Catalyst-free imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement

Article abstract of DOI:10.1002/cjoc.201200604

A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

Full text of DOI:10.1002/cjoc.201200604

FULL PAPER
DOI: 10.1002/cjoc.201200604
Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and
Subsequent [2,3]-Sigmatropic Rearrangement†
Jiang, Yuboa,b,c(江玉波)
Kuang, Chunxiang*,a(匡春香)
Mo, Fanyangc(莫凡洋)
Zhang, Yanc(张艳)
Qiu, Dic(邱迪)
Wang, Jianbo*,c(王剑波)
a Department of Chemistry, Tongji University, Shanghai 200092, China
b Faculty of Science, Kunming University of Science and Technology, Kunming, Yunnan 650093, China
c Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and
Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and sub-
sequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes
smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups
such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.
Keywords allyl sulfonamide, allyl sulfide, transition-metal-free reaction, sigmatropic rearrangement, nitrene
Introduction
sigmatropic rearrangement of sulfide ylides [8] and tran-
sition-metal-free transformations,[9] we have investi-
gated the metal-free imidation of allyl sulfides 1 by us-
ing chloramine-T (TsNClNa) as the nitrogen source.[3]
The subsequent [2,3]-sigmatropic rearrangement affords
allyl sulfonamides 2 in good yields (Scheme 1).
The construction of carbon-nitrogen bond is one of
the major topics in organic synthesis as the nitrogen is
ubiquitous in natural products and biologically active
agents. Similar to the related carbene species, nitrene is
highly reactive species and can undergo various trans-
formations, such as C—H bond insertions and aziridina-
tions.[1] These reactions can serve as useful approaches
toward carbon-nitrogen bond formation. The reaction of
nitrene with sulfides affords sulfilimines, which have
diverse reactivities.[2] When allylsulfides are employed
in this reaction, the corresponding sulfilimines bearing
allylic substituent will undergo [2,3]-sigmatropic rear-
rangement to afford allylic amides.[3] This unique trans-
formation is considered as an interesting method for the
synthesis of allylic amine derivatives.
Scheme 1 Imidation/[2,3]-sigmatropic rearrangement
R1 R2
Na
R3
R2
TsNCl
3H2O
+
R
S
R3
R
N
R1
S
N
R1 R2
Ts
Ts
2
R
S
R3
1
The products contains sulfonamide segment which
Copper-catalyzed formation of sulfimides and se-
lenimides and subsequent [2,3]-sigmatropic rearrange-
ment to the corresponding allylic sulfonamides using
[N-(p-tolylsulfonyl)imino] phenyliodinane (TsN＝IPh)
as nitrogen source has been reported by Uemura and
coworkers.[4] The iron-catalyzed imidation of sulfides
with tert-butoxycarbonyl azide and [2,3]-sigmatropic
rearrangement has been investigated by Bach[5] and van
Vranken[6] respectively. Very recently, the synthesis of
allenamides has been achieved by Armstrong[7] through
this rearrangement by employing CbzNHOTf as the
nitrene precursor.
serves as one of the common structural features in
drugs.[10] Furthermore, they can also be converted to
allyl sulfonamides and allyl amides by removal of the
protecting group (Ts).[5,11]
Results and Discussion
The allyl sulfides were prepared and their reactions
with chloramine-T were investigated. The allyl(phenyl)-
sulfane 1a was selected to optimize the reaction condi-
tions (Table 1). Initially, only trace of product could be
detected when we conducted the reaction in toluene as
the solvent under room temperature (Table 1, Eentry 1).
As the continuation of our own interest in [2,3]-
*
E-mail: wangjb@pku.edu.cn; Tel.: (＋86)-010-62751708; Fax: (＋86)-010-62751708
Received June 20, 2012; accepted July 4, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200604 or from the author.
Dedicated to the 80th Anniversary of Chinese Chemical Society.
†
Chin. J. Chem. 2012, 30, 2029—2035
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Jiang et al.
FULL PAPER
The yield was increased to 50% when we elevated the
reaction temperature to 70 ℃ (Table 2, Eentry 1). We
continued to tried other solvents and found that DCE,
THF, DMF and dioxane could afford moderate yields
(Table 2, Entries 3—6), while MeCN and EtOH af-
forded excellent yields (Table 2, Entries 7—12). Mod-
erate yields can also be obtained when H2O was used as
the solvent under heating or microwave conditions (Ta-
ble 1, Entries 14—16). Notably, more favored yields
can be achieved under room temperature other than 70
℃ when MeCN or EtOH was chosen as the medium
(Table 1, Entries 10, 12).
The optimized reaction conditions (EtOH/room
temperature) were then applied to a series of allyl sul-
fides 1b—1q and the results were summarized in Table
2. All aromatic allyl sulfides reacted smoothly with
chloramines-T and afforded excellent yields. The sub-
stituents on the aromatic ring had some influences on
the reaction. When electron-donating aromatic allyl sul-
fides were subjected to the reaction, the yields slightly
increased (Table 2, Entries 1, 2, 4, 9), while the yields
decreased when the aromatic ring bears electron-with-
drawing group (Table 2, Entries 3, 5). Various substi-
tuted and cyclic allyl sulfides could also be used for the
construction of C—N bonds (Table 2, Entries 6—9).
The benzyl and alkyl allyl sulfides react slowly at room
temperature, they could work successfully when heated
to 70 ℃ (Table 2, Entries 10, 11). Moreover, func-
tional groups such as bromine, hydroxyl, protected
amido and aldehyde on allyl part are tolerant in this
system (Table 2, Entries 12—16). It is worth noting that
this reaction proceeds very fast and could complete
within 10 min in all cases.
Table 1 Optimization of the reaction conditions with 1a
Ts
Na
TsNCl
solvent
temp.
N
PhS
+
3H2O
SPh
1a
2a
Equv. of Temp./
Entry Solvent
Timea Yieldb/%
TsNClNa
1.2
℃
r.t.
70
70
70
r.t.
r.t.
70
70
70
r.t.
70
r.t.
r.t.
70
1
2
3
PhMe
PhMe
DCE
5 h
2 h
1 h
＜5
50
1.2
1.2
1.2
1.2
1.2
1.2
1.3
1.4
1.3
1.3
1.3
1.3
58 (50)c
57
4
THF
10 min
5 min
5 min
5 min
5 min
5 min
10 min
5 min
10 min
12 h
Conclusions
5
6
7
8
DMF
Dioxane
MeCN
MeCN
MeCN
MeCN
EtOH
EtOH
DCM
H2O
50
57
70
78
78
81
80
82
In summary, we have developed a process of metal-
catalyst free imidation of allyl sulfides with Chlor-
amines-T and subsequent [2,3]-sigmatropic rearrange-
ment. Various substituted and functionalized allyl sul-
fonamides or allyl amides can be easily obtained
through this approach. It affords an efficient strategy for
the construction of carbon-nitrogen bond. Compared to
other procedures, this method has wider scope and
higher efficiency.
9
10
11
12
13d
14
15d
16d
＜5
64
1.3
12 h
H2O
H2O
1.3
70 (MW) 5 min
52
58
1.3
100 (MW) 30 min
Experimental
a
b
c
Determined by TLC. Isolated yields. Yield using anhydrous
chloramine-T was given in parentheses. Amount of recovered
staring material was not determined.
d
General
Aryl mercaptans, bromides and chloramine-T were
Table 2 Reaction of 1b—1q with chloramine-T under qptimization conditions
R2 R3
R1 R2
Na
TsNCl
3H2O
S
R1
R
R
N
S
R3
EtOH
Ts
2b 2q
—
1b 1q
—
Entry
1
Allyl sulfide 1
Product 2
Yielda/%
S
N
Ts
90
S
1b
2b
S
N
S
Ts
2
92
1c
2c
2030
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Chin. J. Chem. 2012, 30, 2029—2035

Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent Rearrangement
Continued
Entry
3
Allyl sulfide 1
Product 2
Yielda/%
Cl
S
N
Ts
72
S
Cl
1d
2d
MeO
S
N
Ts
4
5
97
78
S
MeO
1e
1f
2e
S
S
N
Cl
Ts
Cl
2f
S
N
6
7
8
78
77
93
S
Ts
1g
2g
S
N
S
Ts
1h
2h
S
N
S
Ts
1i
2i
S
S
N
9
95
45
91
MeO
Ts
MeO
1j
2j
S
N
S
10b
11b
Ts
1k
2k
S
S
N
Ts
1l
1m
1n
2l
Br
S
Br
S
N
12
13
84
83
Ts
2m
OH
S
N
OH
S
Ts
2n
HO
Ph
S
S
Ph
N
14c
82
OH
Ts
1o
2o
Chin. J. Chem. 2012, 30, 2029—2035
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Jiang et al.
FULL PAPER
Continued
Entry
Allyl sulfide 1
Product 2
Yielda/%
O
O
S
S
N
Ph
N
N
15
84
Ts
O
O
1p
2p
O
O
O
S
S
O
Ph
16b
68
Ph
N
Ts
1q
2q
a Isolated yields. b The reaction was carried out at 70 ℃ c d.r.＝60∶40.
purchased from Alfa Aesar. Chloroform-d and dimeth-
ylsulfoxide-d6 were purchased from Cambridge Isotope
Laboratories. All solvents were distilled prior to use.
THF was freshly distilled from Na before use. All reac-
tions were performed in air atmosphere. For chroma-
tography, 200—300 mesh silica gel (Qingdao, China)
1m:[14-19] To a 15 mL of dry THF was added 12 mmol
of NaH, 10 mmol of thiol (slowly added) and stirred at 0
℃ for 15 min. To the system was then added 12 mmol
of allyl bromide and stirred overnight at room tempera-
ture. The precipitate was removed by filtration and
washed with diethyl ether. After the solvent was re-
moved the residue was purified by column chromatog-
raphy.
1
was employed. H NMR (300 or 200 MHz) and 13C
NMR (75 or 50 MHz) spectra were measured on Varian
1
300 MHz spectrometers; H NMR (400 MHz) and 13C
(4-Chlorophenyl)(cyclohex-2-enyl)sulfane (1f): Col-
1
orless liquid; H NMR (400 MHz, CDCl3) δ: 7.34 (d,
NMR (100 MHz) spectra were measured on Bruker
ARX 400 MHz spectrometer. CDCl3 was used as sol-
vent with tetramethylsilane (TMS) as internal standard.
IR spectra were recorded with a Nicolet 5MX-S infrared
spectrometer.
J＝8.4 Hz, 2H), 7.25 (d, J＝8.5 Hz, 2H), 5.85 (dd, J＝
3.50, 9.9 Hz, 1H), 5.74 (dd, J＝1.8, 10.0 Hz, 1H), 3.81
(s, br, 1H), 2.04—1.58 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ: 134.3, 132.6, 130.7, 128.9, 126.5, 44.2, 28.7,
24.8, 19.3; IR (film) ν: 2933, 1476, 1096, 1013, 815
－
1
Synthesis and spectral data for the substrates 1a—1q
and 3—4
cm ; EI-MS (relative intensity) m/z (%): 224 (11), 143
(16), 108 (18), 81 (100), 53 (14); HRMS calcd for
C12H13ClSK (M＋Na)＋: 263.0058, found 263.0053.
(E)-Ethyl 4-(phenylthio)but-2-enoate (3):[12] A 2.05
mL portion of thiophenol (2.2 g, 20 mmol) and 5.13 g of
(E)-ethyl 4-bromobut-2-enoate (22 mmol) were dis-
solved in 30 mL of dry diethyl ether and cooled to －10
℃. A 2.2 g portion of triethylamine (22 mmol) was
added dropwise during 0.5 h. After being stirred at
－10 ℃ for 30 min, the mixture was refluxed for 1 h
and stirred overnight at room temperature. The precipi-
tate was removed by filtration and washed with diethyl
ether. The filtrate was washed with aqueous NaOH and
dried over MgSO4. After the solvent was removed the
residue was purified by column chromatography. 4.35 g
(98%) of 3 was obtained as a colorless liquid.
Cyclohex-2-enyl(4-methoxyphenyl)sulfane
(1j):
1
Colorless liquid; H NMR (400 MHz, CDCl3) δ: 7.41
(d, J ＝8.7 Hz, 2H), 6.84 (d, J ＝8.62 Hz, 2H),
5.81—5.73 (m, 2H), 3.79 (s, 3H), 3.65 (br s, 1H),
2.00—1.54 (m, 6H); 13C NMR (100 MHz, CDCl3)
δ: 159.3, 135.1, 130.0, 127.2, 125.7, 114.3, 55.2, 45.4,
28.7, 24.9, 19.4; IR (film) ν: 2933, 1492, 1243, 1029,
－
1
823 cm ; EI-MS (relative intensity) m/z (%): 220 (21),
140 (100), 81 (55); HRMS calcd for C13H15OS (M－H)＋:
219.0838, found 219.0838.
(E)-4-(Phenylthio)but-2-en-1-ol (1n):[20] A 0.666 g
(3 mmol) portion of (E)-ethyl-4-(phenylthio) but-2-
enoate (3) was dissolved in 10 mL of dry THF and
cooled to 0 ℃. A 6 mL portion of Dibal-H (6 mmol, 1n
in hexane) was added, and after the mixture was stirred
at 0 ℃ for 1 h, 2 mL of methanol, 10 mL of water, 1
mL of saturated NaOH aqueous, and 10 mL of aqueous
KNa tartrate (30%, W/W) were added successively. The
mixture was stirred at room temperature for 1 h, and the
layers were separated. The aqueous layer was extracted
with 30 mL Et2O for three times, and the combined
(E)-4-(Phenylthio)but-2-enal (4):[13] A 0.72 g (4
mmol) portion of (E)-ethyl-4-(phenylthio)but-2-enoate
(3), 0.672 g NaHCO3 and 2.035 g of DMP were added
to 20 mL of CH2Cl2 under 0 ℃ and the reaction was
conducted by TLC. Flash chromatography provided
crude product which was further purified by column
chromatography providing 0.584 g (82%) 4 as a color-
less liquid.
General procedure for the preparation of 1a —
2032
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Chin. J. Chem. 2012, 30, 2029—2035

Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent Rearrangement
organic layers were washed with water and brine and
dried over MgSO4. After evaporation of the solvent, the
residue was purified by column chromatography. Com-
pound 1n (0.443 g, 82%) was obtained as a colorless
mmol), in benzene (15 mL) was added ethylene glycol
(0.279 g, 4.5 mmol) in benzene (10 mL). The reaction
mixture was heated to reflux and was monitored by
TLC until no starting aldehyde was detected. The reac-
tion mixture was then filtered through a pad of anhy-
drous NaHCO3, and the filter cake was washed with
CH2Cl2 (10 mL×3). Concentration of the filtrate gave
the crude product which was further purified by col-
umn chromatography on silica gel to give 0.373 g of
1
liquid. H NMR (300 MHz, CDCl3) δ: 7.34—7.16 (m,
5H), 5.75—5.70 (m, 2H), 4.04 (d, J＝4.2 Hz, 2H), 3.54
(d, J＝5.8 Hz, 2H), 1.73 (s, 1H); 13C NMR (75 MHz,
CDCl3) δ: 135.6, 132.3, 129.8, 128.7, 126.8, 126.2, 62.7,
35.7.
1
(E)-1-Phenyl-4-(phenylthio)but-2-en-1-ol (1o): In a
25 mL round bottom flask a magnetic stir bar was
placed and the apparatus was flame dried. Then, dried
diethyl ether (10 mL), phenylmagnesium bromide (4.5
mmol, 3 mol/L in diethyl ether) and 0.534 g (3 mmol)
of (E)-4-(phenylthio)-but-2-enal (4) were added to the
flask under 0 ℃. After stirred at room temperature for
30 min, the reaction was quenched by slow addition of a
saturated NH4Cl solution followed by extraction with
diethyl ether (15 mL×3). The combined organic layers
were washed with brine, dried (Na2SO4), concentrated
and the crude product was purified by column chroma-
tography to afford 0.66 g of 1o as a light yellow oil,
1q as a light yellow oil, yield 56%. H NMR (400
MHz, CDCl3) δ: 7.34—7.16 (m, 5H), 3.96—3.83 (m,
4H), 5.97 (td, J＝6.93, 6.93, 15.17 Hz, 1H), 5.57 (dd,
J＝5.8, 15.40 Hz, 1H), 5.21 (d, J＝5.8 Hz, 1H), 3.55
(d, J＝6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3)
δ: 135.5, 131.3, 129.9, 129.4, 128.8, 126.3, 102.8, 64.7,
35.5; EI-MS (relative intensity) m/z (%): 222 (24), 112
(100), 73 (47), 41 (87); IR (film) ν: 1141, 1404, 961,
－
1
738, 687 cm ; HRMS calcd for C12H14O2SK (M＋
Na)＋: 261.0556, found 261.0552.
Synthesis and spectral data for products 2a—2q
General procedure for the reaction of allyl sulfides
with chloramine-T: To a flask was added 1 mmol allyl
sulfides (1), 1.3 mmol chloramine-T, 2 mL of EtOH and
the system was stirred at the assigned temperature. After
the reaction finished, the solvent was removed in vacuo
and the residue was purified by column chromatography
on silica gel to afford the corresponding product.
1
yield 86%. H NMR (300 MHz, CDCl3) δ: 7.33—7.14
(m, 10H), 5.85—5.62 (m, 2H), 5.09 (d, J＝5.4 Hz, 1H),
3.52 (d, J＝6.8 Hz, 2H), 1.97 (d, J＝2.8 Hz, 1H); 13C
NMR (75 MHz, CDCl3) δ: 142.3, 135.3, 135.3, 130.4,
128.7, 128.4, 127.5, 126.6, 126.4, 126.1, 74.2, 36.0; IR
－
1
(film) ν: 967, 699, 738 cm ; EI-MS (relative intensity)
m/z (%): 256 (27), 146 (49), 129 (29), 110 (100), 105
(80), 77 (52), 65 (15); HRMS calcd for C16H16OSNa
(M＋Na)＋: 279.0814, found 279.0807.
N-Allyl-4-methyl-N-(phenylthio)benzenesulfonamide
(2a): Colorless oil; 1H NMR (400 MHz, CDCl3) δ: 7.80
(d, J＝8.3 Hz, 2H), 7.39 (d, J＝7.6 Hz, 2H), 7.33—7.20
(m, 5H), 5.71 (tdd, J＝6.5, 6.47, 10.1, 16.7 Hz, 1H),
5.15 (t, J＝14.1, 14.1 Hz, 2H), 4.15 (d, J＝6.5 Hz, 2H),
2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 144.0,
137.0, 136.1, 132.3, 129.6, 128.9, 127.8, 127.4, 126.3,
119.6, 56.9, 21.5; IR (film) ν: 1349, 1160, 827, 812, 659
(E)-2-(4-(Phenylthio)but-2-enyl)isoindoline-1,3-dione
(1p): Triphenylphosphane (1.179 g, 4.5 mmol) and
phthalimide (0.529 g, 3.6 mmol) were added at room
temperature to a solution of 0.540 g (3 mmol) of
(E)-4-(phenylthio)but-2-en-1-ol (1n) in THF (10 mL).
Diethyl azodicarboxylate (0.783 mg, 4.5 mmol) was
added dropwise to the reaction mixture at 0 ℃. After
complete consumption (the reaction was monitored by
TLC), the solvent was removed in vacuo and the crude
product was purified by column chromatography on
silica gel to afford the corresponding 1p as a white solid,
－
＋
1
cm ; EI-MS (relative intensity) m/z (%): 319 (M , 13),
164 (56), 109 (72), 91 (100), 65 (54), 56 (44), 41 (45);
HRMS calcd for C16H17NO2S2K (M＋Na)＋: 358.0332,
found 358.0326.
N-Allyl-4-methyl-N-(p-tolylthio)benzenesulfonamide
(2b): Colorless oil; 1H NMR (400 MHz, CDCl3) δ: 7.80
(d, J＝8.3 Hz, 2H), 7.35 (d, J＝8.1 Hz, 2H), 7.29 (d,
J＝8.2 Hz, 2H), 7.12 (d, J＝8.1 Hz, 2H), 5.71 (tdd, J＝
6.4, 6.4, 10.1, 16.7 Hz, 1H), 5.16 (dd, J＝5.2, 21.1 Hz,
2H), 4.12 (d, J＝6.4 Hz, 2H), 2.42 (s, 3H), 2.33 (s, 3H);
13C NMR (100 MHz, CDCl3) δ: 143.9, 138.2, 136.4,
133.1, 132.6, 129.6, 129.5, 128.3, 127.8, 119.4, 56.7,
1
0.917 g, yield 99%. m.p. 114—115 ℃; H NMR (400
MHz, CDCl3) δ: 7.84—7.82 (m, 2H), 7.73—7.71 (m,
2H), 7.30—7.26 (m, 2H), 7.17—7.14 (m, 2H), 7.06—
7.02 (m, 1H), 5.81—5.75 (m, 1H), 5.56—5.51 (m, 1H),
4.18 (d, J＝6.3 Hz, 2H), 3.46 (d, J＝7.0 Hz, 2H); 13C
NMR (75 MHz, CDCl3) δ: 167.6, 135.0, 133.8, 132.0,
130.9, 129.7, 128.6, 126.5, 126.4, 123.2, 38.8, 36.2; IR
－
1
21.5, 21.1; IR (film) ν: 1352, 1160, 827, 809, 659 cm ;
EI-MS (relative intensity) m/z (%): 333 (13), 178 (67),
123 (100), 91 (57), 65 (27); HRMS calcd for C17H19N-
O2S2Na (M＋Na)＋: 356.0749, found 356.0742.
－
1
(film) ν: 1709, 1392, 717 cm ; EI-MS (relative inten-
sity) m/z (%): 309 (36), 200 (100), 182 (40), 130 (38),
109 (35), 53 (49); HRMS calcd for C18H15NO2SNa
(M＋Na)＋: 332.0716, found 332.0708.
N-Allyl-4-methyl-N-(o-tolylthio)benzenesulfonamide
1
(2c): Colorless oil; H NMR (400 MHz, CDCl3) δ: 7.82
(E)-2-(3-(Phenylthio)prop-1-enyl)-1,3-dioxolane (1q):
To a 25 mL two-necked, round-bottomed flask,
equipped with a Dean-Stark adapter and a condenser,
containing the (E)-4-(phenylthio)but-2-enal (4) (0.534
g, 3 mmol), p-toluenesulfonic acid (14 mg, 0.075
(d, J＝8.3 Hz, 2H), 7.47 (d, J＝7.8 Hz, 1H), 7.30 (d,
J＝8.1 Hz, 2H), 7.22—7.18 (m, 1H), 7.11—7.06 (m,
2H), 5.71 (tdd, J＝6.5, 6.5, 10.1, 16.7 Hz, 1H), 5.13
(ddd, J＝1.2, 13.6, 11.2 Hz, 2H), 4.16 (d, J＝6.5 Hz,
Chin. J. Chem. 2012, 30, 2029—2035
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2033

Jiang et al.
FULL PAPER
2H), 2.43 (s, 3H), 2.22 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 144.0, 136.2, 136.2, 132.8, 132.1, 130.1,
129.6, 127.8, 126.6, 126.3, 124.4, 119.7, 56.9, 21.6,
methylbenzenesulfonamide (2j): Colorless oil; 1H NMR
(400 MHz, CDCl3) δ: 7.83 (d, J＝8.3 Hz, 2H), 7.57 (d,
J＝8.8 Hz, 2H), 7.30 (d, J＝8.0 Hz, 2H), 6.86 (d, J＝
8.9 Hz, 2H), 5.79—5.75 (m, 1H), 5.04 (s, br, 1H),
4.83—4.81 (m, 1H), 3.81 (s, 3H), 2.43 (s, 3H), 1.95—
1.59 (m, 6H); 13C NMR (100 MHz, CDCl3) δ: 159.9,
143.6, 137.4, 131.9, 129.5, 127.7, 127.6, 114.3, 59.7,
55.3, 24.3, 21.5, 21.3; IR (film) ν: 1590, 1492, 1346,
－
1
18.8; IR (film) ν: 1352, 1166, 827, 812, 659 cm ;
EI-MS (relative intensity) m/z (%): 333 (27), 178 (80),
137 (40), 123 (74), 91 (100), 65 (46), 45 (69); HRMS
calcd for C17H19NO2S2Na (M＋Na)＋: 356.0749, found
356.0749.
－
1
N-Allyl-N-(4-chlorophenylthio)-4-methylbenzenesul-
fonamide (2d): White solid, m.p. 64—65 ℃; H NMR
1251, 1160, 1083, 1028, 873, 854, 812, 729, 665 cm ;
EI-MS (relative intensity) m/z (%): 389 (5), 309 (36),
154 (100), 139 (74), 91 (56), 65 (26); HRMS calcd for
C20H24NO3S2 (M＋H)＋: 390.1192, found 390.1191.
N-Allyl-N-(butylthio)-4-methylbenzenesulfonamide
(2k): Colorless oil; 1H NMR (400 MHz, CDCl3) δ: 7.80
(d, J＝8.3 Hz, 2H), 7.30 (d, J＝8.2 Hz, 2H), 5.77 (tdd,
J＝6.5, 6.5, 10.08, 16.7 Hz, 1H), 5.19 (ddd, J＝1.3,
10.9, 8.7 Hz, 2H), 4.04 (d, J＝6.5 Hz, 2H), 2.88 (t, J＝
7.4 Hz, 2H), 2.43 (s, 3H), 1.59—1.52 (m, 2H),
1.43—1.36 (m, 2H), (t, J＝7.33, 7.33 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ: 143.6, 136.0, 133.1, 129.4,
127.8, 119.1, 57.6, 39.8, 29.1, 21.8, 21.5, 13.6; IR (film)
1
(400 MHz, CDCl3) δ: 7.80 (d, J＝8.3 Hz, 2H), 7.36—
7.26 (m, 6H), 5.70 (tdd, J＝6.5, 6.5, 10.1, 16.7 Hz, 1H),
5.19—5.13 (m, 2H), 4.13 (d, J＝6.5 Hz, 2H), 2.44 (s,
1H); 13C NMR (100 MHz, CDCl3) δ: 144.2, 136.0,
135.6, 133.5, 132.2, 129.6, 129.0, 128.0, 127.7, 119.9,
77.3, 77.0, 76.7, 57.0, 21.5; IR (film) ν: 1474, 1349,
－
1
1086, 812, 659 cm ; EI-MS (relative intensity) m/z (%):
353 (11), 198 (49), 143 (68), 91 (100), 108 (30), 65 (46);
HRMS calcd for C16H16ClNO2S2Na (M ＋ Na)
376.0202, found 376.0203.
N-Allyl-N-(4-methoxyphenylthio)-4-methylbenzene-
sulfonamide (2e): Colorless oil; H NMR (400 MHz,
CDCl3) δ: 7.79 (d, J＝8.3 Hz, 1H), 7.52 (d, J＝8.9 Hz,
2H), 7.30 (d, J＝8.0 Hz, 2H), 6.85 (d, J＝8.9 Hz, 2H),
5.72 (tdd, J＝6.4, 6.4, 10.1, 16.5 Hz, 1H), 5.17 (ddd,
J＝1.3, 9.3, 7.1 Hz, 2H), 4.08 (d, J＝6.4 Hz, 2H), 3.81
(s, 3H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ: 160.6, 143.7, 136.5, 133.6, 132.9, 129.5, 127.7, 126.5,
119.1, 114.4, 56.3, 55.3, 21.5; IR (film) ν: 1590, 1492,
1346, 1245, 1086, 824, 812, 662 cm ; EI-MS (relative
intensity) m/z (%): 349 (12), 194 (56), 139 (100), 91
(50); HRMS calcd for C17H19NO3S2Na (M＋Na)＋:
372.0698, found 372.0699.
＋
:
－
1
1
ν: 1345, 1160, 1089, 912, 827, 812, 732, 662 cm ;
EI-MS (relative intensity) m/z (%): 299 (30), 344 (52),
103 (70), 91 (100), 65 (44), 56 (97), 41 (70), 29 (53);
HRMS calcd for C14H21NO2S2Na (M＋Na)＋: 322.0907,
found 322.0906.
N-Allyl-N-(benzylthio)-4-methylbenzenesulfonamide
(2l): White solid, m.p. 52—53 ℃; 1H NMR (400 MHz,
CDCl3) δ: 7.82 (d, J＝8.3 Hz, 2H), 7.32—7.26 (m, 7H),
5.52 (tdd, J＝6.5, 6.5, 10.4, 16.8 Hz, 1H), 5.06—5.01
(m, 2H), 4.10 (s, 2H), 3.81 (d, J＝6.4 Hz, 2H), 2.42 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 143.7, 136.2,
134.9, 132.7, 129.7, 129.4, 128.6, 127.8, 127.6, 118.9,
57.2, 44.8, 21.5; IR (film) ν: 1349, 1160, 1086, 925, 827,
812, 711, 699, 662 cm ; EI-MS (relative intensity) m/z
(%): 333 (10), 123 (20), 91 (100), 65 (19); HRMS calcd
for C17H19NO2S2Na (M ＋Na) ＋ : 356.0749, found
356.0741.
N-(1-Bromobut-3-en-2-yl)-4-methyl-N-(phenylthio)-
benzenesulfonamide (2m): White solid, m.p. 83—84 ℃;
1H NMR (400 MHz, CDCl3) δ: 7.83 (d, J＝8.3 Hz, 2H),
7.52 (d, J＝7.4 Hz, 2H), 7.34—7.23 (m, 5H), 5.64 (ddd,
J＝7.8, 10.3, 17.3 Hz, 1H), 5.15 (d, J＝10.4 Hz, 2H),
4.91 (q, J＝7.4, 7.4, 7.7 Hz, 1H), 3.45 (dd, J＝6.9, 10.4
Hz, 1H), 3.34 (t, J＝8.7, 8.7 Hz, 1H), 2.42 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 144.2, 137.7, 136.1, 133.2,
129.4, 128.9, 128.1, 127.7, 126.6, 120.6, 66.0, 32.1,
21.6; IR (film) ν: 1358, 1163, 1086, 888, 836, 812, 741,
－
1
N-(4-Chlorophenylthio)-N-(cyclohex-2-enyl)-4-meth-
ylbenzenesulfonamide (2f): White solid, m.p. 79—80
－
1
1
℃; H NMR (400 MHz, CDCl3) δ: 7.84 (d, J＝8.3 Hz,
2H), 7.40 (d, J＝8.6 Hz, 2H), 7.33—7.27 (m, 4H),
5.77—5.73 (m, 1H), 4.92 (br s, 2H), 2.24 (s, 3H),
1.91—1.54 (m, 6H); 13C NMR (100 MHz, CDCl3)
δ: 144.1, 132.6, 129.7, 128.8, 127.6, 126.8, 59.8, 24.2,
21.5, 21.1; IR (film) ν: 1474, 1355, 1166, 1086, 873,
－
1
814, 729, 665 cm ; EI-MS (relative intensity) m/z (%):
393 (12), 313 (66), 91 (100), 65 (44), 41 (42); HRMS
calcd for C19H20ClNO2S2Na (M ＋Na) ＋ : 416.0516,
found 416.0512.
N-(Cyclohex-2-enyl)-4-methyl-N-(phenylthio)ben-
zenesulfonamide (2i): White solid, m.p. 101—102 ℃;
1H NMR (400 MHz, CDCl3) δ: 7.85 (d, J＝8.3 Hz, 2H),
7.44 (d, J＝7.5 Hz, 2H), 7.33—7.30 (m, 4H), 7.21—
7.17 (m, 1H), 5.75—5.72 (m, 1H), 4.93—4.91 (m, 2H),
2.24 (s, 3H), 1.90—1.57 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ: 143.9, 137.0, 137.0, 132.4, 129.6, 128.7,
127.6, 127.0, 126.6, 124.8, 59.8, 24.2, 21.5, 21.2; IR
(film) ν: 1355, 1163, 873, 854, 812, 665 cm ; EI-MS
(relative intensity) m/z (%): 359 (2), 279 (59), 124 (100),
109 (37), 91 (66), 81 (34), 65 (44); HRMS calcd for
C19H21NO2S2Na (M＋Na)＋: 382.0906, found 382.0905.
N-(Cyclohex-2-enyl)-N-(4-methoxyphenylthio)-4-
－
1
668 cm ; EI-MS (relative intensity) m/z (%): 413 (8),
411 (7), 258 (37), 256 (36), 124 (44), 109 (69), 91 (100),
65(63); HRMS calcd for C17H18BrNO2S2Na (M＋Na)＋:
433.9855, found 433.9847.
N-(1-Hydroxybut-3-en-2-yl)-4-methyl-N-(phenyl-
thio)benzenesulfonamide (2n): White solid, m.p.
－
1
1
107—108 ℃; H NMR (400 MHz, CDCl3) δ: 7.83 (d,
J＝8.3 Hz, 2H), 7.58 (s, 2H), 7.36—7.24 (m, 5H), 5.56
(ddd, J＝8.0, 10.0, 17.6 Hz, 1H), 5.09 (d, J＝10.5 Hz,
2H), 4.81 (dt, J＝5.3, 8.0, 7.7 Hz, 1H), 3.70 (t, J＝10.0,
2034
www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2029—2035

Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent Rearrangement
10.0 Hz, 1H), 3.56 (s, 1H), 2.42 (s, 3H), 1.52 (s, 1H);
13C NMR (100 MHz, CDCl3) δ: 144.1, 137.9, 136.2,
132.5, 129.4, 129.1, 128.0, 127.8, 126.7, 119.8, 66.5,
62.7, 21.5; IR (film) ν: 1349, 1160, 1086, 1041, 870,
812, 738, 665 cm ; EI-MS (relative intensity) m/z (%):
349 (7), 318 (40), 164 (58), 124 (44), 109 (78), 91 (100),
65 (57); HRMS calcd for C17H19NO3S2Na (M＋Na)＋:
372.0699, found 372.0690.
References
[1] Reviews on nitrenes: (a) Platz, M. S. In Reactive Intermediate
Chemistry, Eds.: Moss, R. A.; Platz, M. S.; Jones, M., Jr.,
Wiley-Interscience, New Jersey, 2004, p. 501; (b) Müller, P.; Fruit,
C. Chem. Rev. 2003, 103, 2905.
－
1
[2] Gilchrist, T. L.; Moody, C. J. Chem. Rev. 1977, 77, 409.
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Murakami, M.; Katsuki, T. Tetrahedron Lett. 2002, 43, 3947; (e)
Armstrong, A.; Challinor, L.; Moir, J. H. Angew. Chem., Int. Ed.
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mun. 1996, 931; (b) Takada, H.; Oda, M.; Miyake, Y.; Ohe, K.;
Uemura, S. Chem. Commun. 1998, 1557; (c) Takada, H.; Nishiba-
yashi, Y.; Ohe, K.; Uemura, S. J. Org. Chem. 1997, 62, 6512.
[5] Bach, T.; Körber, C. J. Org. Chem. 2000, 65, 2358.
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2003, 68, 4955.
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Chem. 2002, 67, 5621; (b) Zhang, X.; Ma, M.; Wang, J. Tetrahedron:
Asymm. 2003, 14, 891; (c) Zhang, X.; Ma, M.; Wang, J. Chin. J.
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Chem. 2007, 9, 184; (f) Xiao, Q.; Wang, J. Acta Chim. Sinica 2007,
65, 1733 (in Chinese); (g) Liao, M.; Peng, L.; Wang, J. Org. Lett.
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Chem., Int. Ed. 2007, 46, 1905.
N-(1-Hydroxy-1-phenylbut-3-en-2-yl)-4-methyl-N-
(phenylthio) benzenesulfonamide (2o): Colorless oil; 1H
NMR (400 MHz, CDCl3) δ: 7.84 (d, J＝8.2 Hz, 2H),
7.74—7.69 (m, 2H), 7.37—7.21 (m, 10H), 5.52 (ddd,
J＝8.4, 10.4, 17.2 Hz, 1H), (d, J＝10.1 Hz, 2H), 4.70 (s,
1H), 4.57 (s, 1H), 2.39 (s, 3H), 2.30 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ: 144.0, 139.6, 137.5, 136.0, 131.7,
129.2, 129.1, 128.3, 128.1, 128.1, 127.6, 127.4, 120.7,
74.0, 71.7, 21.5; IR (film) ν: 1346, 1160, 1086, 1022,
－
1
906, 812, 732, 699, 668 cm ; EI-MS (relative intensity)
m/z (%): 318 (32), 210 (98), 163 (69), 155 (48), 109
(47), 91 (100), 79 (52), 65 (44); HRMS calcd for
C23H23NO3S2Na (M＋Na)＋: 448.1011, found 448.1003.
N-(1-(1,3-Dioxoisoindolin-2-yl)but-3-en-2-yl)-4-
methyl-N-(phenylthio)benzenesulfonamide (2p): White
1
solid, m.p. 183—185 ℃; H NMR (400 MHz, CDCl3)
δ: 7.78—7.75 (m, 4H), 7.71—7.68 (m, 2H), 7.46 (s, 2H),
7.30—7.11 (m, 5H), 5.77—5.68 (m, 1H), 5.22—5.03
(m, 3H), 3.83 (d, J＝13.4 Hz, 2H), 2.26 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 167.7, 143.8, 138.3, 133.9,
131.8, 129.4, 128.7, 127.8, 127.1, 125.8, 123.2, 120.4,
120.3, 62.4, 39.9, 21.5; EI-MS (relative intensity) m/z
(%): 478 (2), 318 (30), 200 (24), 160 (100), 91 (49);
HRMS calcd for C25H22N2O4S2Na (M＋Na)＋: 501.0905,
found 501.0913.
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(b) Mo, F.; Jiang, Y.; Qiu, D.; Zhang, Y.; Wang, J. Angew. Chem., Int.
Ed. 2010, 49, 1846; (c) Li, H.; Wang, L.; Zhang, Y.; Wang, J. Angew.
Chem., Int. Ed. 2012, 51, 2943.
N-(1-(1,3-Dioxolan-2-yl)allyl)-4-methyl-N-(phenyl-
thio)benzenesulfonamide (2q): Colorless oil; H NMR
[10] Scozzafava, A.; Owa, T.; Mastrolorenzo, A.; Supuran, C. T. Curr.
Med. Chem. 2003, 10, 925.
1
[11] (a) Hamada, T.; Nishida, A.; Yonemitsu, O. J. Am. Chem. Soc. 1986,
108, 140; (b) Vellemäe, E.; Lebedev, O.; Mäeorg, U. Tetrahedron
Lett. 2008, 49, 1373.
[12] Brownbridge, P.; Hunt, P. G.; Warren, S. J. Chem. Soc., Perkin Trans.
1 1986, 1695.
[13] Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.; Piancatelli, G. J.
Org. Chem. 1997, 62, 6974; (c) Su, W.; Li, Y.; Zhang, Y. Synth.
Commun. 2002, 32, 2101.
[14] Su, W.; Li, Y.; Zhang, Y. Synth. Commun. 2002, 32, 2101.
[15] Fleming, I.; Paterson, I.; Pearce, A. J. Chem. Soc., Perkin Trans. 1
1981, 256.
[16] Gais, H.; Bohme, A. J. Org. Chem. 2002, 67, 1153.
[17] Parham, W.; Groen, S. J. Org. Chem. 1964, 29, 2214.
[18] Lin, Y. A.; Chalker, J. M.; Floyd, N.; Bernardes, G. J. L.; Davis, B. G.
J. Am. Chem. Soc. 2008, 130, 9642.
[19] Boger, D. L.; Wysocki, R. J.; Ishizaki, T. J. Am. Chem. Soc. 1990,
112, 5230.
(400 MHz, CDCl3) δ: 7.82 (d, J＝8.2 Hz, 2 H), 7.47 (s,
2H), 7.30—7.12 (m, 5H), 5.82 (ddd, J＝7.8, 10.4, 17.9
Hz, 1H), 5.19 (d, J＝10.5 Hz, 2H), 5.01 (s, 1H),
5.01—4.69 (m, 1H), 3.86—3.83 (m, 4H), 2.41 (s, 3H);
13C NMR (100 MHz, CDCl3) δ: 143.8, 138.2, 136.3,
131.4, 129.2, 128.5, 128.2, 126.9, 125.6, 120.8, 103.1,
65.9, 65.3, 64.5, 21.5; IR (film) ν: 1349, 1163, 1086,
866, 814, 665 cm ; EI-MS (relative intensity) m/z (%):
282 (8), 109 (11), 91 (14), 73 (100), 45 (23); HRMS
calcd for C19H21NO4S2Na (M＋Na)＋: 414.0804, found
414.0800.
－
1
Acknowledgement
The project is supported by NSFC (Nos. 20902005,
20832002, 20772003, 20821062) and 973 Program (No.
2012CB821600).
[20] Oswald, A. A.; Griesbaum, K.; Hdson, B. E. J. Org. Chem. 1963, 28,
2355.
(Pan, B.; Qin, X.)
Chin. J. Chem. 2012, 30, 2029—2035
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2035