydrox-
ysulfenylation of unactivated alkenes has emerged as a new
this strategy, both electron-rich alkenes [12] and electron-deficient
alkenes could be converted to the desired
satisfactory yields [13]. For example, in 2008, Naito et al. reported
an Et3B-promoted hydroxysulfenylation reaction using -unsat-
b-hydroxysulfides in
a,b
urated imines as the thiol radical acceptors under aerobic condi-
tions (Scheme 1a) [13a]. Tang et al. presented the
method for the synthesis of b-hydroxysulfides, which can be used
as important starting materials for a variety of natural products,
hydroxysulfenylation of simple a,b-unsaturated esters/amides un-
fine chemicals and pharmaceuticals [2]. In particular, the nitrogen-
containing b-hydroxysulfides have attracted considerable attention
due to their fascinating biological activities, such as anti-
mycobacterial [3], anti-malarial [4], anti-depressant [5], anti-HIV
[6], antiarrhythmic [7], and other properties [8].
der mild and transition-metal-free conditions using O2 as both the
oxidant and the oxygen source (Scheme 1b) [13b]. Some other
methods have also been explored [14]. For example, Peddinti et al.
reported a metal-free hydroxysulfenylation reaction between sty-
renes and thiols with an iodine/DMSO system [14c].
One of the most straightforward synthetic route to
b
-hydrox-
So far, different types of hydroxysulfenylation reactions have
been studied, but the sulfenylating agents were generally limited to
thiols or disulfides, which were not always easily available or easy
to handle. Also, these reactions generally suffered from narrow
substrate scope or low yields, no need to mention the normally
unpleasant odor of thiols. It is therefore highly desirable to explore
new sulfenylating agents for hydroxysulfenylation of different
olefinic substrates. It is our purpose to develop new methods for
the preparation of different sulfur-containing molecules. Herein we
wish to report a direct hydroxysulfenylation of N-allylsulfonamides
ysulfides is the ring opening of epoxides with thiols [9] or disulfides
[10]. However, this pathway generally suffers from poor regiose-
lectivity, low yields, and the formation of undesirable by-products.
* Corresponding author.
** Corresponding author. State Key Laboratory of Medicinal Chemical Biology,
College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Research, Nankai
University, Tianjin, People's Republic of China.
E-mail address: ymli@nankai.edu.cn (Y.-M. Li).
https://doi.org/10.1016/j.tet.2018.12.044
0040-4020/© 2018 Elsevier Ltd. All rights reserved.

644
Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
Table 1
Optimization of Reaction Conditions.a,b
entry
I or Br source
solvent
yield (%)c
1
2
3
4
5
6
7
8
I2
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE/Diox (1:1)
DCE
10
43
45
42
37
36
55
27
27
44
37
57
trace
52
74
KBrd
TMSBrd
NBSd
CuBr-bpy
CuBr2-bpy
FeBr3-bpy
ZnBr2-bpy
MgBr2-bpy
MnBr2-bpy
FeBr3-bpy
FeBr3-bpy
FeBr3-bpy
FeBr3-bpy
FeBr3-bpy
FeCl3-bpy/ZnI2
FeBr3-bpy
FeBr3-bpy
FeBr3-bpy
FeBr3-bpy
9
10
11
12
13
14
15
16
17
18e
19g
20
Scheme 1. Strategies for sulfenylation of C]C double bonds.
Diox
toluene
using easily available sulfonyl hydrazides as sulfur source.
Diox/H2O (10:1)
Diox/H2O (20:1)
Diox/H2O (20:1)
Diox/EtOH (20:1)
Diox/H2O (20:1)
Diox/H2O (20:1)
Diox/H2O (20:1)
58
28
2. Results and discussion
NDf
ND
72h
Sulfonyl hydrazides are easily available and shelf-stable re-
agents and have been widely employed in organic synthesis [15].
This type of compounds can serve as sulfonylating [16], sulfeny-
lating [17], and arylating agents [18] under appropriate conditions.
For example, Tian et al. reported a sulfenylation reaction of indoles
with sulfonyl hydrazides through the cleavage of sulfur-oxygen and
sulfur-nitrogen bonds (Scheme 2) [19].
Inspired by the literature results, hydroxysulfenylation of
unactivated C]C double bonds were proposed using sulfonyl hy-
drazides as the sulfenylating agents. It was assumed that attack of
sulfenylating agents on C]C double bonds formed a thiiranium ion
(episulfonium ion) intermediate [20], and subsequent acidic hy-
Reaction conditions:
a
1a (0.25 mmol), 2a (0.5 mmol, 2.0 equiv), oxidant (1.0 mmol, 4.0 equiv), I or Br
source (0.2 equiv), bpy ¼ 2,20-dipyridyl, solvent (2.0 mL), at 120 ꢀC under air at-
mosphere for 24 h.
b
In all cases compound 3aa was obtained as a single regioisomer.
Isolated yield based on 1a.
0.4 equiv of catalyst was used.
Styrene was used.
c
d
e
f
ND ¼ not detected.
g
Allyl benzene was used.
h
Reaction carried out under argon atmosphere.
drolysis yielded the desired b-hydroxysulfide products. To test this
isolated in 55% yield when FeBr3-bpy was used as the catalyst
(Table 1, entry 7). The reaction media were also screened. 1,4-
Dioxane/H2O was found to be the most suitable reaction medium
and the desired 3aa was obtained in 74% yield. Reactions in the
absence of H2O (entry 12), or replacing H2O with alcohol (entry 17)
gave product in reduced isolated yield possibly due to the con-
sumption of the oxidant by the solvent alcohol. No reaction was
observed when styrene (entry 18) or allylbenzene (entry 19) was
used as the substrate possibly due to the high reactivity of such
substrates under the designed reaction conditions. Similar isolated
yield was obtained when the reaction was carried out under argon
atmosphere under otherwise identical conditions (entry 20). Re-
actions in toluene, 1,2-dichloroethane (DCE) and other solvents
were not successful.
With the optimized conditions in hand, the synthetic viability of
the reactions was studied with a variety of N-allyl-N-sulfonamides
as the substrates and benzenesulfonyl hydrazide 2a as the sulfur
source. The results are summarized in Table 2. As shown in Table 2,
the hydroxysulfenylation reaction tolerated a wide range of N-allyl-
N-sulfonamides. Substituted phenyl groups, including electron-
donating groups such as 4-Me (1b), 4-tBu (1c), 4-EtO (1d) as well
as electron-withdrawing groups such as 4-F (1g), 4-Cl (1h), 4-Br
(1i) or 4-CF3 (1j) were tested as the N-substituents (R1) of the
substrates. The reactions gave compounds 3ba-3ja in 35e73%
yields. Poor isolated yields were obtained when benzene rings
bearing bulky group (3ca), or m-/o-substituents (3ea, 3fa, 3va),
indicating that steric hindrance of substituents has a great effect on
assumption, hydroxysulfenylation of N-allyl-N-p-tolylbenzene-
sulfonanilide (1a) with benzenesulfonyl hydrazide (2a) was
selected as the model reaction, Na2S2O8 was chosen as the oxidant
based on our understanding of halogen-mediated reactions
(Table 1) [21].
This type of compounds were chosen as model substrates as the
reaction could lead to multi-functional structures which would find
widespread application in organic synthesis and drug design.
Various iodine sources such as I2, KI, NaI, NIS, and CuI-bpy were first
utilized as the catalysts, and the reactions produced the desired b-
hydroxysulfide 3aa as a single regioisomer in merely poor yields
possibly due to the weak oxidation property of iodine (Table 1,
entry 1) [22]. Other facile bromine sources such as KBr, TMSBr or
NBS were then used to replace iodine, and slightly increased yields
were obtained (Table 1, entries 2e4). Encouraged by these results, a
wide range of transition metal bromides with 2,20-dipyridyl ligand
were screened (Table 1, entries 5e10). In general, the catalytic ac-
tivity of metal bromides was significantly enhanced upon addition
of 2,20-dipyridyl ligand, and the desired
b-hydroxysulfide can be
Scheme 2. Sulfenylation of Indoles with Sulfonyl Hydrazides.

Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
645
Table 2
Table 3
Reaction Scope of N-Allyl-N-sulfonamides.a
Reaction Scope of Sulfonyl Hydrazides.a
entry
R3
product
yield (%)b
entry
R1
R2
3
yield (%)b
1
2
3
4
5
6
7
8
9
(2b) 4-MePh
(2c) 3-MePh
(2d) 4-tBuPh
(2e) 4-FPh
3 ab
3ac
3ad
3ae
3af
3 ag
3ah
3ai
66
47
56
74
72
66
54
64
61
22
1
2
3
4
5
6
7
8
(1a) Ph
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
4-MePh
Me
3aa
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
3ja
3ka
3la
3ma
3na
3oa
3pa
3qa
3ra
3sa
74
73
35
60
49
trace
71
73
64
40
75
80
61
63
77
76
44
61
74
67
(1b) 4-MePh
(1c) 4-tBuPh
(1d) 4-EtOPh
(1e)3-MePh
(1f)2-MePh
(1g) 4-FPh
(1h) 4-ClPh
(1i) 4-BrPh
(1j) 4-CF3Ph
(1k) Benzyl
(1l) Et
(1m) n-Butyl
(1n) Cy
(1o) MeO
(1p) Ph
(1q) Ph
(1r) Ph
(2f) 4-ClPh
(2g) 4-BrPh
(2h) 4-CF3Ph
(2i) 4-NO2Ph
(2j) 2-naphthyl
(2k) n-Bu
3aj
3ak
9
10
10
11
12
13
14
15
16
17
18
19
20
Reaction conditions:
a
1a (0.25 mmol), 2 (0.5 mmol, 2.0 equiv), Na2S2O8 (1.0 mmol, 4.0 equiv), FeBr3-
bpy (0.2 equiv), 1, 4-dioxane (2.0 mL), H2O (0.1 mL) at 120 ꢀC under air atmosphere
for 24 h.
b
Isolated yield based on 1a.
4-NO2Ph
CF3
Ph
(1s) Ph
21
22
(1u) H
(1v) 2,4,6-TriMePh
4-MePh
4-MePh
3ua
3va
0
0
Reaction conditions:
a
1 (0.25 mmol), 2a (0.5 mmol, 2.0 equiv), Na2S2O8 (1.0 mmol, 4.0 equiv), FeBr3-
bpy (0.2 equiv), 1,4-dioxane (2.0 mL), H2O (0.1 mL) at 120 ꢀC under air atmosphere
for 24 h.
b
Isolated yield based on 1a.
the reaction. Reactions of substrates bearing benzyl (1k), aliphatic
(1l, 1m, 1n) or alkoxy (1o) groups on nitrogen atoms of the sul-
fonamides could also proceed readily, providing the corresponding
3ka-3oa in satisfactory isolated yields.
Fig. 1. ORTEP drawing of compound 3ai at 30% probability displacement ellipsoid (the
hydrogen atoms are omitted for clarity).
N-Allyl-N-sulfonamides bearing different sulfonyl groups were
also studied. Study showed that the hydroxysulfenylation reaction
could not proceed without sulfonyl groups in the substrates.
Methanesulfonyl group was well suitable for the reaction, and the
desired product 3pa could be obtained in good yield. N-Arylsulfonyl
substrates with electron-withdrawing group CF3- or 4-NO2 in
phenyl ring could also react with 2a, giving the desired products
3qa, 3ra in moderate yields. The reaction of N-homoallyl N-sul-
fonamide 1t was also tested, and the desired product was obtained
in 67% isolated yield (entry 20). No desired product was obtained
when 1u (R1 ¼ H) was subjected to the reaction (entry 21).
The reaction scope of aryl sulfonyl hydrazides (2b-2k) was also
investigated under standard conditions. The results are summa-
rized in Table 3. In addition to p- and m-toluenesulfonyl hydrazides
2b and 2c, other substituted arenesulfonyl hydrazides 2d-2h could
3aa as a model compound. As shown in Scheme 3, valuable func-
tional groups such as sulfone, alkoxy, azido group could be easily
obtained in high yields via conventional functional group trans-
formation reactions (Scheme 3).
also undergo the reaction, giving the desired b-hydroxysulfides in
47e74% yields. The structure of 3ai was further confirmed by X-ray
diffraction analysis (Fig. 1) [22]. In addition, n-butanesulfonyl hy-
drazide 2k could also be used as the hydroxysulfenylating agent to
give the desired product 3ak. This will avoid the use of generally
bad odored thiols.
To demonstrate the application potential of this reaction, several
derivatization reactions were carried out using b-hydroxysulfide
Scheme 3. Derivatization of b
-Hydroxysulfide.a

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Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
To understand the mechanism of the reaction, different control
hydrazide 2, bromine source and a suitable oxidant, sulfenyl bro-
mide intermediate A is first in situ produced [17e-h,19]. This in-
termediate undergoes electrophilic addition to alkene 1 to give
thiiranium ion intermediate B. Subsequent ring-opening of thiira-
reactions were performed. No inhibition was observed when excess
amount (2.0 equiv) of TEMPO or BHT (2, 6-di-tert-butyl-4-methyl-
phenol) was added to the reaction mixture of the model reaction,
suggesting a non-radical process of the reaction. Consistent with
previous studies [23], sulfonothioate 8 and disulfide 9 were formed
when sulfonyl hydrazide 2b decomposed in the presence of bro-
mide and an oxidant (Scheme 4a). Desired product 3 ab was ob-
tained in 35% and 38% yield, respectively, when 8 and 9 were
treated with N-allyl-N-sulfonamide (1a) under model reaction
condition. The yield of these reactions was lower than that with
sulfonyl hydrazide 2b (Scheme 4b), suggesting that the decompo-
sition species 8 or 9 didn't serve as major intermediates in the
nium ion B with H2O under acidic conditions gave
3 as the final product.
b-hydroxysulfide
3. Conclusion
In summary, we have reported a b-hydroxysulfenylation reac-
tion of terminal olefins with sulfonyl hydrazides. In the presence of
a suitable bromine source and an oxidant, a range of sulfonyl hy-
drazides could react with alkenes, providing the desired
b-
formation of
b-hydroxysulfide 3 ab. No target product 3 ab was
hydroxysulfide in moderate to good yields. A variety of functional
groups such as Fꢁ, Clꢁ, Brꢁ, CF3ꢁ, alkoxy could be tolerated. To the
best of our knowledge, this is the first example that sulfonyl hy-
drazides could serve as sulfur source in b-hydroxysulfenylation of
unactivated olefins. Application of this transformation in organic
obtained when epoxide substrate 10 in replace of N-allyl-N-sul-
fonamide 1a was used in this hydroxysulfenylation reaction
(Scheme 4c), suggesting that the epoxide intermediate was not
involved in the reaction.
Kumar et al. showed that molecular oxygen was involved in an
iodine-triggered aerobic oxysulfonylation of styrenes [24]. In the
current reaction system, reactions carried out under air atmosphere
or under argon atmosphere gave product in similar isolated yields
[22], suggesting that O2 made no contribution to the hydrox-
ysulfenylation of N-allylsulfonamides. Reaction in dry 1,4-dioxane
or in 1,4-dioxane/ethanol gave product in reduced isolated yields,
suggesting that H2O played a role in the reaction. Based on these
observations and the previously reported results, a plausible reac-
tion pathway is proposed in Scheme 5. In the presence of sulfonyl
synthesis is underway.
4. Experimental section
4.1. General experimental information
Reactions were carried out with commercially available re-
agents in oven-dried apparatus. 1H and 13C NMR spectra were
recorded on a Bruker DRX 400 spectrometer at 298 K using
deuterated chloroform as solvent and TMS as internal reference.
Column chromatography was performed employing 200e300
mesh silica gel unless otherwise noted. Thin layer chromatography
(TLC) was performed on silica gel GF254. Melting points were
measured on a digital melting-point apparatus without correction
of the thermometer. HRMS analyses were carried out with Varian
FTICR-MS 7.0T. IR spectra were recorded on a BRUKER TENSOR 37.
Unless otherwise indicated, starting materials and reagents used in
the study were purchased and were used as received without
further purification.
4.2. Typical procedure for the b-hydroxysulfenylation of N-allyl-
sulfonamides with sulfonyl hydrazides
A 35 mL Schlenk-type tube (with a Teflon high pressure valve)
equipped with a magnetic stir bar was charged with N-allyl-N-p-
tolylbenzenesulfonamide (1a, 0.25 mmol, 71.8 mg) and benzene
sulfonyl hydrazide (2a, 0.5 mmol, 86.1 mg). Then, FeBr3 (0.05 mmol,
14.7 mg), 2,20-dipyridyl (0.05 mmol, 7.8 mg), Na2S2O8 (1 mmol,
0.238 g), 1,4-dioxane (2 mL), and H2O (0.1 mL) were added to this
system. The tube was then sealed and placed in an oil bath at
120 ꢀC. After the reaction mixture was stirred for 24 h, it was
allowed to cool to ambient temperature (Caution! The tube must be
opened with care!). The reaction mixture was filtered and evapo-
rated to give the crude product. The residue was purified by column
chromatography (ethyl acetate: petroleum ether ¼ 1: 10, v/v) to
afford the desired product 3aa.
Scheme 4. Control Reactions.
4.2.1. N-(2-Hydroxy-3-(phenylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (3aa)
Compound 3aa was prepared according to the general proced-
ure and was isolated as colorless oil (76.5 mg, 74% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 8.3 Hz, 2H), 7.24 - 7.09 (m, 10H), 6.96
- 6.92 (m, 2H), 3.69 - 3.56 (m, 3H), 3.14 (dd, J ¼ 14.0, 4.7 Hz,1H), 2.90
(dd, J ¼ 14.0, 6.9 Hz, 1H), 2.71 (d, J ¼ 3.2 Hz, 1H), 2.35 (s, 3H). 13C
Scheme 5. Possible Pathways of the Reactions.
NMR (101 MHz, CDCl3) d 142.8, 138.6, 133.8, 133.6, 129.0, 128.5,

Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
647
128.2, 128.0, 127.6, 127.1, 126.7, 125.6, 66.9, 54.4, 37.9, 20.6. IR (KBr):
4.2.6. N-(4-Fluorophenyl)-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3ga)
Compound 3ga was prepared according to the general proced-
ure and was isolated as yellow oil (76.5 mg, 71% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
y
¼ 3505.0, 3059.2, 1595.2, 1491.2, 1163.3, 696.4, 549.4 cmꢁ1. HRMS
(ESI) (m/z): [MþH]þ calcd for: C22H24NO3Sþ2 , 414.1192; found:
414.1195.
(400 MHz, CDCl3)
6.87 (m, 3H), 3.67 - 3.61 (m, 1H), 3.60 - 3.52 (m, 2H), 3.12 (dd,
d
7.36 (d, J ¼ 8.3 Hz, 2H), 7.22 - 7.12 (m, 8H), 6.91 -
4.2.2. N-(2-Hydroxy-3-(phenylthio)propyl)-4-methyl-N-(p-tolyl)
benzenesulfonamide (3ba)
Compound 3ba was prepared according to the general proced-
ure and was isolated as colorless oil (78.0 mg, 73% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
J ¼ 14.0, 4.8 Hz, 1H), 2.90 (dd, J ¼ 14.0, 7.1 Hz, 1H), 2.36 (s, 3H), 2.31
(s, 1H). 19F NMR (376 MHz, CDCl3)
d
ꢁ112.6. 13C NMR (101 MHz,
CDCl3)
d
161.96 (d, J ¼ 249.0 Hz), 144.0, 135.63 (d, J ¼ 3.1 Hz), 130.5,
130.4, 130.3, 129.6, 129.1, 127.8, 127.3, 126.8, 124.86 (d, J ¼ 8.4 Hz),
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 8.2 Hz, 2H), 7.21 - 7.09 (m, 7H), 7.00
116.11 (d, J ¼ 22.7 Hz), 67.9, 55.6, 39.1, 21.6. IR (KBr):
y
¼ 3503.0,
3063.6, 1748.5, 1505.3, 1163.7, 812.3, 690.6, 552.1 cmꢁ1. HRMS (ESI)
(m/z): [MþH]þ calcd for: C22H23FNO3Sþ2 , 432.1098; found:
432.1095.
(d, J ¼ 8.2 Hz, 2H), 6.81 (d, J ¼ 8.2 Hz, 2H), 3.68 - 3.62 (m, 1H), 3.60 -
3.55 (m, 2H), 3.12 (dd, J ¼ 13.9, 4.9 Hz, 1H), 2.89 (dd, J ¼ 13.9, 7.2 Hz,
1H), 2.42 (s,1H), 2.35 (s, 3H), 2.25 (s, 3H). 13C NMR (101 MHz, CDCl3)
d
143.7, 138.2, 137.0, 135.1, 134.8, 130.0, 129.8, 129.5, 129.0, 128.4,
127.8, 126.6, 68.0, 55.5, 39.0, 21.6, 21.1. IR (KBr):
y
¼ 3507.2, 3055.8,
4.2.7. N-(4-Chlorophenyl)-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3ha)
Compound 3ha was prepared according to the general proced-
ure and was isolated as yellow oil (81.6 mg, 73% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
1745.7, 1597.7, 1161.9, 587.6, 552.3 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ
calcd for: C23H26NO3Sþ2 , 428.1349; found: 428.1352.
4.2.3. N-(4-(tert-Butyl)phenyl)-N-(2-hydroxy-3-(phenylthio)
propyl)-4-methylbenzenesulfonamide (3ca)
Compound 3ca was prepared according to the general proced-
ure and was isolated as colorless oil (41.1 mg, 35% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.36 (d, J ¼ 8.2 Hz, 2H), 7.21 - 7.12 (m, 9H), 6.86
(d, J ¼ 8.6 Hz, 2H), 3.66 - 3.61 (m, 1H), 3.60 - 3.52 (m, 2H), 3.10 (dd,
J ¼ 14.0, 4.6 Hz, 1H), 2.89 (dd, J ¼ 14.0, 7.1 Hz, 1H), 2.39 (s, 1H), 2.35
(s, 3H). 13C NMR (101 MHz, CDCl3)
d 144.1, 138.3, 134.7, 134.4, 134.0,
130.2, 129.9, 129.6, 129.4, 129.1, 127.7, 126.8, 68.0, 55.3, 39.1, 21.6. IR
(400 MHz, CDCl3)
d
7.39 (d, J ¼ 8.3 Hz, 2H), 7.23 - 7.08 (m, 9H), 6.85
(KBr):
y
¼ 3427.5, 3090.9, 1487.7, 1155.2, 667.6, 582.4, 549.8 cmꢁ1
.
(d, J ¼ 8.6 Hz, 2H), 3.66 - 3.60 (m, 1H), 3.59 - 3.52 (m, 2H), 3.13 (dd,
HRMS (ESI) (m/z): [MþH]þ calcd for: C22H23ClNO3Sþ2 ,448.0802;
J ¼ 14.0, 4.8 Hz, 1H), 2.89 (dd, J ¼ 13.9, 7.1 Hz, 1H), 2.36 (s, 3H), 2.33
found: 448.0797.
(s, 1H), 1.23 (s, 9H).13C NMR (101 MHz, CDCl3)
d 150.2, 142.6, 135.7,
133.9, 133.8, 129.1, 128.5, 127.9, 126.9, 126.8, 125.6, 125.1, 66.7, 54.5,
4.2.8. N-(4-Bromophenyl)-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3ia)
37.9, 33.6, 30.3, 20.6. IR (KBr):
y
¼ 3522.9, 3057.6, 1744.5, 1597.2,
1346.0, 591.2, 550.5 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ calcd for:
Compound 3ia was prepared according to the general procedure
and was isolated as yellow solid (78.2 mg, 64% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). m.p. 80e83 ꢀC.
C
26H32NO3Sþ2 , 470.1817; found: 470.1818.
1H NMR (400 MHz, CDCl3)
d
7.34 (dd, J ¼ 14.8, 8.5 Hz, 4H), 7.21 - 7.11
4.2.4. N-(4-Ethoxyphenyl)-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3da)
Compound 3da was prepared according to the general proced-
ure and was isolated as yellow oil (68.6 mg, 60% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(m, 7H), 6.80 (d, J ¼ 8.7 Hz, 2H), 3.66 - 3.60 (m, 1H), 3.59 - 3.51 (m,
2H), 3.09 (dd, J ¼ 14.0, 4.8 Hz,1H), 2.89 (dd, J ¼ 14.0, 7.1 Hz,1H), 2.73
(s, 1H), 2.35 (s, 3H). 13C NMR (101 MHz, CDCl3)
d 144.1, 138.8, 134.7,
134.4, 132.4, 130.2, 129.7, 129.1, 127.7, 126.8, 122.1, 68.0, 55.3, 39.1,
21.6. IR (KBr):
y
¼ 3554.3, 3069.5, 1483.0, 749.4, 663.7, 581.2,
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 8.1 Hz, 2H), 7.22 - 7.09 (m, 7H), 6.81
550.7 cmꢁ1
.
HRMS
(ESI)
(m/z):
[MþH]þ
calcd
for:
(d, J ¼ 8.9 Hz, 2H), 6.71 - 6.67 (m, 2H), 3.93 (q, J ¼ 7.0 Hz, 2H), 3.69 -
3.62 (m, 1H), 3.59 - 3.51 (m, 1H), 3.12 (dd, J ¼ 13.9, 5.0 Hz, 1H), 2.90
(dd, J ¼ 13.9, 7.2 Hz, 1H), 2.75 (d, J ¼ 3.4 Hz, 1H), 2.35 (s, 3H), 1.34 (t,
C
22H23BrNO3Sþ2 ,492.0297; found: 492.0297.
J ¼ 6.9 Hz, 3H). 13C NMR (101 MHz, CDCl3)
d 158.6, 143.7, 135.1,
4.2.9. N-(2-Hydroxy-3-(phenylthio)propyl)-4-methyl-N-(4-
(trifluoromethyl)phenyl)benzene-sulfonamide (3ja)
Compound 3ja was prepared according to the general procedure
and was isolated as yellow oil (48.1 mg, 40% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
134.8, 131.9, 130.1, 129.8, 129.5, 129.0, 127.8, 126.6, 114.8, 68.0, 63.7,
55.7, 39.0, 21.6, 14.8. IR (KBr):
y
¼ 3509.2, 3056.3, 1750.9, 1599.8,
1161.6, 805.8, 572.8, 547.9 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ calcd
for: C24H28NO4Sþ2 , 458.1454; found: 458.1453.
(400 MHz, CDCl3)
d
7.47 (d, J ¼ 8.4 Hz, 2H), 7.35 (d, J ¼ 8.3 Hz, 2H),
7.21 - 7.11 (m, 7H), 7.08 (d, J ¼ 8.4 Hz, 2H), 3.69 - 3.55 (m, 3H), 3.15 -
4.2.5. N-(2-Hydroxy-3-(phenylthio)propyl)-4-methyl-N-(m-tolyl)
benzenesulfonamide (3ea)
Compound 3ea was prepared according to the general proced-
ure and was isolated as yellow oil (52.3 mg, 49% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
3.06 (m, 1H), 2.93 - 2.84 (m, 1H), 2.36 (s, 3H), 2.18 (s, 1H). 19F NMR
(376 MHz, CDCl3)
d
ꢁ62.6. 13C NMR (101 MHz, CDCl3)
d 143.2, 142.0,
133.5, 133.3, 129.3, 128.80 (q, J ¼ 32.9 Hz), 128.7, 128.1, 127.7,
d
126.70 (q, J ¼ 272.1 Hz), 126.6, 125.9, 125.22 (q, J ¼ 3.3 Hz). IR
(KBr):
y
¼ 3501.4, 3062.5, 1613.8, 1165.5, 662.0, 548.6 cmꢁ1. HRMS
(400 MHz, CDCl3)
d
7.38 (d, J ¼ 8.1 Hz, 2H), 7.21 - 7.15 (m, 5H), 7.13 -
(ESI) (m/z): [MþH]þ calcd for: C23H23F3NO3S2þ, 482.1066; found:
7.00 (m, 4H), 6.81 (s, 1H), 6.66 (d, J ¼ 7.8 Hz, 1H), 3.68 - 3.62 (m, 1H),
3.61 - 3.54 (m, 2H), 3.13 (dd, J ¼ 14.0, 4.8 Hz, 1H), 2.89 (dd, J ¼ 14.0,
7.1 Hz, 1H), 2.74 (d, J ¼ 3.3 Hz, 1H), 2.35 (s, 3H), 2.21 (s, 3H). 13C NMR
482.1061.
4.2.10. N-Benzyl-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3ka)
(101 MHz, CDCl3)
d 143.7, 139.6, 139.2, 135.0, 134.8, 130.0, 129.7,
129.4, 129.0, 128.9, 128.3, 127.8, 126.6, 125.2, 67.9, 55.5, 39.0, 21.6,
Compound 3ka was prepared according to the general proced-
ure and was isolated as yellow oil (80.2 mg, 75% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
21.3. IR (KBr):
y
¼ 3504.3, 3055.4, 1599.6, 1161.5, 812.5, 694.9,
581.4 cmꢁ1.HRMS (ESI) (m/z): [MþH]þ calcd for: C23H26NO3Sþ2 ,
428.1349; found: 428.1351.
(400 MHz, CDCl3)
d
7.63 (d, J ¼ 8.0 Hz, 2H), 7.23 (d, J ¼ 8.0 Hz, 2H),

648
Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
7.19 - 7.10 (m, 10H), 4.40 - 4.13 (m, 2H), 3.52 (dt, J ¼ 12.5, 7.2 Hz, 1H),
3.24 - 3.06 (m, 2H), 2.76 (qd, J ¼ 13.9, 6.3 Hz, 2H), 2.41 (s, 1H), 2.36
4.2.15. N-(2-Hydroxy-3-(phenylthio)propyl)-N-phenylmethane
sulfonamide (3pa)
Compound 3pa was prepared according to the general proced-
ure and was isolated as yellow oil (64.0 mg, 76% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(s, 3H). 13C NMR (101 MHz, CDCl3)
d
143.7, 136.0, 135.9, 135.0, 129.9,
129.6, 129.0, 128.7, 128.6, 128.1, 127.3, 126.5, 68.2, 53.9, 53.4, 38.7,
21.6. IR (KBr):
y
¼ 3503.3, 3061.1, 1597.7, 1336.3, 739.0, 656.8,
549.8 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ calcd for: C23H26NO3Sþ2 ,
(400 MHz, CDCl3)
3.66 (m, 3H), 3.60 (s, 1H), 3.06 (dd, J ¼ 13.8, 4.6 Hz, 1H), 2.91 - 2.80
(m, 4H). 13C NMR (101 MHz, CDCl3)
139.5,134.8,130.2,129.7,129.1,
d 7.33 - 7.23 (m, 5H), 7.22 - 7.08 (m, 5H), 3.84 -
428.1349; found: 428.1349.
d
128.6, 128.4, 126.8, 68.1, 55.6, 39.1, 37.5. IR (KBr):
y
¼ 3499.7, 3059.7,
4.2.11. N-Ethyl-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3la)
Compound 3la was prepared according to the general procedure
and was isolated as yellow oil (73.1 mg, 80% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
1584.8, 1152.1, 962.1, 694.5, 543.9 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ
calcd for: C16H20NO3Sþ2 , 338.0879; found: 338.0878.
4.2.16. N-(2-Hydroxy-3-(phenylthio)propyl)-4-nitro-N-
phenylbenzenesulfonamide (3qa)
Compound 3qa was prepared according to the general proced-
ure and was isolated as yellow oil (48.8 mg, 44% yield) after flash
chromatography (EtOAc/Petroleum ether 20% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.60 (d, J ¼ 8.3 Hz, 2H), 7.31 (d, J ¼ 8.6 Hz, 2H),
7.25 - 7.19 (m, 4H), 7.17 - 7.11 (m, 1H), 3.83 (p, J ¼ 6.6, 5.6 Hz, 1H),
3.26 - 2.93 (m, 6H), 2.34 (s, 3H), 0.99 (t, J ¼ 7.2 Hz, 3H). 13C NMR
(101 MHz, CDCl3)
d 143.5, 136.2, 135.0, 129.9, 129.8, 129.1, 127.2,
(400 MHz, CDCl3)
d
8.21 (d, J ¼ 8.7 Hz, 2H), 7.67 (d, J ¼ 8.7 Hz, 2H),
126.7, 68.9, 52.7, 45.0, 38.8, 21.5, 13.9. IR (KBr):
y
¼ 3503.4, 3058.8,
1383.4, 1185.8, 739.5, 653.3, 551.3 cmꢁ1
. HRMS (ESI) (m/z):
7.28 - 7.12 (m, 8H), 6.93 (dd, J ¼ 7.5,1.8 Hz, 2H), 3.66 (s, 3H), 3.12 (dd,
J ¼ 12.9, 2.9 Hz, 1H), 2.95 - 2.84 (m, 1H), 2.60 (s, 1H). 13C NMR
[MþNa]þ calcd for: C18H23NO3S2Naþ, 388.1012; found: 388.1015.
(101 MHz, CDCl3)
d 150.2, 143.7, 138.6, 134.6, 130.3, 129.6, 129.1,
128.9, 128.8, 128.6, 127.0, 124.1, 67.8, 55.7, 39.2. IR (KBr):
y
¼ 3510.4,
4.2.12. N-Butyl-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3ma)
Compound 3ma was prepared according to the general pro-
cedure and was isolated as yellow oil (60 mg, 61% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
3062.7, 1529.6, 1165.8, 853.5, 607.2, 563.7 cmꢁ1. HRMS (ESI) (m/z):
[MþNa]þ calcd for: C21H20N2O5S2Naþ, 467.0706; found: 467.0710.
4.2.17. 1,1,1-Trifluoro-N-(2-hydroxy-3-(phenylthio)propyl)-N-
phenylmethanesulfonamide (3ra)
Compound 3ra was prepared according to the general proced-
ure and was isolated as yellow oil (59.6 mg, 61% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.59 (d, J ¼ 8.3 Hz, 2H), 7.33 - 7.28 (m, 2H), 7.25 -
7.19 (m, 4H), 7.14 (t, J ¼ 7.3 Hz, 1H), 3.87 - 3.76 (m, 1H), 3.20 (dd,
J ¼ 14.8, 3.8 Hz, 1H), 3.14 - 2.92 (m, 5H), 2.35 (s, 3H), 1.37 (p,
J ¼ 7.5 Hz, 2H), 1.15 (dq, J ¼ 14.5, 7.2 Hz, 2H), 0.75 (t, J ¼ 7.4 Hz, 3H).
(400 MHz, CDCl3)
d 7.34 - 7.29 (m, 3H), 7.26 - 7.14 (m, 7H), 3.83 (d,
13C NMR (101 MHz, CDCl3)
d 143.5, 135.9, 134.9, 129.9, 129.8, 129.1,
J ¼ 6.0 Hz, 2H), 3.63 (dq, J ¼ 11.6, 5.7 Hz, 1H), 3.03 (dd, J ¼ 14.0,
127.3, 126.7, 68.9, 53.6, 50.5, 38.8, 30.6, 21.5, 19.8, 13.6. IR (KBr):
4.3 Hz, 1H), 2.83 (dd, J ¼ 14.0, 7.5 Hz, 1H), 2.42 (d, J ¼ 4.7 Hz, 1H). 13
C
y
¼ 3503.1, 2958.9, 1598.0, 1156.9, 741.0, 655.9, 550.4 cmꢁ1. HRMS
NMR (101 MHz, CDCl3)
d 137.0, 134.3, 130.9, 129.7, 129.4, 129.2,
(ESI) (m/z): [MþH]þ calcd for: C20H28NO3Sþ2 , 394.1505; found:
128.9, 127.3, 120.4(q, J ¼ 322.8 Hz), 67.1, 57.3, 39.6. IR (KBr):
394.1508.
y
¼ 3554.6, 3063.2, 1492.4, 1194.3, 695.5, 602.6 cmꢁ1. HRMS (ESI)
(m/z): [MþNa]þ calcd for: C16H16F3NO3S2Naþ, 414.0416; found:
4.2.13. N-Cyclohexyl-N-(2-hydroxy-3-(phenylthio)propyl)-4-
methylbenzenesulfonamide (3na)
414.0420.
Compound 3na was prepared according to the general proced-
ure and was isolated as yellow oil (66.1 mg, 63% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
4.2.18. N-(2-Hydroxy-3-(phenylthio)propyl)-N-
phenylbenzenesulfonamide (3sa)
Compound 3sa was prepared according to the general proced-
ure and was isolated as yellow oil (73.9 mg, 74% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.62 (d, J ¼ 8.3 Hz, 2H), 7.32 (d, J ¼ 7.3 Hz, 2H),
7.22 (t, J ¼ 7.7 Hz, 4H), 7.12 (t, J ¼ 7.3 Hz,1H), 3.91 - 3.82 (m, 1H), 3.61
- 3.52 (m, 1H), 3.49 (d, J ¼ 2.8 Hz, 1H), 3.32 (dd, J ¼ 15.4, 3.4 Hz, 1H),
3.16 - 3.02 (m, 2H), 2.96 (dd, J ¼ 13.9, 6.8 Hz, 1H), 2.34 (s, 3H), 1.63 -
1.44 (m, 4H), 1.35 - 1.24 (m, 1H), 1.19 - 1.08 (m, 4H), 0.95 - 0.81 (m,
(400 MHz, CDCl3)
d
7.55 - 7.46 (m, 3H), 7.38 (t, J ¼ 7.3 Hz, 2H), 7.26 -
7.10 (m, 8H), 6.95 - 6.90 (m, 2H), 3.68 - 3.55 (m, 3H), 3.14 (dd,
J ¼ 14.0, 3.8 Hz, 1H), 2.90 (dd, J ¼ 14.0, 6.5 Hz, 1H), 2.72 (s, 1H). 13
C
1H). 13C NMR (101 MHz, CDCl3)
d
143.4, 137.4, 135.3, 129.8, 129.6,
NMR (101 MHz, CDCl3)
d 139.5, 137.7, 134.9, 133.0, 130.1, 129.2,
129.1, 127.1, 126.5, 70.2, 58.7, 48.6, 38.6, 32.1, 30.8, 26.1, 25.9, 25.2,
129.0, 128.9, 128.6, 128.3, 127.7, 126.7, 68.0, 55.5, 39.1. IR (KBr):
y
¼ 3509.2, 3056.3, 1508.0, 1161.6, 805.8, 572.8, 547.9 cmꢁ1. HRMS
21.5. IR (KBr):
y
¼ 3489.9, 2932.5, 1451.4, 814.4, 662.1,
572.6 cmꢁ1.HRMS (ESI) (m/z): [MþH]þ calcd for: C22H30NO3Sþ2 ,
(ESI) (m/z): [MþH]þ calcd for: C21H22NO3Sþ2 , 400.1036; found:
420.1662; found: 420.1665.
400.1037.
4.2.14. N-(2-Hydroxy-3-(phenylthio)propyl)-N-methoxy-4-
methylbenzenesulfonamide (3oa)
4.2.19. N-(3-Hydroxy-4-(phenylthio)butyl)-4-methyl-N-
phenylbenzenesulfonamide (3ta)
Compound 3oa was prepared according to the general proced-
ure and was isolated as yellow oil (70.6 mg, 77% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
Compound 3ta was prepared according to the general procedure
and was isolated as yellow oil (71.6 mg, 67% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(400 MHz, CDCl3)
d
7.63 (d, J ¼ 8.3 Hz, 2H), 7.32 (d, J ¼ 7.2 Hz, 2H),
(400 MHz, CDCl3)
- 6.82 (m, 2H), 3.90 - 3.71 (m, 2H), 3.50 - 3.40 (m, 1H), 2.99 (d,
d
7.38 (d, J ¼ 7.8 Hz, 2H), 7.29 - 7.12 (m, 10H), 6.93
7.28 - 7.14 (m, 5H), 3.88 - 3.80 (m, 1H), 3.73 (s, 3H), 3.11 (dd, J ¼ 14.0,
4.6 Hz, 1H), 3.03 - 2.86 (m, 3H), 2.67 (s, 1H), 2.37 (s, 3H). 13C NMR
J ¼ 13.7 Hz, 1H), 2.89 - 2.75 (m, 2H), 2.35 (s, 3H), 1.68 - 1.56 (m, 1H),
(101 MHz, CDCl3)
d
145.1, 134.9, 130.5, 129.6, 129.5, 129.1, 127.8,
1.53 - 1.42 (m, 1H). 13C NMR (101 MHz, CDCl3)
d 143.5, 138.8, 135.2,
126.9, 67.2, 65.1, 58.0, 39.6, 21.7. IR (KBr):
y
¼ 3516.8, 3057.5, 1596.9,
135.0, 129.9, 129.5, 129.1, 128.7, 128.2, 128.0, 127.7, 126.6, 66.3, 47.3,
1352.3, 1167.7, 744.3, 578.0 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ calcd
41.3, 34.3, 21.6. IR (KBr):
y
¼ 3513.3, 3059.8, 1379.6, 1163.4, 696.3,
for: C17H22NO4Sþ2 ,368.0985; found: 368.0989.
543.9 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ calcd for: C23H26NO3Sþ2 ,

Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
649
428.1349; found: 428.1346.
6H), 7.11 (s, 3H), 6.96 - 6.89 (m, 2H), 3.71 - 3.48 (m, 3H), 3.10 (dd,
J ¼ 14.0, 4.7 Hz, 1H), 2.88 (dd, J ¼ 14.0, 6.9 Hz, 1H), 2.69 (s, 1H), 2.36
4.2.20. N-(2-Hydroxy-3-(p-tolylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (3 ab)
Compound 3 ab was prepared according to the general pro-
cedure and was isolated as yellow oil (70.8 mg, 66% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(s, 3H). 13C NMR (101 MHz, CDCl3)
d 143.9, 139.7, 134.6, 133.6, 132.8,
131.5, 129.5, 129.2, 129.1, 128.6, 128.2, 127.8, 68.0, 55.4, 39.2, 21.6. IR
(KBr):
y
¼ 3506.2, 3063.0, 1476.4, 1157.7, 657.9, 575.9 cmꢁ1. HRMS
(ESI) (m/z): [MþH]þ calcd for: C22H23ClNO3Sþ2 , 448.0802; found:
448.0805.
(400 MHz, CDCl3)
(d, J ¼ 7.7 Hz, 2H), 6.97 - 6.90 (m, 4H), 3.65 - 3.53 (m, 3H), 3.10 - 3.00
(m, 1H), 2.89 - 2.79 (m, 1H), 2.76 (s, 1H), 2.34 (s, 3H), 2.22 (s, 3H). 13
NMR (101 MHz, CDCl3) 143.8,139.7,136.9,134.7,131.1,130.9,129.8,
d
7.36 (d, J ¼ 7.9 Hz, 2H), 7.22 - 7.13 (m, 5H), 7.08
4.2.25. N-(3-((4-Bromophenyl)thio)-2-hydroxypropyl)-4-methyl-
N-phenylbenzenesulfonamide (3 ag)
C
d
Compound 3 ag was prepared according to the general pro-
cedure and was isolated as yellow solid (81.3 mg, 66% yield) after
flash chromatography (EtOAc/Petroleum ether 10% v/v). m.p.
129.5, 129.2, 128.7, 128.1, 127.8, 67.9, 55.4, 39.7, 21.6, 21.1. IR (KBr):
y
¼ 3507.1, 3029.5, 1695.7, 1163.2, 697.2, 657.9, 573.8 cmꢁ1. HRMS
(ESI) (m/z): [MþH]þ calcd for: C23H26NO3Sþ2 , 428.1349; found:
88e90 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.36 (d, J ¼ 8.2 Hz, 2H), 7.27 -
428.1352.
7.15 (m, 7H), 7.07 - 7.02 (m, 2H), 6.95 - 6.90 (m, 2H), 3.68 - 3.62 (m,
1H), 3.61 - 3.57 (m, 2H), 3.10 (dd, J ¼ 14.0, 4.8 Hz, 1H), 2.88 (dd,
J ¼ 14.0, 7.0 Hz, 1H), 2.72 (d, J ¼ 3.0 Hz, 1H), 2.35 (s, 3H). 13C NMR
4.2.21. N-(2-Hydroxy-3-(m-tolylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (3ac)
(101 MHz, CDCl3)
d 143.9, 139.7, 134.6, 134.3, 132.1, 131.6, 129.5,
Compound 3ac was prepared according to the general proced-
ure and was isolated as yellow oil (50.2 mg, 47% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
129.2, 128.6, 128.2, 127.8, 120.6, 68.0, 55.4, 39.0, 21.6. IR (KBr):
y
¼ 3482.5, 3063.4, 1473.2, 1155.7, 812.0, 695.9, 548.8 cmꢁ1. HRMS
(ESI) (m/z): [MþH]þ calcd for: C22H23BrNO3Sþ2 , 494.0277; found:
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 8.2 Hz, 2H), 7.23 - 7.16 (m, 6H), 7.02
494.0278.
(t, J ¼ 9.1 Hz, 2H), 6.97 - 6.90 (m, 3H), 3.67 - 3.58 (m, 3H), 3.12 (dd,
J ¼ 14.0, 4.7 Hz, 1H), 2.88 (dd, J ¼ 13.9, 6.9 Hz,1H), 2.71 (d, J ¼ 2.9 Hz,
4.2.26. N-(2-Hydroxy-3-((4-(trifluoromethyl)phenyl)thio)propyl)
-4-methyl-N-phenylbenzene- sulfonamide (3ah)
1H), 2.35 (s, 3H), 2.21 (s, 3H). 13C NMR (101 MHz, CDCl3)
d 143.8,
139.7, 138.9, 134.7, 134.6, 130.8, 129.5, 129.2, 128.9, 128.6, 128.2,
Compound 3ah was prepared according to the general proced-
ure and was isolated as yellow solid (64.9 mg, 54% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). m.p.
127.8, 127.6, 127.2, 68.0, 55.5, 39.0, 21.6, 21.3. IR (KBr):
y
¼ 3507.3,
3034.2, 1594.0, 1163.2, 657.7, 573.7, 549.1 cmꢁ1.HRMS (ESI) (m/z):
[MþH]þ calcd for: C23H26NO3Sþ2 , 428.1349; found: 428.1348.
104e106 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.37 (t, J ¼ 7.3 Hz, 4H), 7.27
- 7.14 (m, 7H), 6.99 - 6.94 (m, 2H), 3.73 (p, J ¼ 5.8 Hz, 1H), 3.63 (d,
J ¼ 5.9 Hz, 2H), 3.20 (dd, J ¼ 14.0, 4.8 Hz, 1H), 2.97 (dd, J ¼ 14.0,
7.2 Hz, 1H), 2.73 (s, 1H), 2.36 (s, 3H). 19F NMR (376 MHz, CDCl3)
4.2.22. N-(3-((4-(tert-Butyl)phenyl)thio)-2-hydroxypropyl)-4-
methyl-N-phenylbenzenesulfonamide (3ad)
Compound 3ad was prepared according to the general proced-
ure and was isolated as yellow oil (65.7 mg, 56% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
d
ꢁ62.5. 13C NMR (101 MHz, CDCl3)
d 144.0, 140.8, 139.7, 134.4,
129.6, 129.3, 128.5, 128.3, 127.8, 125.7(q, J ¼ 3.8 Hz), 122.7(q,
J ¼ 273.0 Hz), 68.1, 55.5, 37.6, 21.6. IR (KBr):
y
¼ 3516.8, 3064.4,
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 7.9 Hz, 2H), 7.24 - 7.09 (m, 9H), 6.97 -
1604.7, 1327.5, 1111.3, 659.3, 577.3 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ
6.91 (m, 2H), 3.68 - 3.54 (m, 3H), 3.14 - 3.04 (m, 1H), 2.86 (dd,
calcd for: C23H23F3NO3S2þ, 482.1066; found: 482.1068.
J ¼ 14.5, 5.3 Hz, 1H), 2.69 (s, 1H), 2.35 (s, 3H), 1.21 (s, 9H). 13C NMR
(101 MHz, CDCl3)
d
150.1, 143.8, 139.7, 134.7, 131.0, 130.4, 129.5,
4.2.27. N-(2-Hydroxy-3-((4-nitrophenyl)thio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (3ai)
129.2, 128.7, 128.2, 127.8, 126.1, 67.8, 55.4, 39.4, 34.5, 31.3, 21.6. IR
(KBr):
y
¼ 3523.6, 3029.0, 1595.7, 1163.1, 814.2, 696.4, 547.7 cmꢁ1
.
Compound 3ai was prepared according to the general procedure
and was isolated as yellow solid (73.3 mg, 64% yield) after flash
chromatography (EtOAc/Petroleum ether 20% v/v). m.p.
HRMS (ESI) (m/z): [MþH]þ calcd for: C26H32NO3Sþ2 , 470.1818;
found: 470.1820.
147e149 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.98 (d, J ¼ 8.7 Hz, 2H), 7.37
4.2.23. N-(3-((4-Fluorophenyl)thio)-2-hydroxypropyl)-4-methyl-
N-phenylbenzenesulfonamide (3ae)
Compound 3ae was prepared according to the general proced-
ure and was isolated as yellow oil (79.7 mg, 74% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
(d, J ¼ 8.0 Hz, 2H), 7.28 - 7.15 (m, 7H), 7.03 - 6.95 (m, 2H), 3.83 (p,
J ¼ 5.9 Hz, 1H), 3.72 - 3.58 (m, 2H), 3.25 (dd, J ¼ 13.9, 4.6 Hz, 1H),
3.03 (dd, J ¼ 13.9, 7.3 Hz, 1H), 2.78 (s, 1H), 2.36 (s, 3H). 13C NMR
(101 MHz, CDCl3)
d 146.2, 145.3, 144.1, 139.7, 134.2, 129.6, 129.4,
128.5, 128.4, 127.8, 126.9, 124.0, 68.2, 55.6, 36.8, 21.6. IR (KBr):
(400 MHz, CDCl3)
d
7.37 (d, J ¼ 7.8 Hz, 2H), 7.25 - 7.15 (m, 7H), 6.94 -
y
¼ 3502.6, 3097.7, 1576.6, 1163.1, 655.7, 573.6, 546.8 cmꢁ1. HRMS
6.90 (m, 2H), 6.85 (t, J ¼ 8.3 Hz, 2H), 3.66 - 3.54 (m, 3H), 3.09 - 3.01
(ESI) (m/z): [MþH]þ calcd for: C22H23N2O5Sþ2 ,459.1043; found:
(m, 1H), 2.89 - 2.80 (m, 1H), 2.55 (s, 1H), 2.36 (s, 3H). 19F NMR
459.1043.
(376 MHz, CDCl3)
d
ꢁ114.5.13C NMR (101 MHz, CDCl3)
d
162.09 (d,
Crystal data for 3ai (CCDC 1846073): C22H22N2O5S2, M ¼ 458.53,
J ¼ 247.5 Hz), 143.8, 139.7, 134.7, 133.18 (d, J ¼ 8.1 Hz), 129.86 (d,
a ¼ 10.4036(1), b ¼ 11.2817(1), c ¼ 11.6539(1),
a
¼ 104.622(1),
J ¼ 3.4 Hz),129.5, 129.2, 128.6, 128.2, 127.8, 116.15 (d, J ¼ 21.8 Hz),
b
¼ 113.129(1),
g
¼ 107.996(1), V ¼ 1081.58(2), T ¼ 120.00(10) K,
68.0, 55.4, 40.2, 21.6. IR (KBr):
y
¼ 3506.5, 3064.1, 1590.9, 1163.4,
space group P-1, Z ¼ 2,
m
(CuK
a
) ¼ 2.551 mmꢁ1, 40294 reflections
658.0, 573.8 cmꢁ1
.
HRMS (ESI) (m/z): [MþH]þ calcd for:
measured, 3948 independent reflections (Rint ¼ 0.0267). The final
C
22H23FNO3Sþ2 , 432.1098; found: 432.1094.
R1 values were 0.0371 (I > 2s(I)). The final wR(F [2]) values were
0.1028 (I > 2 (I)). The final R1 values were 0.0377 (all data). The final
s
4.2.24. N-(3-((4-Chlorophenyl)thio)-2-hydroxypropyl)-4-methyl-
N-phenylbenzenesulfonamide (3af)
wR(F [2]) values were 0.1032 (all data). The goodness of fit on F [2]
was 1.054.
Compound 3af was prepared according to the general procedure
and was isolated as yellow solid (80.6 mg, 72% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). m.p. 69e71 ꢀC.
4.2.28. N-(2-Hydroxy-3-(naphthalen-2-ylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (3aj).
1H NMR (400 MHz, CDCl3)
d
7.36 (d, J ¼ 8.3 Hz, 2H), 7.25 - 7.16 (m,
Compound 3aj was prepared according to the general procedure

650
Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
and was isolated as yellow solid (70.6 mg, 61% yield) after flash
126.9, 118.0, 113.2, 68.3, 48.6, 39.5. IR (KBr):
y
¼ 3277.5, 3126.6,
chromatography (EtOAc/Petroleum ether 10% v/v). m.p.
1604.3, 1436.6, 1066.5, 751.1, 728.8, 686.1 cmꢁ1. HRMS (ESI) (m/z):
[MþH]þ calcd for: C15H18NOSþ, 260.1104; found: 260.1109.
107e109 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.68 (d, J ¼ 7.1 Hz, 1H), 7.60
(d, J ¼ 8.8 Hz, 3H), 7.41 - 7.29 (m, 4H), 7.26 (d, J ¼ 8.6 Hz, 1H), 7.17 -
7.05 (m, 5H), 6.89 (d, J ¼ 6.5 Hz, 2H), 3.74 - 3.66 (m, 1H), 3.65 - 3.57
(m, 2H), 3.21 (dd, J ¼ 13.9, 4.1 Hz, 1H), 2.97 (dd, J ¼ 13.9, 7.0 Hz, 1H),
4.5. N-(2-Methoxy-3-(phenylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (6)
2.83 (s, 1H), 2.30 (s, 3H). 13C NMR (101 MHz, CDCl3)
d 143.8, 139.7,
134.6, 133.6, 132.5, 132.0, 129.5, 129.2, 128.7, 128.6, 128.3, 128.2,
127.8, 127.8, 127.7, 127.2, 126.7, 126.0, 68.1, 55.5, 38.9, 21.6. IR (KBr):
To a solution of 3aa (63 mg, 0.15 mmol) in absolute THF (10 mL),
NaH (60% in mineral oil, 12 mg, 0.3 mmol) and MeI (42 mg,
0.3 mmol) were added under argon at 0 ꢀC. The reaction mixture
was warmed to room temperature and stirred for 1 h. After addition
of water, the aqueous phase was extracted with EtOAc (3 ꢂ 25 mL).
The combined organic layers were dried over Na2SO4, filtered and
the solvent was removed in vacuo. The residue was purified by flash
chromatography (EtOAc/Petroleum ether 5% v/v) yielding the
product 6 as a colorless oil (59.6 mg, 93%).1H NMR (400 MHz,
y
¼ 3520.6, 3054.5, 1623.7, 1490.0, 815.0, 659.3, 574.7 cmꢁ1. HRMS
(ESI) (m/z): [MþH]þ calcd for: C26H26NO3Sþ2 , 464.1349; found:
464.1348.
4.2.29. N-(3-(Butylthio)-2-hydroxypropyl)-4-methyl-N-
phenylbenzenesulfonamide (3ak)
Compound 3ak was prepared according to the general proced-
ure and was isolated as yellow oil (21.6 mg, 22% yield) after flash
chromatography (EtOAc/Petroleum ether 10% v/v). 1H NMR
CDCl3)
d
7.36 (d, J ¼ 8.2 Hz, 2H), 7.23 - 7.13 (m, 8H), 7.13 - 7.06 (m,
1H), 6.95 - 6.89 (m, 2H), 3.68 (dd, J ¼ 13.9, 6.0 Hz, 1H), 3.58 (dd,
J ¼ 13.9, 5.8 Hz, 1H), 3.35 (p, J ¼ 5.9 Hz, 1H), 3.16 (s, 3H), 3.08 (dd,
(400 MHz, CDCl3)
d
7.39 (d, J ¼ 7.6 Hz, 2H), 7.26 - 7.23 (m, 2H), 7.22 -
J ¼ 13.7, 5.2 Hz, 1H), 2.94 (dd, J ¼ 13.7, 6.2 Hz, 1H), 2.34 (s, 3H). 13
C
7.15 (m, 3H), 7.02 - 6.97 (m, 2H), 3.72 - 3.51 (m, 3H), 2.81 - 2.66 (m,
2H), 2.49 (dd, J ¼ 13.6, 7.4 Hz,1H), 2.42 - 2.32 (m, 5H),1.42 (p, J ¼ 7.3,
6.8 Hz, 2H), 1.27 (q, J ¼ 7.5 Hz, 2H), 0.81 (t, J ¼ 7.1 Hz, 3H). 13C NMR
NMR (101 MHz, CDCl3)
d 143.6, 139.9, 136.0, 134.9, 130.0, 129.4,
129.1, 128.9, 128.6, 127.9, 127.8, 126.4, 78.6, 57.8, 53.1, 36.5, 21.6. IR
(KBr):
y
¼ 3059.6, 1595.5, 1163.9, 696.7, 657.8, 573.9, 549.6 cmꢁ1
.
(101 MHz, CDCl3)
d 143.8, 139.8, 134.7, 129.5, 129.2, 128.7, 128.2,
HRMS (ESI) (m/z): [MþNa]þ calcd for: C23H25NO3S2Naþ, 450.1168;
127.8, 68.0, 55.6, 36.9, 32.2, 31.7, 21.9, 21.6, 13.7. IR (KBr):
y
¼ 3505.3,
2927.3,1725.9,1163.8, 698.0, 574.3 cmꢁ1. HRMS (ESI) (m/z): [MþH]þ
found: 450.1172.
calcd for: C20H28NO3Sþ2 , 394.1505; found: 394.1506.
4.6. N-(2-azido-3-(phenylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (7)
4.3. N-(2-Hydroxy-3-(naphthalen-2-ylthio)propyl)-4-methyl-N-
phenylbenzenesulfonamide (4)
To a solution of 3aa (120 mg, 0.3 mmol) in 10 mL of dry CH2Cl2,
TEA (37 mg, 0.36 mmol), MsCl (41 mg, 0.36 mmol) were added
under argon at 0 ꢀC. The suspension was stirred at room tempera-
ture for 1 h, then poured onto 15 mL of DCM. The reaction mixture
was washed with brine (2 ꢂ 20 mL), then dried over Na2SO4,
filtered and evaporated to obtain intermediate product. The prod-
uct was used in next step without farther purified. Dissolved the
intermediate product in 5 mL DMF and 5 mL H2O, NaN3 (23 mg,
0.36 mmol) was added. The suspension was stirred at 80 ꢀC over-
night, then poured onto 20 mL of EtOAc. The reaction mixture was
washed with brine. The organic layers were dried over Na2SO4,
filtered and the solvent was removed in vacuo. The residue was
purified by flash chromatography (EtOAc/Petroleum ether 5% v/v)
yielding the product 7 as a colorless oil (111.8 mg, 85%).1H NMR
In a 50 mL flask were added 3aa (63 mg, 0.15 mmol), m-CPBA
(76 mg, 0.33 mmol) and dry CH2Cl2 (10 mL). The resulting mixture
was stirred at room temperature overnight. Then CH2Cl2 (20 mL)
was added and the mixture was washed with aqueous Na2S2O3 and
aqueous NaHCO3. The CH2Cl2 layer was dried with MgSO4, and
concentrated to give crude residue, which was purified by flash
column chromatography (EtOAc/Petroleum ether 20% v/v) to give 4
(61 mg, 91%). White solid. m.p. 153e155 ꢀC. 1H NMR (400 MHz,
CDCl3)
d
7.83 - 7.76 (m, 2H), 7.66 - 7.58 (m, 1H), 7.49 (t, J ¼ 7.8 Hz,
2H), 7.33 (d, J ¼ 8.3 Hz, 2H), 7.21 - 7.11 (m, 5H), 6.78 - 6.68 (m, 2H),
3.95 (ddd, J ¼ 14.2, 5.2, 2.6 Hz, 1H), 3.68 (dd, J ¼ 13.8, 7.7 Hz, 1H),
3.57 (dd, J ¼ 14.7, 2.3 Hz, 1H), 3.45 (dd, J ¼ 13.8, 5.2 Hz, 1H), 3.40 (d,
J ¼ 2.6 Hz, 1H), 3.24 (dd, J ¼ 14.7, 9.0 Hz, 1H), 2.34 (s, 3H). 13C NMR
(101 MHz, CDCl3)
d 144.1, 139.1, 138.8, 134.5, 134.1, 129.6, 129.5,
(400 MHz, CDCl3) d 7.31 - 7.10 (m,12H), 6.96 - 6.89 (m, 2H), 3.71 (dd,
129.3, 128.5, 128.4, 128.1, 127.7, 64.5, 59.8, 54.9, 21.6. IR (KBr):
J ¼ 13.9, 9.4 Hz,1H), 3.60 (d, J ¼ 4.7 Hz, 2H), 3.50 (dd, J ¼ 14.0, 5.0 Hz,
y
¼ 3510.1, 3063.0, 1594.1, 1115.8, 692.4, 591.2, 529.5 cmꢁ1. HRMS
1H), 3.29 (dq, J ¼ 9.5, 4.7 Hz, 1H), 2.34 (s, 3H). 13C NMR (101 MHz,
(ESI) (m/z): [MþNa]þ calcd for: C22H23NO5S2Naþ, 468.0910; found:
CDCl3)
d 143.8, 139.5, 134.3, 132.7, 132.0, 129.5, 129.2, 129.2, 128.5,
468.0913.
128.2, 127.8, 127.6, 52.2, 51.8, 47.3, 21.6. IR (KBr):
y
¼ 3060.4, 2922.0,
2102.8, 1595.7, 656.1, 572.2 cmꢁ1. HRMS (ESI) (m/z): [MþNa]þ calcd
4.4. 1-(Phenylamino)-3-(phenylthio)propan-2-ol (5)
for: C22H22N4O2S2Naþ, 461.1076; found: 461.1080.
In a 50 mL flask were added 3aa (120 mg, 0.3 mmol), magne-
sium powder (80 mg, 3 mmol) and anhydrous methanol (10 mL).
The mixture was sonicated for 12 h. The reaction mixture was
diluted with CH2Cl2 (50 mL), then extracted with saturated NH4Cl
solution (30 mL). The organic layer was washed with saturated
NaHCO3 solution (20 mL) and brine (20 mL), then dried over Na2SO4
and the solvent removed in vacuo. Purification by flash chroma-
tography (EtOAc/Petroleum ether 10% v/v) gave 5 (63 mg, 80%)as a
Acknowledgments
We acknowledge financial support from the National Natural
Science Foundation of China (NSFC 21672106, NSFC 21272121) and
Tianjin Municipal Commission of Science and Technology, China
(15JCZDJC33300). Y.M.L. acknowledges the support from Key Lab-
oratory of Synthetic Chemistry of Natural Substances, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences, China.
white solid. m.p. 62e64 ꢀC. 1H NMR (400 MHz, CDCl3)
d 7.33 (d,
J ¼ 7.7 Hz, 2H), 7.23 (t, J ¼ 7.5 Hz, 2H), 7.18 - 7.14 (m, 1H), 7.10 (t,
J ¼ 7.8 Hz, 2H), 6.65 (t, J ¼ 7.3 Hz, 1H), 6.54 (d, J ¼ 7.9 Hz, 2H), 3.93 (s,
1H), 3.87 (tt, J ¼ 7.7, 4.2 Hz, 1H), 3.29 (dd, J ¼ 12.9, 3.6 Hz, 1H), 3.08
(ddd, J ¼ 14.5, 9.3, 6.0 Hz, 2H), 2.96 (dd, J ¼ 13.8, 7.9 Hz, 1H), 2.60 (s,
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2018.12.044.
1H). 13C NMR (101 MHz, CDCl3)
d 148.0, 134.9, 130.2, 129.3, 129.2,

Z.-Q. Xu et al. / Tetrahedron 75 (2019) 643e651
651
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