Regioselective and oxidant-free sulfinylation of indoles and pyrroles with sulfinamides

Article abstract of DOI:10.1039/c9ob00526a

An unexpected time-controlled highly selective C3-or C2-sulfinylation of pyrroles with sulfinamides is reported for the first time. The sulfinylation of indoles with sulfinamides using this protocol is oxidant-free and can be performed under obviously more feasible conditions (1.2 equiv. of indoles, 10 min) in comparison with the precedent procedure (3-20 equiv. of indoles, 16-18 h, ammonium persulfate as oxidant, hv). A variety of functional groups were tolerated, and various C2-thioindoles and C2/3-thiopyrroles were obtained in moderate to excellent yields.

Full text of DOI:10.1039/c9ob00526a

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Regioselective and oxidant-free sulfinylation of indoles and
pyrroles with sulfinamides
Yuan-Zhao Ji,a Jin-Yu Zhang,a Hui-Jing Li,*a Chunguang Han,a Yi-Kun Yang,a and Yan-Chao Wu*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
An unexpected time-controlled highly selective C3- or C2-sulfinylation of pyrroles with sulfinamides is reported for the first
time. The sulfinylation of indoles with sulfinamides using this protocol is oxidant-free and under obviously more feasible
conditions (1.2 equiv. of indoles, 10 min) in comparison to the precedent procedure (3–20 equiv. of indoles, 16–18 h,
ammonium persulfate as oxidant, hv). A variety of functional groups were tolerated, and various C2-thioindoles and C2/3-
thiopyrroles were obtained in moderate to excellent yields.
DOI: 10.1039/x0xx00000x
www.rsc.org/
1990 as Prilosec in the United States.4m Esomeprazole, a single
enantiomer of omeprazole has also been launched as Nexium in
2000 by AstraZeneca.4m Besides, Sulindac has been approved by
Introduction
Sulfoxides are among the most versatile building blocks in
organic synthesis.1 They have been a subject of consistent
interest due to the presence of their structural motifs in a large
number of natural products,2 ligands,3 pharmaceuticals,4 and
function materials5 (Scheme 1). Sulfoxides display a broad range
of biological activities, such as antihypertension,4a antibacteria,
antifungi, anti-atherosclerosis4b-4e,4l,4n and anti-ulcer4k,4m,4o
properties. As representative sulfoxide, omeprazole, the first
proton-pump inhibitor used in clinical practice, has been
launched in 1988 as Losec in Europe, and in
the FDA as a anti-inflammatory drug (NSAID).4l
The significance and prevalence of this class of compounds
has served to stimulate continual interest in synthetic
community.6-10 In general, sulfoxides could be produced by
oxidation of sulfides,6 nucleophilic substitution on sulfinyl
derivatives, such as sulfinyl chlorides and sulfinates, with
organometallic reacgents7 or aromatic compounds.8 In addition,
the other systhesis of sulfoxides, including the use of palladium-
catalyzed protocols9, has also been reported.10 However, these
methods often suffer from certain drawbacks such as using
unstable organometallic agents or sulfinyl chlorides as starting
materials, and limited substrate scopes.
Compared with other sulfinylation agents such as sulfinyl
chlorides, sulfinamides are more stable and easier to handle. As
a consequence, a quite amount of efforts have been dedicated
to the use of sulfinamides as synthetic intermediates in organic
systhesis.11 In recently years, much new strategies by using
sulfinamides as starting materials have emerged with the goal
widening the reaction scope and improving overall synthetic
efficiency.12 Inspiringly, König and
Pharmaceuticals
OH
O
O
S
N
N
N
N
H
O
F
omeprazole4i
O
O
O
N
S
O
N
S
O
H
esomeprazole4i
Ligands
sulindac4h
O
p-Tol
a) König's work 12c
O
N
S
S
O
O
O
O
O
R2
R1
O
S
indoles
(3-20 equiv.)
pyrroles
(5-20 equiv.)
O
S
O
S
N
Bu
S
Ar
Ar
Ar
N
H
p-Tol
(NH4)2S2O8, hv,
25 oC, 16-18 h
(NH4)2S2O8, hv,
25 oC, 16-18 h
O
O
N
R1
bis-sulfoxide ligand3a sulfoxide-oxazoline ligand3g
Scheme 1. Selected useful sulfoxides.
b) This work
R1
O
S
N
10 min
Ar
Ar
R2
pyrroles
(1.2 equiv.)
indoles
(1.2 equiv.)
O
S
O
O
S
Bu
S
Ar
N
H
Ar
TMSCl,
TMSCl,
25 oC, 10 min
N
R1
0 o
C
a. School of Marine Science and Technology, Harbin Institute of Technology, Weihai
264209, P. R. China. E-mail: lihuijing@iccas.ac.cn
N
4-12 h
R1
b. Beijing National Laboratory for Molecular Sciences, Institute of Chemistry Chinese
Academy of Sciences, Beijing 100190, P. R. China. E-mail: ycwu@iccas.ac.cn
Electronic Supplementary Information (ESI) available: Experimental procedures,
characterization data, and copies of NMR spectra. See DOI: 10.1039/x0xx00000x
Scheme 2. Synthesis of sulfoxides from sulfinamides.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Journal Name
co-worker reported an elegant synthesis of sulfoxides from increase was observed when the loading of indoleV2ieaw eArxticcleeeOdnleinde
sulfinamides and heteroarenes in the presence of ammonium 1.2 equivalents (entries 1–4). A series ofDoOtIh: 1e0r.1s0il3i9c/oCn9OreBa0g0e52n6tAs
persulfate as oxidant by the visible-light accelerated (Scheme such as TIPSCl, DMSCl and TMSOTf were further investigated for
2a).12c The reaction could tolerate N-protected and unprotected this reaction, but no better results were obtained in comparison
of indoles. However, up to 20 equivalents of indoles along with to that with the use of TMSCl as the promoter (entries 2 and 5–
an oxidant are required in this reaction, which limits its 7). The solvent played an important role in this reaction. With
application. To overcome this inherent problem, development the use of CH3NO2, CH3CN, and THF in comparison to CH2Cl2,
of a practical strategy for the synthesis of sulfoxides becomes a lower yields were observed (entries 2 and 8–10). Further
high priority. Herein we would like to report a regioselective and parameters optimization identified the most effective TMSCl
oxidant-free sulfinylation of indoles and pyrroles with loading as 1.8 equivalents (entries 2 and 11–17). With the use
sulfinamides (Scheme 2b).
of sulfinamides 1b–d in comparison with sulfinamide 1a,
relatively lower yields were observed (entries 2 and 18–20).
Furthermore, scaling up N-butyl-4-methylbenzenesulfinamide
(1a) to 1.06 g (5.0 mmol) the reaction provided the yield at an
excellent level (entry 21).
Results and discussion
The reaction of N-butyl-4-methylbenzenesulfinamide (1a) with
1-methyl-1H-indole (2a) was used as a probe for evaluating the
reaction conditions, and the representative results are
summarized in Table 1. The treatment of sulfinamide (1a) with
indole 2a in the presence of TMSCl (3.0 equiv.) at room
temperature under air for 10 min afforded sulfoxide 3a in 80%
yield (entry 1). The yield of sulfoxide 3a was further increased
up to 86% when the loading of indole 2a was increased from 1.0
equivalent to 1.2 equivalents (entries 1–2). No further
The optimized reaction conditions proved to be effective
O
S
R1
TMSCl
O
S
R1
(1.8 equiv.)
Bu
Ar
+
Ar
N
N
R2
H
CH2Cl2, air,
N
R2
25 oC, 10 min
1
2
3
O
O
O
S
S
S
N
R
N
R
N
R
Cl
Table 1. Optimization of the reaction conditionsa
3a
R = Me, , 83%
3c
R = Me, , 90%
3e
R = Me, , 83%
3b
3d
3f
R = H, , 89%
R = H, , 94%
R = H, , 91%
O
S
O
S
O
S
O
S
O
S
promoter (Y equiv.)
+
R
solvent, air,
25 °C, 10 min
N
N
N
R
N
R
N
R
F
F3C
O2N
1
2a
3a
a
3g
R = Me, , 84%
3i
R = Me, , 84%
3k
R = Me, , 86%
a
3h
3j
3l
R = H, , 93%
R = H, , 90%
R = H, , 90%
Entry
1c
Sulfinamide 1
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1a (R = nBuNH)
1b (R = nPrNH)
1c (R = iPr2N)
Promoter (Y equiv.)
TMSCl (3.0)
TMSCl (3.0)
TMSCl (3.0)
TMSCl (3.0)
TIPSCl (3.0)
DMSCl (3.0)
TMSOTf (3.0)
TMSCl (3.0)
TMSCl (3.0)
TMSCl (3.0)
TMSCl (0.1)
TMSCl (0.5)
TMSCl (1.0)
TMSCl (1.5)
TMSCl (1.8)
TMSCl (2.0)
TMSCl (2.5)
TMSCl (1.8)
TMSCl (1.8)
TMSCl (1.8)
TMSCl (1.8)
Solvent
Yield (%)b
80
86
O
S
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH3NO2
CH3CN
THF
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
O
S
O
S
O2N
2d
3e
S
N
N
R
86
86
45
N
R
R
4f
a
a
b
3m
3o
3q
R = Me,
, 84%
a
R = Me, , 85%
R = Me, , 52%
b
5d
a
3n
3p
3r
R = H, , 85%
R = H, , 86%
R = H, , 59%
6d
83
76
40
OMe
7d
Br
O
O
S
O
S
8d
S
9d
67
70
OMe
N
R
N
R
N
R
10d
11d
12d
13d
14d
15d
16d
17d
18d
19d
20d
21d
3s
3u
3w
R = Me, , 31%
R = Me, , 87%
R = Me, , 82%
7
38
70
79
86 (83g)
86
R = H, 3t, 93%
R = H, 3v, 87%
R = H, 3x, 42%
Br
O
S
O
S
O
S
Cl
F
N
R
N
R
N
R
86
74
3y
3aa
3ac
, 70%
R = Me, , 63%
R = Me,
, 60%
R = Me,
3z
3ab
3ad
R = H, , 84%
R = H, , 90%
R = H,
, 71%
69
83
82g,h
O
S
O
S
1d (R = BnNH)
1a (R = nBuNH)
N
R
N
Bn
a
General conditions: 1a (0.2 mmol), 2a (0.2–0.4 mmol), and silicon reagent
(0.02–0.6 mmol) in solvent (1.0 mL) at 25 °C for 10 min. b Crude determined by
1H NMR spectroscopy using 0.2 mmol of CH2Br2 as a standard. c 0.2 mmol of 2a.
d 0.24 mmol of 2a. e 0.3 mmol of 2a. f 0.4 mmol of 2a. g Isolated yield. h Reaction
was carried out at 1.06 g scale of 1a (5.0 mmol). TMS = trimethylsilyl. TIPS =
triisopropylsilyl. DMS = dimethylsilyl. THF = tetrahydrofuran.
3ae,
3ag
, 70%
R = Me,
85%
3af
R = H,
, 88%
Scheme 3. TMSCl-promoted sulfinylation of indoles 2 with sulfinamides 1. General
conditions: 1 (0.2 mmol), 2 (0.24 mmol), and TMSCl (0.36 mmol) in CH2Cl2 (1.0 mL) at 25
0.72 mmol of TMSCl was used.
benzylmethanesulfinamide was used instead of N-butylmethanesulfinamide.
a
b
°C for 10 min. Isolated yields.
N-
2 | J. Name., 2012, 00, 1-3
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TMSCl
TMSCl
O
S
O
R
O
S
for a wide range of sulfinamides 1 and indoles 2, and the
representative results are summarized in Scheme 3. Aromatic
sulfinamides with their aromatic rings bearing hydrogen atoms,
electron-donating and electron-withdrawing groups reacted
smoothly with N-protected or unprotected indoles in the
presence of TMSCl (1.8 equiv.) to afford sulfoxides 3a–n in 83–
94% yields within 10 min. An N-butylthiophene-2-sulfinamide
was also investigated, which reacted equally well with N-
protected or unprotected indoles to give sulfoxides 3o and 3p
in 85% and 86% yields, respectively. Treatment of N-
benzylmethanesulfinamide with N-protected or unprotected
indoles give sulfoxides 3q and 3r in 52% and 59% yields,
respectively. A wide variety of indoles with substituent groups
such as methoxyl, halogen and methyl at 2-, 4-, 5-, 6- and 7-
positions reacted smoothly with sulfinamide 1a under the
standard conditions to give sulfoxides 3s–af in good yields. N-
Substituted indole with benzyl reacted with sulfinamide 1a
under the standard conditions to generate sulfoxide 3ag in 70%
yield. It is noteworthy that higher yields were observed with the
use of N-unprotected indoles in comparison to N-protected
indoles. These reactions are extremely easy to perform under
mild reaction conditions without the need for using inert
atmosphere.
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(1.8 equiv.)
(1.8 equiv.)
S
N
Bu
DOI: 10.1039/C9OB00526A
Ar
Ar
+
Ar
N
H
N
R
CH2Cl2, air,
CH2Cl2, air,
N
0 oC,
0 oC,
10 min
4 h
R
7
1
2
8
C2-sulfinylation
O
O
S
O
S
S
N
N
N
N
Cl
7a
7b
7c
, 71%
, 76%
, 54%
O
S
O
S
O
S
R
H
N
N
F
7d
7e
R = H, , 69%
7g
, 64%
, 45%
7f
R = Bn, , 57%
C3-sulfinylation
O
S
O
S
O
S
N
N
N
Cl
a
a
8a
8b
8c
, 67%
, 73%
, 73%
O
S
O
S
O
S
N
NH
N
F
R
b
8d
8e
R = H, , 62%
8g
, 71%
, 67%
a
8f
R = Bn, , 61%
A plausible reaction mechanism for the oxidant-free
sulfinylation of indoles 2 with sulfinamides 1 is illustrated in
Scheme 4. Sulfinamides 1 were converted to intermediates 4 by
chelating with one equivalent of TMSCl. Electrophilic
substitution reaction of indoles 2 at the C-3 position with the
intermediates 4 generated compounds 5, in which another
equivalent of TMSCl was used as the Lewis acid to promote the
release of amine. Loss of a proton from compounds 5 afforded
intermediates 6, in which one equivalent of TMSCl was
recovered. Finally, detachment of TMSCl from 6 afforded
sulfoxides 3 (Scheme 4). The reversible process was terminated
by aqueous work-up with the consumption of one equivalent of
TMSCl.
To future expand the substrate scope of this sulfinylation
protocol, the feasibility of this sulfoxide synthesis was also
checked by using a serial of pyrroles 2 as the substrates (Scheme
5). Reaction of sulfinamides 1 with N-protect or unprotected
pyrroles 2 in the presence of TMSCl (1.8 equiv.) at 0 °C for 10
min afforded 2-substituted products 7a–g in moderate to good
yields. This result of C2-sulfinylation presented above is
consistent with the literature reported by König.12c In addition,
the minor 3-substituted products was
Scheme 5. TMSCl-promoted sulfinylation of pyrroles 2 with sulfinamides 1. General
conditions: 1 (0.2 mmol), 2 (0.24 mmol), and TMSCl (0.36 mmol) in CH2Cl2 (1.0 mL) at 0
°C for 10 min (for 7) or 12 h (for 8). Isolated yields. a 5 h. b 0.72 mmol of TMSCl was used
for 12 h.
also observed under the same conditions (0 °C, 10 min).
Interestingly, the reactions exclusively afforded 3-substituted
products 8a–g in good yields under the identical conditions,
albeit with a longer reaction time (i.e., 10 min versus 4–12 h).
The result indicated that our sulfoxide synthetic protocol
exhibited a time-controlled selective C3- or C2-sulfinylation of
pyrroles 2 with sulfinamides 1.
To glean an insight into the reaction mechanism, several
control experiments were performed as shown in Scheme 6.
The reaction of sulfinamide 1a with 1-methyl-1H-pyrrole (2a)
O
S
NHBu
TMSCl
(1.8 equiv.)
1a
7a
+
8a
(a)
CH2Cl2, 0 oC, 12 h
BHT (1.0 equiv.)
BHT (2.0 equiv.)
0%
0%
70%
70%
N
2a
ClTMS
Ar
ClTMS
O
O
S
BHT (2.0 equiv.)
O
S
O
S
H
2 TMSCl
R
TMSCl
NHBu
S
N
TMSCl (1.8 equiv.)
8a
51%
(b)
(c)
Ar
NHBu
Ar
- BuNHTMS
CH2Cl2, 0 oC, 2 h
N
R
Cl
1
4
5
7a
N
O
S
2
O
S
R
TMSCl (1.8 equiv.)
N
ClTMS
Ar
O
O
CH2Cl2, 0 o
C
BuNHTMS
-TMSCl
N
R
S
S
Ar
-BuNHH
-TMSCl
R = Me, 7a
R = H, 7e
R = Me, 8a, 52%a
R = H, 8e, 53%b
N
R
N
6
3
R
Scheme 6. Control experiments. Isolated yields. a 2 h. b 4 h.
Scheme 4. Proposed mechanism for the sulfinylation of indoles 2 with sulfinamides 1.
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ClTMS
Ar
ClTMS
Conclusions
View Article Online
DOI: 10.1039/C9OB00526A
O
S
O
S
O
S
R
2 TMSCl
TMSCl
NHBu
N
Cl
In summary, we have developed an oxidant-free, fast and
regioselective 3-arylsulfinylindole synthesis from sulfinamides
and indoles in the presence of trimethylsilyl chloride. The
synthetic protocol offers attractive industrial prospects as the
reaction took place at room temperature without the need for
using transition metal catalysts and inert atmosphere. The
reaction tolerates a wide range of heteroarene substrates that
react with readily available and stable sulfinamides for the
synthesis of sulfoxides with good to excellent yields. Most
importantly, a highly selective C3- or C2-sulfinylation of pyrroles
with sulfinamides has been accomplished here for the first time
by controlling the reaction time.
Ar
NHBu
Ar
- BuNHTMS
H
1
4
9
N
R
ClTMS
2
O
S
R
O
S
O
S
R
BuNHTMS
N
N
Ar
Ar
Ar
-BuNHH
-TMSCl
-TMSCl
10
7
8
N
R
-TMSCl
TMSCl
ClTMS
Ar
ClTMS
O
S
O
O
S
R
S
H
N
Ar
Ar
N
R
N
R
11
12
13
Scheme 7. Proposed mechanism for the sulfinylation of pyrroles 2 with sulfinamides 1.
Experimental
General Information
still took place in the presence of radical scavenger BHT
(butylated hydroxytoluene, Scheme 5a). Furthermore, reaction
of 2-substituted sulfoxide product 7a in the presence radical
scavenger BHT, 3-substituted sulfoxide 8a was obtained in 51%
yield (Scheme 5b). These results ruled out the possibility of a
radical process. By treating of 2-substituted sulfoxide products
7a and 7e in the presence of TMSCl (1.8 equiv.) in CH2Cl2 at 0 °C,
3-substituted sulfoxide products 8a and 8e were generated in
52% and 53% yields, respectively (Scheme 5c). The result
indicated that the reactions probably undergo a rearrangement
from 2-substituted sulfinylpyrroles to 3-substituted
sulfinylpyrroles.
Based on the control experiments mentioned above and
related reports8b,8d in the literature, a possible reaction pathway
for the time-controlled selective C3- or C2-sulfinylation of
pyrroles 2 with sulfinamides 1 is shown in Scheme 7. Chelation
of sulfinamides 1 with TMSCl formed intermediates 4, which
underwent nucleophilic substitution reaction with pyrroles 2
generated compounds 9. Loss of a proton from compounds 9
afforded intermediates 10. Finally, detachment of TMSCl from
Common reagents and materials were purchased from
commercial sources and were used without further purification.
TLC plates were visualized by exposure to ultra violet light (UV).
IR spectra were recorded by using an Electrothemal Nicolet 380
spectrometer. High-resolution mass spectra (HRMS) were
recorded by using an Electrothemal LTQ-Orbitrap mass
spectrometer. Melting points were measured by using a Gongyi
X-5 microscopy digital melting point apparatus and are
1
uncorrected. H NMR and 13C NMR spectra were obtained by
using a Bruker Avance III 400 MHz or a JNM-ECZ400S/L1 400
MHz NMR spectrometer. Chemical shifts for protons are
reported in parts per million ( scale) and are referenced to
residual protium in the NMR solvents [CDCl3:  7.26, DMSO-d6:
 2.50]. Chemical shifts for carbon resonances are reported in
parts per million ( scale) and are referenced to the carbon
resonances of the solvent (CDCl3:  77.0, DMSO-d6:  39.43).
Data are represented as follows: chemical shift, multiplicity (s =
singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br =
broad), integration, and coupling constant in Hertz (Hz).
General procedure for the preparation of sulfinamides 1a–1c
and 1e–1g12c
To a three-necked round bottomed flask was added sodium
arylsulfinate (2 mmol, 1 equiv.) in anhydrous toluene (5 mL)
under argon atmosphere. After cooling the solution to 0 °C
oxalyl chloride (2.2 mmol, 1.1 equiv.) was added dropwise. The
reaction mixture was heated to room temperature during 1 h to
generate sulfinyl chloride in situ. A second round bottomed
flask was charged with the corresponding amine (2.4 mmol, 1.2
equiv.) and trimethylamine (3.0 mmol, 1.5 equiv.) in anhydrous
toluene (6 mL). To this flask, the in situ generated sulfinyl
chloride was added dropwise at 0 °C. The reaction mixture was
stirred for 1 h at room temperature and then poured in H2O (5
mL) and extracted with EtOAc (5 mL) three times. The combined
organic layers were dried over anhydrous Na2SO4 and
concerntrated in vacuo. The crude product was purified by flash
chromatography on silica gel (100–200 mesh). The product was
identified by NMR and HRMS spectra.
the intermediates 10 afforded C2-arylsulfinylpyrroles
7
(Scheme 7). The reversible process was terminated by aqueous
work-up with the consumption of one equivalent of TMSCl.
Considering the electron density at the C2-position of pyrroles
2 is usually more than that at the C3-position,13 the C2-
arylsulfinylpyrroles 7 should be the kinetically controlled
products. On the other hand, tautomerization of compounds 10
might form a small concentration of intermediates 11,8b which
would potentially allow an intramolecular nucleophilic
substitution reaction to occur with the assistance of the imine
ammonium functionality of intermediates 11 to generate
carbenes 12. The intramolecular 1,2-H shift of carbenes 12
would in turn form intermediates 13.14 Finally, detachment of
TMSCl from 13 afforded the C3-arylsulfinylpyrroles 8 (Scheme
7). The reversible process was terminated by aqueous work-up
with the consumption of one equivalent of TMSCl. As the C2-
arylsulfinylpyrroles 7 are possible the kinetically controlled
products, the C3-arylsulfinylpyrroles
thermodynamic products.
8
might be the
N-butyl-4-methylbenzenesulfinamide (1a): White solid, 311.0
mg, 73% yield; 1H NMR (400 MHz, CDCl3) : 7.57 (d, J = 7.9 Hz,
4 | J. Name., 2012, 00, 1-3
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2H), 7.28 (d, J = 7.8 Hz, 2H), 4.18 (s, 1H), 3.13–3.05 (m, 1H), 125.9, 44.4, 21.2; HRMS (ESI) m/z: Calcd for C14H15NaNOS
View Article Online
2.84–2.76 (m, 1H), 2.40 (s, 3H), 1.51–1.44 (m, 2H), 1.35–1.25 (m, [M+Na]+: 268.0767. Found: 268.0771.
DOI: 10.1039/C9OB00526A
2H), 0.85 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) : 141.1, General procedure for the preparation of sulfinamide 1h-1j12c
140.9, 129.3, 125.8, 40.6, 32.4, 21.2, 19.8, 13.5; HRMS (ESI) m/z: To a solution of sulfonyl chloride (2 mmol, 1.0 equiv.) and
Calcd for C11H17NaNOS [M+Na]+: 234.0923. Found: 234.0919.
triethylamine (4 mmol, 2.0 equiv.) in anhydrous CH2Cl2 (6 mL) at
4-Methyl-N-propylbenzenesulfinamide (1b): White solid, 0 °C under argon atmosphere, was added a solution of butan-1-
275.8 mg, 70% yield; 1H NMR (400 MHz, CDCl3) : 7.53 (d, J = 8.2 amine (2 mmol, 1.0 equiv.) and triphenylphosphine (2 mmol,
Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H), 4.32 (s, 1H), 3.04–2.96 (m, 1H), 1.0 equiv.) in anhydrous CH2Cl2 (6 mL) over a period of 12 min.
2.76–2.68 (m, 1H), 2.35 (s, 3H), 1.51–1.42 (m, 2H), 0.83 (t, J = The reaction mixture was stirred for 18 h. The reaction mixture
7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) : 141.1, 140.8, 129.2, was concentrated by rotavap. The crude product was purified
125.7, 42.6, 23.6, 21.1, 11.1; HRMS (ESI) m/z: Calcd for by flash chromatography on silica gel (100–200 mesh) to give
C10H15NaNOS [M+Na]+: 220.0767. Found: 220.0769.
the desired sulfinamide.
N,N-diisopropyl-4-methylbenzenesulfinamide (1c): White N-butyl-4-(trifluoromethyl)benzenesulfinamide (1h): White
solid, 258.1 mg, 54% yield; 1H NMR (400 MHz, CDCl3) : 7.49 (d, solid, 296.8 mg, 56% yield; 1H NMR (400 MHz, CDCl3) : 7.83 (d,
J = 8.2 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 3.57–3.47 (m, 2H), 2.36 J = 8.1 Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 4.28–4.19 (m, 1H), 3.18–
(s, 3H), 1.37 (d, J = 6.8 Hz, 6H), 1.08 (d, J = 6.8 Hz, 6H); 13C NMR 3.04 (m, 1H), 2.79–2.70 (m, 1H), 1.51–1.44 (m, 2H), 1.36–1.26
(100 MHz, CDCl3) : 141.4, 140.2, 129.2, 126.4, 46.3, 23.7, 23.6, (m, 2H), 0.85 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) :
21.1; HRMS (ESI) m/z: Calcd for C13H21NaNOS [M+Na]+: 148.4, 132.8 (q, JC-F = 32.8 Hz), 126.7, 125.8 (q, JC-F = 3.7 Hz),
262.1236. Found: 262.1231.
123.6 (q, JC-F = 272.6 Hz), 40.9, 32.4, 19.9, 13.6; HRMS (ESI) m/z:
N-butylbenzenesulfinamide (1e): Yellow liquid, 279.7 mg, 71% Calcd for C11H14F3NaNOS [M+Na]+: 288.0640. Found: 288.0648.
yield; 1H NMR (400 MHz, CDCl3) : 7.71–7.69 (m, 2H), 7.51–7.44 N-butyl-4-nitrobenzenesulfinamide (1i): Yellow solid, 246.8 mg,
(m, 3H), 4.07 (s, 1H), 3.15–3.07 (m, 1H), 2.85–2.77 (m, 1H), 51% yield; 1H NMR (400 MHz, CDCl3) : 8.35–8.32 (m, 2H), 7.91–
1.51–1.44 (m, 2H), 1.35–1.24 (m, 2H), 0.85 (t, J = 7.3 Hz, 3H); 13
C
7.87 (m, 2H), 4.35–4.32 (m, 1H), 3.17–3.08 (m, 1H), 2.76–2.68
NMR (100 MHz, CDCl3) : 144.2, 130.6, 128.6, 125.8, 40.7, 32.4, (m, 1H), 1.52–1.44 (m, 2H), 1.36–1.26 (m, 2H), 0.85 (t, J = 7.5 Hz,
19.8, 13.5; HRMS (ESI) m/z: Calcd for C10H15NaNOS [M+Na]+: 3H); 13C NMR (100 MHz, CDCl3) : 151.2, 149.4, 127.4, 123.9,
220.0767. Found: 220.0762.
40.9, 32.4, 19.9, 13.6; HRMS (ESI) m/z: Calcd for C10H14NaN2O3S
N-butyl-4-chlorobenzenesulfinamide (1f): Yellow liquid, 300.3 [M+Na]+: 265.0617. Found: 265.0623.
mg, 65% yield; 1H NMR (400 MHz, CDCl3) : 7.64–7.62 (m, 2H), N-butyl-3-nitrobenzenesulfinamide (1j): Yellow solid, 174.2 mg,
7.48–7.46 (m, 2H), 4.07–4.06 (m, 1H), 3.14–3.06 (m, 1H), 2.82– 36% yield; 1H NMR (400 MHz, CDCl3) : 8.53 (t, J = 2.0 Hz, 1H),
2.74 (m, 1H), 1.52–1.44 (m, 2H), 1.35–1.24 (m, 2H), 0.86 (t, J = 8.32 (ddd, J = 8.2, 2.2, 1.1 Hz, 1H), 8.03 (dt, J = 7.8, 1.4 Hz, 1H),
7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) : 142.8, 137.1, 128.9, 7.70 (t, J = 7.9 Hz, 1H), 4.51–4.38 (m, 1H), 3.15–3.07 (m, 1H),
127.4, 40.7, 32.4, 19.8, 13.5; HRMS (ESI) m/z: Calcd for 2.77–2.69 (m, 1H), 1.52–1.45 (m, 2H), 1.36–1.25 (m, 2H), 0.84
C10H14ClNaN0S [M+Na]+: 254.0377. Found: 254.0380.
(t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) : 148.4, 147.1,
N-butyl-4-fluorobenzenesulfinamide (1g): Yellow liquid, 236.5 132.1, 129.9, 125.5, 121.5, 40.8, 32.4, 19.8, 13.5; HRMS (ESI)
mg, 55% yield; 1H NMR (400 MHz, CDCl3) : 7.67–7.64 (m, 2H), m/z: Calcd for C10H14NaN2O3S [M+Na]+: 265.0617. Found:
7.17–7.12 (m, 3H), 4.28 (s, 1H), 3.10–3.02 (m, 1H), 2.79–2.71 (m, 265.0619.
1H), 1.49–1.41 (m, 2H), 1.32–1.23 (m, 2H), 0.83 (t, J = 7.3 Hz, 3H); General procedure for the preparation of sulfinamide 1k12c
13C NMR (100 MHz, CDCl3) : 164.2 (d, JC-F = 250.9 Hz), 139.8 (d, To a solution of thiophene-2-sulfonyl chloride (2 mmol, 1.0
JC-F = 2.8 Hz), 128.2 (d, JC-F = 8.9 Hz), 115.8 (d, JC-F = 22.3 Hz), 40.5, equiv.) in anhydrous CH2Cl2 (6 mL) at 0 °C under argon
32.4, 19.8, 13.5; HRMS (ESI) m/z: Calcd for C10H14FNaNOS atmosphere, was added a solution of butan-1-amine (2 mmol,
[M+Na]+: 238.0672. Found: 238.0675.
General procedure for the preparation of sulfinamide 1d11a
1.0 equiv.), triphenylphosphine (2 mmol, 1.0 equiv.) and
triethylamine (2 mmol, 2.0 equiv.) in anhydrous CH2Cl2 (6 mL)
To a solution of p-toluensulfonyl chloride (190 mg, 1 mmol, 1 over a period of 12 min. The reaction mixture was stirred for 18
equiv) and triethylamine (1.4 mL, 10 mmol, 10 equiv.) in CH2Cl2 h. The reaction mixture was concentrated by rotavap. The crude
(3.0 mL) solution at 0 °C under argon atmosphere, was added a product was purified by flash chromatography on silica gel
solution of triphenylphosphine (262 mg, 1 mmol, 1equiv.) and (100–200 mesh) to give the desired sulfinamide.
benzylic amine (109 µl, 1 mmol, 1 equiv.) in CH2Cl2 (3.0 mL) N-butylthiophene-2-sulfinamide (1k): Yellow liquid, 263.9 mg,
solution over a period of 1 h. After addition, TLC showed all of 65% yield; 1H NMR (400 MHz, CDCl3) : 7.55 (d, J = 4.9 Hz, 1H),
the sulfonyl chloride was consumed. The reaction mixture was 7.37 (d, J = 3.5 Hz, 1H), 7.09 (t, J = 4.2 Hz, 1H), 4.43–4.41 (m, 1H),
concentrated by rotavap. The crude product was purified by 3.21–3.13 (m, 1H), 3.03–2.94 (m, 1H), 1.56–1.49 (m, 2H), 1.38–
flash chromatography on silica gel (100–200 mesh) to give the 1.29 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3)
desired sulfinamide.
: 147.2, 131.0, 129.7, 127.7, 41.0, 32.5, 19.8, 13.5; HRMS (ESI)
N-benzyl-4-methylbenzenesulfinamide (1d): White solid, 303.8 m/z: Calcd for C8H13NaNOS2 [M+Na]+: 226.0331. Found:
mg, 62% yield; 1H NMR (400 MHz, CDCl3) : 7.63 (d, J = 8.0 Hz, 226.0333.
2H), 7.31–7.24 (m, 7H), 4.44 (s, 1H), 4.22 (dd, J = 13.5, 5.1 Hz, General procedure for the preparation of sulfinamide 1l15
1H), 3.88 (dd, J = 13.5, 7.2 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 The dimethyl disulfide (10 mmol, 1.0 equiv.) and acetic acid (20
MHz, CDCl3) : 141.2, 140.7, 137.7, 129.5, 128.5, 128.2, 127.5, mmol, 2.0 equiv.) were mixed and cooled to -20 °C. Sulfuryl
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chloride (31 mmol, 3.1 equiv.) was added dropwise with stirring 3452, 3053, 2922, 2850, 2359, 1516, 1473, 1458, 1033, 997, 742,
View Article Online
-1
+
DOI: 10.1039/C9OB00526A
over a period of 30 min. The reaction mixture was then stirred 695 cm ; HRMS (ESI) m/z: Calcd for C15H13NaNOS [M+Na] :
for 3 h at -20 °C and then allowed to warm to room temperature 278.0610. Found: 278.0613.
over a period of about 2 h. Evolution of SO2 and HCl was 3-(Phenylsulfinyl)-1H-indole (3d): White solid, m.p. = 126–
observed during this time. The mixture was warmed to 35 °C for 128 °C; 45.3 mg, 94% yield; 1H NMR (400 MHz, DMSO-d6)
1 h. The resulting acetyl chloride was evaporated under reduced :11.97 (s, 1H), 8.13 (d, J = 2.7 Hz, 1H), 7.66 (d, J = 7.4 Hz, 2H),
pressure, providing the desired product methanesulfinic 7.56–7.42 (m, 4H), 7.26 (d, J = 8.0 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H),
chloride as a liquid which was used without further purification. 6.96 (t, J = 7.5 Hz, 1H); 13C NMR (100 MHz, DMSO-d6) : 144.8,
The crude product methanesulfinic chloride in CH2Cl2 (7 mL) was 136.9, 130.7, 129.8, 128.8, 124.3, 123.1, 122.7, 120.5, 118.9,
added dropwise to a solution of benzylamine (40 mmol, 2.0 116.2, 112.6; FTIR (film): 3164, 2918, 2851, 1455, 1424, 1243,
equiv.) in CH2Cl2 (40 mL) at -78 °C. The mixture was stirred for 3 1016, 993, 742 cm-1; HRMS (ESI) m/z: Calcd for C14H11NaNOS
h at room temperature. The solution was filtered and the [M+Na]+: 264.0454. Found: 264.0451.
filtrate was washed with water and then dried over anhydrous 3-((4-Chlorophenyl)sulfinyl)-1-methyl-1H-indole (3e): White
Na2SO4, filtered, and concentrated. The residue was purified by solid, m.p. = 144–146 °C; 48.0 mg, 83% yield; 1H NMR (400 MHz,
flash chromatography on silica gel (100–200 mesh) to afford the CDCl3) : 7.66 (d, J = 8.3 Hz, 2H), 7.55 (s, 1H), 7.47–7.42 (m, 3H),
desired sulfinamide.
7.36 (d, J = 8.3 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.12 (t, J = 7.5 Hz,
N-benzylmethanesulfinamide (1l): Yellow liquid, 2.54g, 75% 1H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) : 142.9, 137.7,
yield; 1H NMR (400 MHz, CDCl3) : 7.31–7.24 (m, 5H), 4.43–4.40 136.1, 132.9, 129.0, 126.2, 124.0, 123.4, 121.5, 119.6, 115.7,
(m, 1H), 4.28–4.17 (m, 2H), 2.60 (s, 3H); 13C NMR (100 MHz, 110.2, 33.3; FTIR (film): 3455, 3052, 2924, 1515, 1471, 1457,
CDCl3) : 137.9, 128.6, 128.0, 127.6, 45.8, 41.6; HRMS (ESI) m/z: 1085, 1031, 1008, 975, 821, 765, 738 cm-1; HRMS (ESI) m/z:
Calcd for C8H11NaNOS [M+Na]+: 192.0454. Found: 192.0459.
Calcd for C15H12NaClNOS [M+Na]+: 312.0220. Found: 312.0218.
Experimental Procedure of Sulfoxides 3a-3ag
3-((4-Chlorophenyl)sulfinyl)-1H-indole (3f): White solid, m.p. =
1
The mixture of an arylsulfiniamide (0.2 mmol, 1 equiv.), an 128–130 °C; 50.1 mg, 91% yield; H NMR (400 MHz, CDCl3) :
indole (0.24 mmol, 1.2 equiv.) and TMSCl (0.36 mmol, 1.8 equiv.) 10.42 (s, 1H), 7.58 (d, J = 7.9 Hz, 2H), 7.43 (d, J = 7.9 Hz, 2H), 7.30
in CH2Cl2 (1.0 mL) was stirred at 25 °C for 10 min, then water (5 (d, J = 7.9 Hz, 1H), 724–7.22 (m, 2H), 7.13 (t, J = 7.6 Hz, 1H), 7.01
mL) and dichloromethane (10 mL) were added. The two layers (t, J = 7.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) : 141.7, 137.1,
were separated, and the aqueous phase was extracted with 136.4, 130.3, 129.2, 126.3, 123.6, 123.1, 121.6, 119.0, 115.3,
dichloromethane (3 × 10 mL). The combined organic extracts 112.6; FTIR (film): 3159, 2923, 2849, 1473, 1424, 1004, 742 cm-
were washed by brine, dried over anhydrous Na2SO4, filtered, 1; HRMS (ESI) m/z: Calcd for C14H10NaClNOS [M+Na]+: 298.0064.
and concentrated. The residue was purified by flash Found: 298.0068.
chromatography on silica gel (100–200 mesh) to afford the 3-((4-Fluorophenyl)sulfinyl)-1-methyl-1H-indole (3g): White
desired sulfoxide.
solid, m.p. = 130–132 °C; 45.9 mg, 84% yield; 1H NMR (400 MHz,
1-Methyl-3-(p-tolylsulfinyl)-1H-indole (3a): White solid, m.p. = CDCl3) : 7.69 (dd, J = 8.7, 5.1 Hz, 2H), 7.51 (s, 1H), 7.40 (d, J =
1
138–139 °C; 44.7 mg, 83% yield; H NMR (400 MHz, CDCl3) : 8.0 Hz, 1H), 7.33 (d, J = 8.3 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H), 7.14
7.62 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H),7.34–7.24 (m, 4H), (t, J = 8.6 Hz, 2H), 7.08 (t, J = 7.5 Hz, 1H), 3.78 (s, 3H); 13C NMR
7.12–7.08 (m, 1H), 3.79 (s, 3H), 2.40 (s, 3H); 13C NMR (100 MHz, (100 MHz, CDCl3) : 163.7 (d, JC-F = 250.7 Hz), 139.8 (d, JC-F = 2.9
CDCl3) : 140.9, 140.3, 137.6, 132.5, 129.5, 124.8, 124.3, 123.2, Hz), 137.8, 132.8, 127.1 (d, JC-F = 8.8 Hz), 124.1, 123.4, 121.5,
121.3, 119.8, 116.5, 110.0, 33.2, 21.2; FTIR (film): 3458, 3051, 119.7, 116.2, 116.1 (d, JC-F = 22.6 Hz, 1C), 110.1, 33.3; FTIR (film):
2921, 1515, 1458, 1173, 1033, 1013, 810, 765, 742, 621 cm-1; 3438, 3093, 2924, 1586, 1516, 1488, 1458, 1247, 1221, 1031,
HRMS (ESI) m/z: Calcd for C16H15NaNOS [M+Na]+: 292.0767. 1011, 833, 765, 742 cm-1; HRMS (ESI) m/z: Calcd for
Found: 292.0765.
C15H12NaFNOS [M+Na]+: 296.0516. Found: 296.0513.
3-(p-Tolylsulfinyl)-1H-indole (3b): White solid, m.p. = 120– 3-((4-Fluorophenyl)sulfinyl)-1H-indole (3h): Pale yellow oil,
1
122 °C; 45.4 mg, 89% yield; 1H NMR (400 MHz, CDCl3) : 10.49 48.2 mg, 93% yield; H NMR (400 MHz, CDCl3) : 10.72 (s, 1H),
(s, 1H), 7.54 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.0 Hz, 1H), 7.26 (d, J 7.66 (dd, J = 8.7, 5.1 Hz, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.26–7.23
= 8.1 Hz, 2H), 7.21 (d, J = 8.2 Hz, 1H), 7.16 (d, J = 2.3 Hz, 1H), 7.10 (m, 2H), 7.19–7.11 (m, 5H), 7.02 (t, J = 7.6 Hz, 1H);13C NMR (100
(t, J = 7.6 Hz, 1H), 6.98 (t, J = 7.5 Hz, 1H), 2.38 (s, 3H); 13C NMR MHz, CDCl3) : 163.8 (d, JC-F = 250.8 Hz), 138.5, 137.2, 130.4,
(100 MHz, CDCl3) : 140.5, 139.8, 137.1, 130.0, 129.6, 124.9, 127.1 (d, JC-F = 8.8 Hz), 123.5, 123.1, 121.5, 118.9, 116.2 (d, JC-F
123.4, 123.3, 121.3, 119.1, 115.8, 112.5, 21.2; FTIR (film): 3166, = 22.6 Hz), 115.2, 112.6; FTIR (film): 3398, 2062, 2924, 1587,
2978, 2920, 2852, 1491, 1426, 1081, 1021, 1002, 809, 763, 743 1487, 1223, 1140, 1010, 823, 744 cm-1; HRMS (ESI) m/z: Calcd
cm-1; HRMS (ESI) m/z: Calcd for C15H13NaNOS [M+Na]+: for C14H10NaFNOS [M+Na]+: 282.0359. Found: 282.0362.
278.0610. Found:278.0611.
1-Methyl-3-((4-(trifluoromethyl)phenyl)sulfinyl)-1H-indole
1-Methyl-3-(phenylsulfinyl)-1H-indole (3c): White solid, m.p. = (3i): White solid, m.p. = 149–151 °C; 54.3 mg, 84% yield; 1H NMR
1
126–128 °C; 45.9 mg, 90% yield; H NMR (400 MHz, CDCl3) : (400 MHz, CDCl3) : 7.83 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.3 Hz,
7.72 (d, J = 6.9 Hz, 2H), 7.50–7.41 (m, 5H), 7.32 (d, J = 8.2 Hz, 2H), 7.58 (s, 1H), 7.39 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.3 Hz, 1H),
1H), 7.25 (t, J = 7.6 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 3.80 (s, 3H); 7.30–7.25 (m, 1H), 7.11–7.07 (m, 1H), 3.83 (s, 3H);13C NMR (100
13C NMR (100 MHz, CDCl3) : 144.1, 137.6, 132.8, 130.0, 128.7, MHz, CDCl3) : 149.0, 137.8, 133.3, 131.9 (q, JC-F = 32.7 Hz),
124.8, 124.2, 123.2, 121.3, 119.7, 116.2, 110.0, 33.2; FTIR (film): 125.8, (q, JC-F = 3.7 Hz),125.3, 124.1, 123.63, 123.58 (q, JC-F
=
6 | J. Name., 2012, 00, 1-3
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271.0 Hz), 121.8, 119.7, 115.5, 110.3, 33.5; FTIR (film): 2924, 7.30 (dd, J = 7.6, 1.0 Hz, 1H), 7.15 (dd, J = 7.5, 1.0VHiezw,A1rtHicl)e,O7n.l0in9e
2358, 1518, 1398, 1322, 1168, 1060, 1034, 745 cm-1; HRMS (ESI) (dd, J = 5.0, 3.7 Hz, 1H), 3.85 (s, 3H); 13C NMR (100 MHz, CDCl3)
DOI: 10.1039/C9OB00526A
m/z: Calcd for C16H12NaF3NOS [M+Na]+: 346.0484. Found: : 147.6, 137.8, 131.5, 130.8, 129.5, 127.3, 124.2, 123.4, 121.4,
346.0490.
119.9, 116.6, 110.2, 33.4; FTIR (film): 3096, 2922, 2236, 1516,
3-((4-(Trifluoromethyl)phenyl)sulfinyl)-1H-indole (3j): White 1483, 1335, 1036, 907, 729 cm-1; HRMS (ESI) m/z: Calcd for
solid, m.p. = 127–129 °C; 55.6 mg, 90% yield; 1H NMR (400 MHz, C13H11NaNOS2 [M+Na]+: 284.0174. Found: 284.0172.
DMSO-d6) : 12.08 (s, 1H), 8.24 (d, J = 2.9 Hz, 1H), 7.89–7.84 (m, 3-(Thiophen-2-ylsulfinyl)-1H-indole (3p): 0.72 mmol of TMSCl
4H), 7.49 (d, J = 8.2 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.16 (t, J = was used. Pale yellow oil, 42.5 mg, 86% yield; 1H NMR (400 MHz,
7.2 Hz, 1H); 6.97 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, DMSO- DMSO-d6) : 12.00 (s, 1H), 8.07 (t, J = 3.2 Hz, 1H), 7.85–7.84 (m,
d6) : 150.1, 137.1, 131.5, 130.0 (q, JC-F = 32.1 Hz), 125.9, (q, JC-F 1H), 7.53–7.45 (m, 3H), 7.23–7.04 (m, 3H); 13C NMR (100 MHz,
= 3.9 Hz), 125.4, 123. 8 (q, JC-F = 271.5 Hz), 123.0, 120.9, 118.7, DMSO-d6) : 148.2, 137.0, 131.1, 129.5, 128.8, 127.6, 123.0,
115.2, 112.8; FTIR (film): 3165, 2981, 2359, 1605, 1321, 1125, 122.8, 120.6, 119.1, 116.7, 112.6; FTIR (film): 3177, 2923, 2851,
1059, 1006, 747 cm-1; HRMS (ESI) m/z: Calcd for C15H10NaF3NOS 2362, 1659, 1422, 1244, 1008, 744 cm-1; HRMS (ESI) m/z: Calcd
[M+Na]+: 332.0327. Found: 332.0332.
for C12H9NaNOS2 [M+Na]+: 270.0018. Found: 227.0021.
1-Methyl-3-((4-nitrophenyl)sulfinyl)-1H-indole (3k): 0.72 1-Methyl-3-(methylsulfinyl)-1H-indole (3q): Pale yellow oil,
mmol of TMSCl was used. Yellow solid, m.p. = 144–146 °C; 51.6 20.0 mg, 52% yield; 1H NMR (400 MHz, DMSO-d6) : 7.92 (s, 1H),
mg, 86% yield; 1H NMR (400 MHz, CDCl3) : 8.28 (d, J = 8.8 Hz, 7.88 (d, J = 8.3 Hz, 1H), 7.57 (d, J = 8.3 Hz, 1H), 7.30 (t, J = 7.6 Hz,
2H), 7.86 (d, J = 8.8 Hz, 2H), 7.64 (s, 1H), 7.35–7.24 (m, 3H), 7.07 1H), 7.20 (t, J = 7.5, 1.0 Hz, 1H), 3.83 (s, 3H), 2.95 (s, 3H); 13
C
(t, J = 7.5 Hz, 1H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) : NMR (100 MHz, DMSO-d6) : 137.3, 130.8, 123.9, 122.7, 120.7,
152.2, 148.7, 137.8, 133.6, 125.9, 123.9, 123.8, 121.9, 119.5, 119.2, 115.9, 111.0, 40.5, 32.9; FTIR (film): 3401, 2360, 1562,
114.7, 110.4, 33.5; FTIR (film): 3094, 2926, 2359, 1517, 1343, 1519, 1264, 1023, 1000, 746 cm-1; HRMS (ESI) m/z: Calcd for
1041, 852, 747 cm-1; HRMS (ESI) m/z: Calcd for C15H12NaN2O3S C10H11NaNOS [M+Na]+: 216.0454. Found: 216.0457.
[M+Na]+: 323.0461. Found: 323.0465.
3-(Methylsulfinyl)-1H-indole (3r): Pale yellow oil, 21.1 mg, 59%
3-((4-Nitrophenyl)sulfinyl)-1H-indole (3l): 0.72 mmol of TMSCl yield; 1H NMR (400 MHz, DMSO-d6) : 11.85 (s, 1H), 7.90 (s, 1H),
was used. Yellow solid, m.p. = 149–151 °C; 51.5 mg, 90% yield; 7.88 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.23 (t, J = 7.6 Hz,
1H NMR (400 MHz, DMSO-d6) : 12.12 (s, 1H), 8.33 (d, J = 8.4 Hz, 1H), 7.15 (t, J = 7.5, 1H), 2.96 (s, 3H); 13C NMR (100 MHz, DMSO-
2H), 8.27 (d, J = 2.8 Hz, 1H), 7.89 (d, J = 8.5 Hz, 2H), 7.50 (d, J = d6) : 136.8, 127.1, 123.6, 122.6, 120.4, 119.0, 116.9, 112.6, 40.3;
8.2 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H); 7.16 (t, J = 7.6 Hz, 1H), 6.97 FTIR (film): 3419, 2359, 1652, 1023, 1003, 751 cm-1; HRMS (ESI)
(t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, DMSO-d6) : 152.6, 148.3, m/z: Calcd for C9H9NaNOS[M+Na]+: 202.0297. Found: 202.0302.
137.1, 131.8, 125.9, 124.0, 123.0, 122.9, 121.0, 118.7, 114.8, 5-Methoxy-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3s): White
112.9; FTIR (film): 3413, 2358, 1524, 1345, 1025, 1005, 749 cm- solid, m.p. = 147–149 °C; 52.1 mg, 87% yield; 1H NMR (400 MHz,
1; HRMS (ESI) m/z: Calcd for C14H10NaN2O3S [M+Na]+: 309.0304. CDCl3) : 7.62 (d, J = 8.2 Hz, 2H), 7.42 (s, 1H), 7.29 (d, J = 7.7 Hz,
Found: 309.0308.
2H), 7.20 (d, J = 8.9 Hz, 1H), 6.89 (dd, J = 8.9, 2.4 Hz, 1H), 6.85
1-Methyl-3-((3-nitrophenyl)sulfinyl)-1H-indole (3m): 0.72 (d, J = 2.3 Hz, 1H), 3.77 (s, 3H), 3.68 (s, 3H), 2.40 (s, 3H);13C NMR
mmol of TMSCl was used. Pale yellow oil, 50.4 mg, 84% yield; 1H (100 MHz, CDCl3) : 155.0, 140.7, 140.2, 132.8, 132.7, 129.4,
NMR (400 MHz, CDCl3) : 8.48 (t, J = 2.0 Hz, 1H), 7.26–7.23 (m, 125.0, 124.9, 115.8, 113.7, 110.8, 101.0, 55.4, 33.4, 21.2; FTIR
1H), 8.09 (d, J = 7.8 Hz, 1H), 7.68–7.65 (m, 2H), 7.35 (d, J = 8.7 (film): 3457, 3094, 2921, 1513, 1491, 1462, 1371, 1061, 1034,
Hz, 2H), 7.26 (t, J = 8.1 Hz, 1H), 7.07 (t, J = 8.0 Hz, 1H), 3.84 (s, 1014, 976, 809, 790, 635 cm-1; HRMS (ESI) m/z: Calcd for
3H); 13C NMR (100 MHz, CDCl3) : 148.4, 147.6, 137.9, 133.6, C17H17NaNO2S [M+Na]+: 322.0872. Found: 322.0869.
130.6, 129.9, 124.7, 123.8, 123.7, 121.9, 120.1, 119.5, 114.8, 5-Methoxy-3-(p-tolylsulfinyl)-1H-indole (3t): Yellow solid, m.p.
110.5, 33.5; FTIR (film): 3091, 2927, 1526, 1457, 1348, 1037, 731 = 120–122 °C; 53.0 mg, 93% yield; 1H NMR (400 MHz, CDCl3) :
cm-1; HRMS (ESI) m/z: Calcd for C15H12NaN2O3S [M+Na]+: 10.64 (s, 1H), 7.55 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 7.15
323.0461. Found: 323.0468.
(d, J = 3.0 Hz, 1H), 7.08 (d, J = 8.8 Hz, 1H), 6.74–6.70 (m, 2H),
3-((3-Nitrophenyl)sulfinyl)-1H-indole (3n): 0.72 mmol of TMSCl 3.55 (s, 3H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3) : 154.8,
was used. Pale yellow oil, 48.6 mg, 85% yield; 1H NMR (400 MHz, 140.5, 139.8, 131.9, 130.2, 129.6, 124.9, 124.1, 115.5, 113.7,
DMSO-d6) : 12.10 (s, 1H), 8.49 (t, J = 2.0 Hz, 1H), 8.31 (ddd, J = 113.2, 100.4, 55.3, 21.2; FTIR (film): 3156, 2926, 2830, 1585,
8.2, 2.4, 1.0 Hz, 1H), 8.26 (s, 1H), 7.98 (dt, J = 7.9, 1.3 Hz, 1H), 1487, 1466, 1438, 1294, 1208, 1172, 1022, 1001, 808, 631 cm-1;
7.78 (t, J = 8.0 Hz, 1H); 7.49 (d, J = 8.1 Hz, 1H), 7.22–7.14 (m, 2H), HRMS (ESI) m/z: Calcd for C16H15NaNO2S [M+Na]+: 308.0716.
6.99–6.95 (m, 1H);13C NMR (100 MHz, DMSO-d6) : 148.1, 147.7, Found: 308.0714.
137.0, 131.9, 130.8, 130.7, 124.8, 123.0, 122.9, 121.0, 119.0, 7-Methoxy-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3u): Pale
118.7, 114.9, 112.8; FTIR (film): 3414, 2925, 1717, 1351, 1275, yellow oil, 49.1 mg, 82% yield; 1H NMR (400 MHz, CDCl3) : 7.58
1051, 1025, 1006, 749 cm-1; HRMS (ESI) m/z: Calcd for (d, J = 8.2 Hz, 2H), 7.32 (s, 1H), 7.26 (d, J = 8.0 Hz, 2H), 7.03 (dd,
C14H10NaN2O3S [M+Na]+: 309.0304. Found: 309.0310.
J = 8.1, 0.8 Hz, 1H), 6.94 (t, J = 7.9 Hz, 1H), 6.62 (d, J = 7.7 Hz,
1-Methyl-3-(thiophen-2-ylsulfinyl)-1H-indole (3o): 0.72 mmol 1H), 4.05 (s, 3H), 3.88 (s, 3H),2.38 (s, 3H); 13C NMR (100 MHz,
of TMSCl was used. Pale yellow oil, 44.4 mg, 85% yield; 1H NMR CDCl3) : 147.9, 141.0, 140.2, 133.2, 129.5, 127.4, 126.8, 124.9,
(400 MHz, CDCl3) : 7.58 (d, J = 9.8 Hz, 2H), 7.55 (dd, J = 5.0, 1.2 122.0, 116.3, 112.2, 103.8, 55.3, 37.2, 21.2; FTIR (film): 3424,
Hz, 1H), 7.52 (dd, J = 3.7, 1.2 Hz, 1H), 7.37 (d, J = 8.3 Hz, 1H), 3099, 2922, 2850, 1578, 1493, 1415, 1370, 1322, 1260, 1171,
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Organic & Biomolecular Chemistry
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ARTICLE
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1103, 1036, 1013, 810, 779, 732 cm-1; HRMS (ESI) m/z: Calcd for 1014, 829, 807, 648 cm-1; HRMS (ESI) m/z: Calcd for
View Article Online
C17H17NaNO2S [M+Na]+: 322.0872. Found: 322.0875.
C16H14NaClNOS [M+Na]+: 326.0377. FounDdO: I3:2106..1003397/9C.9OB00526A
7-Methoxy-3-(p-tolylsulfinyl)-1H-indole (3v): Yellow solid, m.p. 6-Chloro-3-(p-tolylsulfinyl)-1H-indole (3ab): Yellow solid, m.p.
= 120–123 °C; 49.6 mg, 87% yield; 1H NMR (400 MHz, CDCl3) : = 119–121 °C; 41.1 mg, 71% yield; 1H NMR (400 MHz, CDCl3) :
10.03 (s, 1H), 7.57 (d, J = 8.2 Hz, 2H), 7.43 (d, J = 2.9 Hz, 1H), 7.24 10.28 (s, 1H), 7.53 (d, J = 8.1 Hz, 2H), 7.30–7.26 (m, 3H), 7.24 (d,
(d, J = 8.0 Hz, 2H), 7.00–6.91 (m, 3H), 6.59 (d, J = 7.5 Hz, 1H), J = 8.6 Hz, 1H), 7.18 (d, J = 1.0 Hz, 1H), 6.97 (dd, J = 8.6, 1.4 Hz,
3.81 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3) : 146.4, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) : 140.9, 139.7,
140.6, 140.3, 129.5, 128.7, 127.5, 125.0, 124.9, 121.9, 117.6, 137.4, 130.0, 129.8, 129.5, 124.8, 122.2, 121.9, 120.0, 116.9,
111.9, 103.1, 55.2, 21.2; FTIR (film): 3110, 2920, 2850, 1581, 112.4, 21.3; FTIR (film): 3151, 3103, 2923, 1666, 1615, 1492,
1493, 1424, 1255, 1099, 1002, 780, 731 cm-1; HRMS (ESI) m/z: 1443, 1403, 1270, 1081, 1021, 1006, 908, 806, 785 cm-1; HRMS
Calcd for C16H15NaNO2S [M+Na]+: 308.0716. Found: 308.0714.
(ESI) m/z: Calcd for C15H12NaClNOS [M+Na]+: 312.0220. Found:
4-Bromo-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3w): Pale 312.0222.
yellow oil, 21.6 mg, 31% yield; 1H NMR (400 MHz, CDCl3) : 7.64 6-Fluoro-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3ac): White
(d, J = 7.7 Hz, 2H), 7.38–7.36 (m, 2H), 7.30–7.25 (m, 3H), 7.18 (t, solid, m.p. = 143–145 °C; 40.2 mg, 70% yield; 1H NMR (400 MHz,
J = 7.7Hz, 1H), 3.77 (s, 3H), 2.38 (s, 3H);13C NMR (100 MHz, CDCl3) CDCl3) : 7.60 (d, J = 8.1 Hz, 2H), 7.49 (s, 1H), 7.38 (dd, J = 8.8,
: 142.5, 140.9, 138.3, 132.1, 129.5, 125.6, 125.3, 125.1, 123.7, 5.2 Hz, 1H), 7.29 (d, J = 8.1 Hz, 2H), 7.01 (dd, J = 9.3, 2.0 Hz, 1H),
119.0, 113.1, 109.3, 33.6, 21.3; FTIR (film): 3455, 3105, 2921, 6.85 (dt, J = 9.3, 2.1 Hz, 1H), 3.78 (s, 3H), 2.41 (s, 3H); 13C NMR
1556, 1508, 1434, 1417, 1332, 1290, 1197, 1033, 1014, 963, 809, (100 MHz, CDCl3) : 160.3 (d, JC-F = 241.0 Hz), 140.8, 140.5, 138.0
772, 732 cm-1; HRMS (ESI) m/z: Calcd for C16H14NaBrNOS (d, JC-F = 11.9 Hz), 132.9, 129.6, 124.8, 121.0 (d, JC-F = 10.1 Hz),
[M+Na]+: 369.9872. Found: 369.9875.
120.6, 117.1 (d, JC-F = 3.0 Hz), 110.2 (d, JC-F = 24.7 Hz), 96.7 (d,
4-Bromo-3-(p-tolylsulfinyl)-1H-indole (3x): Pale yellow oil, 28.0 JC-F = 26.5 Hz), 33.4, 21.2; FTIR (film): 3440, 3102, 2923, 2853,
1
mg, 42% yield; H NMR (400 MHz, CDCl3) : 10.93 (s, 1H), 7.58 1622, 1583, 1516, 1491, 1462, 1335, 1244, 1098, 1033, 1014,
(d, J = 8.2 Hz, 2H), 7.30–7.26 (m, 3H), 7.23 (d, J = 8.0 Hz, 1H), 897, 828, 808, 689 cm-1; HRMS (ESI) m/z: Calcd for
7.01 (d, J = 1.0 Hz, 1H), 6.98 (t, J = 7.9 Hz, 1H), 2.43 (s, 3H); 13
C
C16H14NaFNOS [M+Na]+: 310.0672. Found: 310.0675.
NMR (100 MHz, CDCl3) : 141.3, 140.8, 137.8, 129.7, 128.9, 6-Fluoro-3-(p-tolylsulfinyl)-1H-indole (3ad): Yellow solid, m.p.
125.8, 125.2, 124.7, 123.9, 118.3, 112.3, 111.8, 21.3; FTIR (film): = 102–104 °C; 45.9 mg, 84% yield; 1H NMR (400 MHz, CDCl3) :
2924, 2853, 2366, 1616, 1490, 1178, 1123, 1008, 683 cm-1; 10.78 (s, 1H), 7.53 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H),
HRMS (ESI) m/z: Calcd for C15H12NaBrNOS [M+Na]+: 355.9715. 7.24–7.21 (m, 2H), 6.85 (dd, J = 9.3, 1.9 Hz, 1H), 6.73 (dt, J = 9.3,
Found: 355.9711.
2.1 Hz, 1H), 2.39 (s, 3H); 13C NMR (100 MHz, CDCl3) : 160.2 (d,
5-Bromo-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3y): White JC-F = 240.5 Hz), 140.8, 139.5, 137.4 (d, JC-F = 12.5 Hz), 130.3 (d,
solid, m.p. = 142–144 °C; 43.7 mg, 63% yield; 1H NMR (400 MHz, JC-F = 2.5 Hz), 129.8, 124.8, 120.0 (d, JC-F = 10.0 Hz), 119.7, 116.2,
CDCl3) : 7.65 (s, 1H), 7.59 (d, J = 7.8 Hz, 2H), 7.44 (s, 1H), 7.34– 110.3 (d, JC-F = 24.7 Hz), 98.9 (d, JC-F = 26.2 Hz), 21.3; FTIR (film):
7.29 (m, 3H), 7.18 (d, J = 8.5 Hz, 1H), 3.78 (s, 3H), 2.41 (s, 3H); 3128, 3091, 3060, 2920, 1626, 1592, 1513, 1448, 1417, 1340,
13C NMR (100 MHz, CDCl3) : 140.6, 140.5, 136.3, 133.1, 129.6, 1240, 1145, 1022, 1002, 950, 805, 615 cm-1; HRMS (ESI) m/z:
126.2, 125.8, 124.6, 122.2, 116.4, 114.7, 111.5, 33.4, 21.2; FTIR Calcd for C15H12NaFNOS [M+Na]+: 296.0516. Found: 296.0514.
(film): 3444, 2922, 1619, 1513, 1486, 1448, 1219, 1132, 1031, 1,2-Dimethyl-3-(p-tolylsulfinyl)-1H-indole (3ae): White solid,
1014, 809 cm-1; HRMS (ESI) m/z: Calcd for C16H14NaBrNOS m.p. = 128–130 °C; 48.1 mg, 85% yield; 1H NMR (400 MHz, CDCl3)
[M+Na]+: 369.9872. Found: 369.9869.
: 7.53 (d, J = 8.2 Hz, 2H), 7.30–7.23 (m, 4H), 7.16 (t, J = 7.7 Hz,
5-Bromo-3-(p-tolylsulfinyl)-1H-indole (3z): Yellow solid, m.p. = 1H), 6.98 (t, J = 7.5 Hz, 1H), 3.68 (s, 3H), 2.68 (s, 3H), 2.37 (s, 3H);
1
125–127 °C; 60.0 mg, 90% yield; H NMR (400 MHz, CDCl3) : 13C NMR (100 MHz, CDCl3) : 142.3, 141.1, 139.6, 137.1, 129.4,
11.08 (s, 1H), 7.52 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 1.5 Hz, 1H), 7.29 124.7, 123.9, 122.3, 121.1, 119.3, 112.6, 109.3, 29.6, 21.1, 10.9;
(d, J = 8.1 Hz, 2H), 7.17 (d, J = 2.9 Hz, 1H), 7.15 (dd, J = 8.7, 1.8 FTIR (film): 3049, 2918, 1526, 1474, 1399, 1037, 1015, 760, 740
Hz, 1H), 7.03 (d, J = 8.7 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, cm-1; HRMS (ESI) m/z: Calcd for C17H17NaNOS [M+Na]+:
CDCl3) : 141.0, 139.1, 135.8, 130.7, 129.9, 126.3, 124.9, 124.7, 306.0923. Found: 306.0925.
121.5, 115.4, 114.6, 114.1, 21.3; FTIR (film): 3145, 2920, 2870, 2-Methyl-3-(p-tolylsulfinyl)-1H-indole (3af): Yellow solid, m.p.
1492, 1453, 1412, 1295, 1112, 1080, 1021, 1002, 885, 806, 732 = 120–122 °C; 47.4 mg, 88% yield; 1H NMR (400 MHz, CDCl3) :
cm-1; HRMS (ESI) m/z: Calcd for C15H12NaBrNOS [M+Na]+: 9.99 (s, 1H), 7.54 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.19
355.9715. Found: 355.9713.
(t, J = 7.7 Hz, 2H), 7.05 (t, J = 7.6 Hz, 1H), 6.92 (t, J = 7.6 Hz, 1H),
6-Chloro-1-methyl-3-(p-tolylsulfinyl)-1H-indole (3aa): Yellow 2.40 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3) : 142.3,
solid, m.p. = 134–136 °C; 36.7 mg, 60% yield; 1H NMR (400 MHz, 140.1, 140.0, 135.8, 129.6, 124.8, 124.3, 122.5, 121.0, 118.9,
CDCl3) : 7.59 (d, J = 8.1 Hz, 2H), 7.49 (s, 1H), 7.37 (d, J = 8.6 Hz, 111.7, 111.4, 21.2, 11.6; FTIR (film): 3178, 3103, 2924, 1618,
1H), 7.33 (d, J = 1.5 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.06 (dd, J = 1490, 1451, 1409, 1289, 1082, 1003, 923, 808, 743 cm-1; HRMS
8.6, 1.6 Hz, 1H), 3.78 (s, 3H), 2.40 (s, 3H); 13C NMR (100 MHz, (ESI) m/z: Calcd for C16H15NaNOS [M+Na]+: 292.0767. Found:
CDCl3) : 140.7, 140.5, 138.1, 133.0, 129.5, 129.3, 124.7, 122.7, 292.0763.
121.9, 120.7, 117.2, 110.1, 33.3, 21.2; FTIR (film): 3484, 3101, 1-Benzyl-3-(p-tolylsulfinyl)-1H-indole (3ag): White solid, m.p. =
1
2922, 1608, 1514, 1491, 1460, 1331, 1174, 1080, 1070, 1035, 140–142 °C; 48.3 mg, 70% yield; H NMR (400 MHz, CDCl3) :
7.64 (d, J = 7.9 Hz, 2H), 7.59 (s, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.35–
8 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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7.29 (m, 6H), 7.21 (t, J = 7.7 Hz, 1H), 7.17 (d, J = 7.2 Hz, 1H), 7.09 1009, 808, 738 cm-1; HRMS (ESI) m/z: Calcd for C11H11NaNOS
View Article Online
(t, J = 7.5 Hz, 1H), 5.31 (s, 2H), 2.40 (s, 3H); 13C NMR (100 MHz, [M+Na]+: 228.0454. Found: 228.0457.
DOI: 10.1039/C9OB00526A
CDCl3) : 140.8, 140.3, 137.3, 135.6, 131.9, 129.5, 128.9, 128.0, 1-Benzyl-2-(p-tolylsulfinyl)-1H-pyrrole (7f): Pale yellow oil,
126.9, 124.8, 124.4, 123.3, 121.4, 120.0, 117.2, 110.5, 50.5, 21.2; 33.6 mg, 57% yield; 1H NMR (400 MHz, CDCl3) : 7.39 (d, J = 8.2
FTIR (film): 3456, 3031, 2922, 1510, 1455, 1386, 1162, 1080, Hz, 2H), 7.24–7.18 (m, 5H), 6.97–6.94 (m, 2H), 6.74–6.73 (m, 1H),
1034, 1014, 810, 761, 742, 732, 697 cm-1; HRMS (ESI) m/z: Calcd 6.51 (dd, J = 2.8, 1.7 Hz, 1H), 6.17 (dd, J = 3.7, 2.9 Hz, 1H), 5.29
for C22H19NaNOS [M+Na]+: 368.1080. Found: 368.1084.
Experimental Procedure of Sulfoxides 7a-7g and 8a-8g
(d, J = 15.5 Hz, 1H), 5.12 (d, J = 15.5 Hz, 1H), 2.36 (s, 3H); 13C
NMR (100 MHz, CDCl3) : 140.5, 139.8, 136.6, 131.0, 129.5,
The mixture of an arylsulfiniamide (0.2 mmol, 1 equiv.), a 128.5, 127.6, 127.5, 127.3, 124.7, 116.4, 108.8, 50.9, 21.2; FTIR
pyrrole (0.24 mmol, 1.2 equiv.) and TMSCl (0.36 mmol, 1.8 (film): 3031, 2923, 1454, 1287, 1080, 1038, 810, 728 cm-1; HRMS
equiv.) in CH2Cl2 (1.0 mL) was stirred at 0 °C for 10 min (for 7) or (ESI) m/z: Calcd for C18H17NaNOS [M+Na]+: 318.0923. Found:
4 h (for 8), then water (5 mL) and dichloromethane (10 mL) were 318.0927.
added. The two layers were separated, and the aqueous phase 2-Methyl-5-(p-tolylsulfinyl)-1H-pyrrole (7g): Pale yellow oil,
1
was extracted with dichloromethane (3 × 10 mL). The combined 28.1 mg, 64% yield; H NMR (400 MHz, CDCl3) : 10.46 (s, 1H),
organic extracts were washed by brine, dried over anhydrous 7.50 (d, J = 7.9 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 6.48–6.46 (m,
Na2SO4, filtered, and concentrated. The residue was purified by 1H), 5.80 (t, J = 3.0 Hz, 1H), 2.39 (s, 3H), 2.12 (s, 3H); 13C NMR
flash chromatography on silica gel (100–200 mesh) to afford the (100 MHz, CDCl3) : 140.7, 140.1, 136.0, 129.6, 126.8, 124.9,
desired sulfoxide.
116.0, 107.1, 21.3, 12.9; FTIR (film): 3177, 2924, 2359, 1566,
1-Methyl-2-(p-tolylsulfinyl)-1H-pyrrole (7a): White solid, m.p. 1274, 1148, 1024, 764 cm-1; HRMS (ESI) m/z: Calcd for
= 47–49 °C; 33.3 mg, 76% yield; 1H NMR (400 MHz, CDCl3) : 7.43 C12H13NaNOS [M+Na]+: 242.0610. Found: 242.0617.
(d, J = 7.9 Hz, 2H), 7.29 (d, J = 7.9 Hz, 2H), 6.74 (s, 1H), 6.53–6.52 1-Methyl-3-(p-tolylsulfinyl)-1H-pyrrole (8a): White solid, m.p.
(m, 1H), 6.12 (s, 1H), 3.56 (s, 3H), 2.40 (s, 3H);13C NMR (100 MHz, = 84–86 °C; 32.0 mg, 73% yield; 1H NMR (400 MHz, CDCl3) : 7.56
CDCl3) : 140.5, 139.6, 129.6, 128.8, 124.8, 117.1, 108.0, 34.6, (d, J = 8.1 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 6.98 (s, 1H), 6.61 (d, J
21.2; FTIR (film): 2949, 2359, 2342, 1739, 1372, 1274, 1238, = 2.3 Hz, 1H), 6.18 (dd, J = 2.6, 1.7 Hz, 1H), 3.66 (s, 3H), 2.42 (s,
1045, 764, 668 cm-1; HRMS (ESI) m/z: Calcd for C12H13NaNOS 3H); 13C NMR (100 MHz, CDCl3) : 141.8, 140.2, 129.3, 126.8,
[M+Na]+: 242.0610. Found: 242.0611.
124.4, 124.2, 123.8, 107.3, 36.4, 21.1; FTIR (film): 3452, 3105,
1-Methyl-2-(phenylsulfinyl)-1H-pyrrole (7b): Yellow solid, m.p. 2922, 1673, 1516,1493, 1420, 1121, 1080, 1034, 1013, 810, 706,
1
= 57–59 °C; 22.1 mg, 54% yield; H NMR (400 MHz, CDCl3) : 635 cm-1; HRMS (ESI) m/z: Calcd for C12H13NaNOS [M+Na]+:
7.55–7.53 (m, 2H), 7.49–7.42 (m, 3H), 6.74 (s, 1H), 6.55 (dd, J = 242.0610. Found: 242.0607.
3.7, 1.4 Hz, 1H), 6.13–6.11 (m, 1H), 3.53 (s, 3H); 13C NMR (100 1-Methyl-3-(phenylsulfinyl)-1H-pyrrole (8b): The reaction was
MHz, CDCl3) : 143.0, 130.1, 129.4, 129.0, 128.9, 124.8, 117.4, performed for 5 h. White solid, m.p. = 82–84 °C; 30.0 mg, 73%
108.1, 34.6; FTIR (film): 3102, 2926, 1442, 1291, 1082, 1035, 731 yield; H NMR (400 MHz, CDCl3) : 7.64 (d, J = 6.8 Hz, 2H), 7.48–
cm-1; HRMS (ESI) m/z: Calcd for C11H11NaNOS [M+Na]+: 7.40 (m, 3H), 6.97 (m, 2H), 6.58 (t, J = 2.3 Hz, 1H), 6.14 (dd, J =
228.0454. Found: 228.0457.
2.6, 1.6 Hz, 1H), 3.63 (s, 3H);13C NMR (100 MHz, CDCl3) : 145.0,
2-((4-Chlorophenyl)sulfinyl)-1-methyl-1H-pyrrole (7c): Pale 130.0, 128.7, 126.6, 124.5, 124.5, 124.0, 107.6, 36.5; FTIR (film):
1
yellow oil, 33.9 mg, 71% yield; H NMR (400 MHz, CDCl3) : 3445, 3108, 2920, 1670, 1515, 1442, 1419, 1304, 1121, 1081,
7.49–7.43 (m, 4H), 6.75 (s, 1H), 6.55 (dd, J = 3.8, 1.6 Hz, 1H), 1032, 996, 750, 691, 632 cm-1; HRMS (ESI) m/z: Calcd for
6.13–6.12 (m, 1H); 13C NMR (100 MHz, CDCl3) : 141.7, 136.4, C11H11NaNOS [M+Na]+: 228.0454. Found: 228.0452.
129.3, 129.1, 128.9, 126.3, 117.6, 108.2, 34.6; FTIR (film): 3101, 3-((4-Chlorophenyl)sulfinyl)-1-methyl-1H-pyrrole (8c): The
2925, 1471, 1290, 1088, 1037, 1009, 823, 737 cm-1; HRMS (ESI) reaction was performed for 5 h. Yellow solid, m.p. = 64–66 °C;
m/z: Calcd for C11H10NaClNOS [M+Na]+: 262.0064. Found: 32.0 mg, 67% yield; 1H NMR (400 MHz, CDCl3) : 7.55 (d, J = 8.5
262.0061.
Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 6.98 (s, 1H), 6.58 (t, J = 2.4 Hz,
2-((4-Fluorophenyl)sulfinyl)-1-methyl-1H-pyrrole (7d): Pale 1H), 6.11 (t, J = 2.2 Hz, 1H), 3.62 (s, 3H); 13C NMR (100 MHz,
yellow oil, 20.1 mg, 45% yield; 1H NMR (400 MHz, CDCl3) : 7.53 CDCl3) : 143.7, 136.0, 128.9, 126.1, 125.9, 124.7, 124.2, 107.4,
(dd, J = 8.6, 5.1 Hz, 2H), 7.18 (t, J = 8.6 Hz, 2H), 6.76 (s, 1H), 6.52 36.5; FTIR (film): 3457, 3109, 2923, 2235, 1515, 1472, 1419,
(dd, J = 3.7, 1.4 Hz, 1H), 6.13–6.12 (m, 1H), 3.56 (s, 3H);13C NMR 1120, 1077, 1034, 1009, 907, 820, 793, 738, 726, 632 cm-1;
(100 MHz, CDCl3) : 163.8 (d, JC-F = 250.8 Hz), 138.5 (d, JC-F = 3.0 HRMS (ESI) m/z: Calcd for C11H10NaClNOS [M+Na]+: 262.0064.
Hz), 129.3, 129.2, 127.1 (d, JC-F = 8.7 Hz), 117.4, 116.2 (d, JC-F
=
Found: 262.0062.
22.6 Hz), 108.2, 34.6; FTIR (film): 3099, 2925, 1588, 1488, 1290, 3-((4-Fluorophenyl)sulfinyl)-1-methyl-1H-pyrrole (8d): Pale
1
1222, 1037, 835, 732 cm-1; HRMS (ESI) m/z: Calcd for yellow oil, 30.0 mg, 67% yield; H NMR (400 MHz, CDCl3) :
C11H10NaFNOS [M+Na]+: 246.0359. Found: 246.0363.
7.64–7.60 (m, 2H), 7.17–7.12 (m, 2H), 6.97 (s, 1H), 6.59 (t, J =
2-(p-Tolylsulfinyl)-1H-pyrrole (7e): White solid, m.p. = 100–102 2.4 Hz, 1H), 6.12–6.11 (m, 1H), 3.64 (s, 3H); 13C NMR (100 MHz,
°C; 28.3 mg, 69% yield; 1H NMR (400 MHz, CDCl3) : 10.75 (s, 1H), CDCl3) : 163.7 (d, JC-F = 250.1 Hz), 140.7 (d, JC-F = 3.1 Hz), 126.7
7.53 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 7.8 Hz, 2H), 6.92 (s, 1H), 6.54 (d, JC-F = 8.7 Hz), 126.5, 124.5, 124.1, 115.9 (d, JC-F = 22.6 Hz),
(s, 1H), 6.18 (d, J = 2.0 Hz, 1H), 2.41 (s, 3H); 13C NMR (100 MHz, 107.4, 36.5; FTIR (film): 3443, 3109, 2922, 1673, 1558, 1516,
CDCl3) : 141.0, 140.0, 129.7, 129.3, 124.9, 124.4, 114.3, 109.0, 1489, 1420, 1220, 1152, 1121, 1080, 1032, 1010, 835, 812, 635
21.3; FTIR (film): 3178, 3049, 2936, 2854, 1492, 1081, 1022,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
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Organic & Biomolecular Chemistry
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Journal Name
cm-1; HRMS (ESI) m/z: Calcd for C11H10NaFNOS [M+Na]+:
246.0359. Found: 262.0362.
Lett. 2018, 20, 1134; k) Y. C. Zhu, Y. Li, B. C. Zhang, F. X. Zhang,
Y. N. Yang and X. S. Wang, Angew. Chem. Int. VEiedw. A2rt0ic1le8O, n5lin7e,
DOI: 10.1039/C9OB00526A
5129.
3-(p-Tolylsulfinyl)-1H-pyrrole (8e): White solid, m.p. = 150–152
°C; 25.4 mg, 62% yield; 1H NMR (400 MHz, CDCl3) : 10.06 (s, 1H),
7.53 (d, J = 8.1 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 1.1
Hz, 1H), 6.69 (d, J = 1.7 Hz, 1H), 6.16 (s, 1H), 2.42 (s, 3H);13C NMR
(100 MHz, CDCl3) : 141.3, 140.6, 129.5, 124.7, 121.8, 121.8,
120.5, 106.6, 21.3; FTIR (film): 3189, 3050, 2922, 2850, 1491,
1082, 1042, 1021, 1008, 808, 636 cm-1; HRMS (ESI) m/z: Calcd
for C11H11NaNOS [M+Na]+: 228.0454. Found: 228.0456.
1-Benzyl-3-(p-tolylsulfinyl)-1H-pyrrole (8f): The reaction was
performed for 5 h. White solid, m.p. = 103–105 °C; 36.0 mg, 61%
yield; 1H NMR (400 MHz, CDCl3) : 7.56 (d, J = 8.1 Hz, 2H), 7.38–
7.32 (m, 3H), 7.29 (d, J = 8.0 Hz, 1H), 7.15–7.13 (m, 2H), 7.08 (t,
J = 1.8 Hz, 1H), 6.67 (t, J = 2.5 Hz, 1H), 6.19 (dd, J = 2.8, 1.8 Hz,
1H), 5.03 (s, 2H), 2.41 (s, 3H);13C NMR (100 MHz, CDCl3) : 141.9,
140.3, 136.1, 129.4, 128.8, 128.0, 127.2, 127.1, 124.5, 123.8,
123.3, 107.5, 53.7, 21.2; FTIR (film): 3449, 3106, 3031, 2922,
1505, 1454, 1397, 1114, 1080, 1031, 1014, 907, 809, 708, 634
cm-1; HRMS (ESI) m/z: Calcd for C18H17NaNOS [M+Na]+:
318.0923. Found: 318.0920.
2-Methyl-4-(p-tolylsulfinyl)-1H-pyrrole (8g): 0.72 mmol of
TMSCl was used for 12 h. Pale yellow oil, 31.1 mg, 71% yield; 1H
NMR (400 MHz, CDCl3) : 10.13 (s, 1H), 7.47 (d, J = 8.1 Hz, 2H),
7.25 (d, J = 7.6 Hz, 2H), 6.45–6.43 (m, 1H), 5.89–5.87 (m, 1H),
2.38 (s, 3H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) : 141.3,
140.1, 133.6, 129.5, 124.6, 118.3, 106.6, 103.6, 21.3, 11.0; FTIR
(film): 3187, 3101, 2959, 2857, 1492, 1205, 1082, 1005, 808, 729
cm-1; HRMS (ESI) m/z: Calcd for C12H13NaNOS [M+Na]+:
242.0610. Found: 242.0615.
2
3
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This project was funded by the National Natural Science
Foundation of China (21672046 and 21372054), the
Fundamental Research Funds for the Central Universities
(HIT.NSRIF.201701), and the Foundation from Huancui District
of Wehai City.
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