Visible-Light Photoredox Catalysis: Direct Synthesis of Sulfonated Oxindoles from N-Arylacrylamides and Arylsulfinic Acids by Means of a Cascade C-S/C-C Formation Process

Article abstract of DOI:10.1002/asia.201500498

A novel photocatalytic synthesis of sulfonated oxindoles from N-arylacrylamides and arylsulfinic acids was developed by means of a cascade C-S/C-C bond-formation process. This method provides mild, efficient, and atom-economical access to various sulfonated oxindoles in water. Let there be light! A novel photocatalytic synthesis of sulfonated oxindoles from N-arylacrylamides and arylsulfinic acids was developed by means of a cascade C-S/C-C bond-formation process. This method provides mild, efficient, and atom-economical access to various sulfonated oxindoles in water (see scheme).

Full text of DOI:10.1002/asia.201500498

DOI: 10.1002/asia.201500498
Full Paper
Photoredox Catalysis
Visible-Light Photoredox Catalysis: Direct Synthesis of Sulfonated
Oxindoles from N-Arylacrylamides and Arylsulfinic Acids by
Means of a Cascade CÀS/CÀC Formation Process
Dong Xia,[a] Tao Miao,*[a] Pinhua Li,[a] and Lei Wang*[a, b]
Abstract: A novel photocatalytic synthesis of sulfonated ox-
indoles from N-arylacrylamides and arylsulfinic acids was de-
veloped by means of a cascade CÀS/CÀC bond-formation
process. This method provides mild, efficient, and atom-eco-
nomical access to various sulfonated oxindoles in water.
Introduction
activity, and represents one of the privileged scaffolds for drug
discovery and library design.[9] Considerable efforts have been
directed toward the development of efficient protocols for
their synthesis with transition-metal-catalyzed cyclizations as
well as radical-initiated processes.[10] Although many studies
have improved this type of reaction, a milder and more effi-
cient method for the synthesis of functionalized oxindoles is
highly desirable.
The development of a visible-light photocatalytic approach for
direct carbon–carbon and carbon–heteroatom bond formation
is undoubtedly a topic of great interest in organic synthesis,
because visible light is a mild, environmentally benign, opera-
tionally simple, infinitely available source, and has promising
applications in science and industry.[1] However, the direct use
of visible light in organic reactions is limited owing to the in-
ability of many organic molecules to absorb photons in the
visible region. To solve this long-standing problem, photocata-
lysts such as [Ru(bpy)3Cl2][2] (bpy=2,2’-bipyridine) and Eosin Y[3]
have often been employed through their visible-light-driven
single-electron transfer (SET) to sensitize organic molecules in
photochemical reactions. Since the pioneering studies by Mac-
Millan,[4] Stephenson,[5] Yoon,[6] and others[7] on the applications
of photocatalysts in the carbon–heteroatom and carbon–
carbon bond formations through visible-light photoredox
transformations, this topic has already demonstrated remark-
able achievements. Recently, visible-light photoredox catalysis
applied in the difunctionalization of alkenes has provided
a powerful strategy for the synthesis of the target organic
compounds.[8] The direct functionalization of arylacrylamides
with free radicals has the potential to incite cyclization and
promises a new pathway for the synthesis of oxindole, which
is an important class of N-heterocycle with unique biological
Arylsulfinic acids (or salts) are relatively stable, easy to
handle, and have been widely used as important starting ma-
terials for the formation of CÀC or CÀS bonds.[11] During the
past few years, extensive attention have been paid to the
preparation of organic sulfones using arylsulfinic acids (or
salts) as sulfonylation reagents. Among the methods available
for their synthesis, two different pathways have been devel-
oped. First, Pd- or Cu-catalyzed cross-coupling of sodium are-
nesulfinates with arylhalides, arylboron reagents, and allylic
amines provided an effective approach to sulfones.[12] Second,
oxidative addition of sulfonyl radicals to carbon–carbon multi-
ple bonds have emerged as powerful alternatives for the syn-
thesis of functionalized sulfones by treatment with radical ini-
tiators such as O2 or K2S2O8.[13] Despite extensive progress in
the preparation of sulfones, to the best of our knowledge, visi-
ble-light photoredox-catalyzed synthesis of organic sulfones
from their corresponding arylsulfinic acids is rare.[14] Herein, we
wish to report a visible-light photocatalytic difunctionalization
of arylacrylamides with arylsulfinic acids to offer important sul-
fonated oxindoles by means of a cascade CÀS/CÀC bond-for-
mation process under mild reaction conditions (Scheme 1).
[a] D. Xia, T. Miao, P. Li, Prof. Dr. L. Wang
Department of Chemistry
Huaibei Normal University
Huaibei, Anhui 235000 (P.R. China)
Fax: (+86)561-3090518
E-mail: leiwang@chnu.edu.cn
taomiaochem@163.com
[b] Prof. Dr. L. Wang
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Shanghai 200032 (P.R. China)
Scheme 1. The general scheme for the visible-light photocatalytic difunc-
tionalization of arylacrylamides with arylsulfinic acids under mild reaction
conditions.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/asia.201500498.
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vent, CH3CN gave 3a in 29% yield, and toluene generated 3a
in 42% yield (Table 1, entries 13 and 14). In the absence of visi-
ble light or Na2-Eosin Y, no product 3a could be formed in the
model reaction (Table 1, entries 15 and 16). Furthermore, when
[Ru(bpy)3Cl2] was used as a photocatalyst under optimized
conditions, the yield of 3a decreased to 41% (Table 1,
entry 17). When Eosin Y was used instead of Na2-Eosin Y, 3a
was provided in 45% yield owing to its poor solubility in water
(Table 1, entry 18).
Results and Discussion
At first, Na2-Eosin Y was chosen as a photocatalyst for the
model reaction of p-tolylsulfinic acid (1a) with N-methyl-N-
phenylmethacrylamide (2a) to optimize the reaction condi-
tions. In the presence of Na2-Eosin Y (2.0 mol%), this cascade
sulfonylation and radical CÀH functionalization reaction could
occur in water at room temperature by irradiation with a 5 W
white-light-emitting diode (LED), thereby providing the desired
product 3a in 27% yield (Table 1, entry 1). To our delight, an
82% yield of 3a was achieved when one equivalent of tert-
butyl hydroperoxide (TBHP, 70% aqueous) was added to the
reaction system (Table 1, entry 2). Further exploration of a varie-
ty of commercially available oxidants indicated that TBHP was
superior to the others, including O2, H2O2, 1,4-benzoquinone
(BQ), and di-tert-butyl peroxide (DTBP). They gave inferior re-
sults and led to the formation of 3a in 31–40% yields (Table 1,
entries 3–6). The inorganic oxidant K2S2O8 was less effective
and produced 3a in 26% yield, and PhI(OAc)2 did not work in
the reaction (Table 1, entries 7 and 8). Next, the effect of the
solvent on the model reaction was examined. Among the sol-
vents screened, we were pleased to find that water was the
best solvent, which is important from the perspective of green
chemistry. When the model reaction was carried out in dime-
thylformamide (DMF), dimethylsulfoxide (DMSO), 1,4-dioxane,
or C2H5OH, 11–38% yields of 3a were obtained (Table 1, en-
tries 9–12). By using CH3CN or toluene instead of H2O as sol-
With the optimized conditions in hand, we turned our atten-
tion to investigating the scope of the substrates. As shown in
Table 2, a variety of substituted arylsulfinic acids bearing
methyl, tert-butyl, methoxy, and acetyl amino groups on the
aromatic rings were treated effectively with N-methyl-N-phe-
nylmethacrylamide (2a) and afforded the corresponding sulfo-
nated oxindoles 3a–e in good yields (62–85%). In addition, the
reaction was tolerant of halogen substituents including fluoro,
chloro, and bromo groups on the para positions of arylsulfinic
acids, and the corresponding products (3 f, 3g, and 3i) were
obtained in 76–90% yields, which can be used further in the
transition-metal-catalyzed functionalization. It should be noted
that sterically hindered substituted arylsulfinic acids, such as 2-
chlorobenzenesulfinic acid, are a suitable substrate in this pro-
cess, thereby leading to the desired product 3h in 73% yield.
The combination of trifluoromethyl (CF3), a useful structural
motif in many biologically active molecules,[15] and a chloro (Cl)
group on arylsulfinic acid reacted with 2a to generate the cor-
Table 2. The reaction scope of arylsulfinic acids with N-methyl-N-phenyl-
methacrylamide (2a).[a]
Table 1. Optimization of the reaction conditions.[a]
Entry
Oxidant
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
–
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
DMF
DMSO
1,4-dioxane
C2H5OH
CH3CN
toluene
H2O
H2O
H2O
H2O
27
82
40
32
35
31
26
0
38
26
33
11
29
42
0[c]
0[d]
41[e]
45[f]
TBHP
O2
H2O2
BQ
DTBP
K2S2O8
PhI(OAc)2
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
9
10
11
12
13
14
15
16
17
18
[a] Reaction was performed with 1a (0.50 mmol), 2a (0.25 mmol), and
Na2-Eosin Y (2 mol%) in solvent (1.0 mL) under 5 W white light emitting
diode (LED) irradiation at room temperature for 6 h. [b] Isolated yield.
[c] In the darkness. [d] In the absence of Na2-Eosin Y. [e] [Ru(bpy)2Cl2]
(3 mol%) was used. [f] Eosin Y (2 mol%) was used.
[a] Reaction conditions:
(2 mol%), TBHP (0.25 mmol), H2O (1.0 mL), 5 W white-light-emitting diode
(LED), at room temperature for 6 h. [b] Isolated yield.
1 (0.50 mmol), 2a (0.25 mmol), Na2-Eosin Y
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responding product 3i in 78% yield. The bulkier 1-naphthylsul-
finic acid also reacted with 2a effectively to offer the desired
oxindoles 3k in 91% yield. Aliphatic sulfinic acids such as n-bu-
tylsulfinic acid could also be used in the reaction to give the
desired product 3l in 65% yield.
Table 3. The reaction scope of arylacrylamides with p-tolylsulfinic acid
(1a).[a]
To further investigate the scope of arylacrylamides, a series
of N-substituted arylacrylamides was treated with p-tolylsulfinic
acid (1a) under optimized reaction conditions, and the results
are summarized in Table 3. N-Methylarylacrylamides containing
both electron-donating and electron-withdrawing groups on
the para position of the benzene rings underwent cascade CÀ
S/CÀC bond-formation reactions smoothly with 1a to produce
the corresponding products (3m–y) in good yields. Disubsti-
tuted arylacrylamide also worked well with 1a in this process,
affording oxindoles 3n and 3s with 75 and 70% yields, respec-
tively. An examination of different N-protecting groups re-
vealed that methyl, n-butyl, and benzyl groups were compati-
ble with the transformation, but N-free arylacrylamide failed
(3ae). To our delight, the naphthalene acrylamide was also the
appropriate substrate for the reaction and provided the antici-
pated product 3ag in 70% yield. It is noteworthy that the cyc-
lization of tetrahydroquinoline could afford tricyclic sulfonated
oxindole 3af in 60% yield. Interestingly, the N-methylarylacry-
lamide substrate with a substituent at the meta position gener-
ated oxindole 3v in 75% yield with high regioselectivity.
To clarify the mechanism of this process, a radical-trapping
reagent, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), was
added to the system and the reaction was completely inhibit-
ed, which suggests that free-radical intermediates were in-
volved in the reaction. Based on our observations and litera-
ture reports, a plausible mechanism is proposed in Scheme 2.
Firstly, the excited-state Eosin Y* formed under visible-light ir-
radiation donates an electron to TBHP to give the tert-butyloxy
radical. Then the obtained tert-butyloxy radical abstracts a hy-
drogen from arylsulfinic acid (1) to generate an oxygen-cen-
tered radical resonating with the sulfonyl radical (A). Subse-
quently, the addition of sulfonyl radical A to activated alkene
2a affords alkyl radical B, followed by intramolecular cycliza-
tion with an aryl ring. This leads to the formation of radical in-
[a] Reaction conditions: 1a (0.50 mmol),
2 (0.25 mmol), Na2-Eosin Y
(2 mol%), TBHP (0.25 mmol), H2O (1.0 mL), 5 W white-light-emitting diode
(LED), at room temperature for 6 h. [b] Isolated yield.
Scheme 2. The proposed reaction mechanism for the visible-light photocata-
lytic difunctionalization of arylacrylamides with arylsulfinic acids.
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termediate C, which is oxidized by a cation radical of Eosin Y
1,3-Dimethyl-3-[(phenylsulfonyl)methyl]indolin-2-one (3b)[17]
(Eosin Y +) to form cationic intermediate D through a SET pro-
C
White solid; 1H NMR (400 MHz, CDCl3): d=7.53 (t, J=7.3 Hz, 1H),
7.49 (d, J=7.8 Hz, 2H), 7.37 (t, J=7.5 Hz, 2H), 7.28 (t, J=7.8 Hz,
1H), 7.03 (d, J=7.3 Hz, 1H), 6.91–6.84 (m, 2H), 3.89 (d, J=14.6 Hz,
1H), 3.70 (d, J=14.6 Hz, 1H), 3.17 (s, 3H), 1.39 ppm (s, 3H);
13C NMR (100 MHz, CDCl3): d=177.5, 143.2, 139.9, 133.2, 129.4,
128.8, 128.5, 127.7, 124.0, 122.4, 108.3, 61.8, 45.5, 26.4, 25.3 ppm.
cess. Finally, cationic intermediate D loses a proton to produce
the final product sulfonated oxindole 3, along with water.
Conclusion
In conclusion, a novel visible-light photocatalytic synthesis of
sulfonated oxindoles from arylacrylamides and arylsulfinic acids
has been developed by means of a cascade CÀS/CÀC bond-for-
mation process. This method provides mild, efficient, and envi-
ronmentally friendly access to functionalized oxindoles in good
to excellent yields, while avoiding the use of metal catalysts,
organic solvents, and high reaction temperatures. Further stud-
ies on the clarification of the reaction mechanism and applica-
tion of this kind of transformation in the preparation of other
sulfur-containing compounds are currently underway.
3-({[4-(tert-Butyl)phenyl]sulfonyl}methyl)-1,3-dimethyl indolin-
2-one (3c)[18]
1
White solid; H NMR (400 MHz, CDCl3): d=7.40 (d, J=8.2 Hz, 2H),
7.36 (d, J=8.2 Hz, 2H), 7.26 (t, J=6.6 Hz, 1H), 7.03 (d, J=7.2 Hz,
1H), 6.87–6.82 (m, 2H), 3.86 (d, J=14.6 Hz, 1H), 3.68 (d, J=14.6 Hz,
1H), 3.16 (s, 3H), 1.38 (s, 3H), 1.31 ppm (s, 9H); 13C NMR (100 MHz,
CDCl3): d=177.5, 157.0, 143.2, 136.8, 129.5, 128.4, 127.5, 125.8,
124.0, 122.3, 108.2, 61.8, 45.5, 35.0, 30.9, 26.4, 25.3 ppm.
3-{[(4-Methoxyphenyl)sulfonyl]methyl}-1,3-dimethyl indolin-2-
one (3d)[18]
Experimental Section
General
1
White solid; H NMR (400 MHz, CDCl3): d=7.36 (d, J=8.6 Hz, 2H),
All reactions were carried out in air. H and 13C NMR spectra were
1
7.28–7.24 (m, 1H), 7.04 (d, J=7.3 Hz, 1H), 6.90 (t, J=7.6 Hz, 1H),
6.84–6.78 (m, 3H), 3.87–3.82 (m, 4H), 3.66 (d, J=14.6 Hz, 1H), 3.14
(s, 3H), 1.36 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.7,
163.5, 143.2, 131.4, 130.0, 129.6, 128.6, 124.1, 122.5, 114.1, 108.4,
62.0, 55.7, 45.6, 26.5, 25.6 ppm.
measured on a Bruker Avance NMR spectrometer (400 or 100 MHz,
respectively) in CDCl3 solvent and recorded relative to the internal
standard tetramethylsilane. High-resolution mass spectroscopic
data of the products were collected on an Agilent Technolo-
gies 6540 UHD Accurate-Mass Q-TOF LC/MS using ESI.
N-(4-{[(1,3-Dimethyl-2-oxoindolin-3-yl)methyl]sulfonyl}pheny-
l)acetamide (3e)[13d]
Preparation of the Starting Materials
K2CO3 (anhydrous, 1.5 mmol) and acyl chloride (1.5 mmol) were
added to a stirred solution of N-methylaniline (1.0 mmol) in tolu-
ene (2.0 mL). The mixture was heated to 808C for 12 h. After com-
pletion, the reaction was quenched with H2O and extracted with
EtOAc. The extract was washed with brine and dried over MgSO4,
which was then concentrated under reduced pressure and purified
by silica gel flash chromatography to afford N-methyl-N-phenylme-
thacrylamide.[16]
1
White solid; H NMR (400 MHz, CDCl3): d=8.17 (s, 1H), 7.53 (d, J=
8.4 Hz, 2H), 7.35 (d, J=8.4 Hz, 2H), 7.28 (t, J=7.8 Hz, 1H), 7.05 (d,
J=7.4 Hz, 1H), 6.92 (t, J=7.5 Hz, 2H), 6.86 (d, J=7.9 Hz, 1H), 3.86
(d, J=14.6 Hz, 1H), 3.69 (d, J=14.7 Hz, 1H), 3.16 (s, 3H), 2.17 (s,
3H), 1.38 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.8, 169.1,
143.1, 133.9, 129.4, 129.0, 128.8, 124.1, 122.7, 119.1, 108.6, 62.0,
45.7, 26.6, 25.6, 24.7 ppm.
Typical Procedure for the Synthesis of Oxindoles
3-{[(4-Fluorophenyl)sulfonyl]methyl}-1,3-dimethyl indolin-2-
one (3 f)[19]
A
reaction tube was charged with p-tolylsulfinic acid (1a,
0.50 mmol), N-methyl-N-phenylmethacrylamide (2a, 0.25 mmol),
and Na2-Eosin Y (3.4 mg, 2 mol%). Then H2O (1.0 mL) and TBHP
(0.25 mmol) were added to the mixture, and were stirred for 6 h
under 5 W white light emitting diode (LED) irradiation at room
temperature in a photocatalytic reactor. The reaction mixture was
then extracted with EtOAc (5 mL) and H2O (5 mL), and the organic
layer was then concentrated under vacuum to give the resulting
material, which was purified by column chromatography (petrole-
um ether/EtOAc 3:1) to give the desired product 3a.
1
White solid; H NMR (400 MHz, CDCl3): d=7.49–7.45 (m, 2H), 7.30
(t, J=7.6 Hz, 1H), 7.06–7.00 (m, 3H), 6.92 (t, J=7.5 Hz, 1H), 6.86 (d,
J=7.8 Hz, 1H), 3.91 (d, J=14.6 Hz, 1H), 3.69 (d, J=14.6 Hz, 1H),
3.19 (s, 3H), 1.39 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.5,
165.5 (d, J=254.7 Hz), 143.3, 135.93 (d, J=3.1 Hz), 130.71 (d, J=
9.7 Hz), 129.4, 128.8, 124.0, 122.5, 116.14 (d, J=22.5 Hz), 108.5,
62.0, 45.6, 26.6, 25.5 ppm.
1,3-Dimethyl-3-(tosylmethyl)indolin-2-one (3a)[17]
3-{[(4-Chlorophenyl)sulfonyl]methyl}-1,3-dimethylindolin-2-one
(3g)[13d]
1
White solid; H NMR (400 MHz, CDCl3): d=7.38 (d, J=7.8 Hz, 2H),
1
7.29 (t, J=7.8 Hz, 1H), 7.17 (d, J=7.8 Hz, 2H), 7.09 (d, J=7.3 Hz,
1H), 6.93 (t, J=7.5 Hz, 1H), 6.85 (d, J=7.8 Hz, 1H), 3.86 (d, J=
14.5 Hz, 1H), 3.67 (d, J=14.5 Hz, 1H), 3.16 (s, 3H), 2.40 (s, 3H),
1.39 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.5, 144.2, 143.1,
136.9, 129.5, 129.4, 128.5, 127.7, 124.1, 122.4, 108.3, 61.8, 45.5, 26.4,
25.4, 21.5 ppm.
White solid; H NMR (400 MHz, CDCl3): d=7.38 (d, J=8.6 Hz, 2H),
7.33–7.27 (m, 3H), 6.99 (d, J=7.3 Hz, 1H), 6.90 (t, J=7.5 Hz, 1H),
6.85 (d, J=7.8 Hz, 1H), 3.90 (d, J=14.6 Hz, 1H), 3.69 (d, J=14.6 Hz,
1H), 3.17 (s, 3H), 1.38 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
177.3, 143.2, 140.0, 138.2, 129.2, 129.0, 128.6, 123.9, 122.4, 108.3,
61.9, 45.5, 26.4, 25.4 ppm.
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3-{[(2-Chlorophenyl)sulfonyl]methyl}-1,3-dimethylindolin-2-one
1,3,4,6-Tetramethyl-3-(tosylmethyl)indolin-2-one (3n)
(3h)[18]
1
White solid; H NMR (400 MHz, CDCl3): d=7.37 (d, J=8.2 Hz, 2H),
1
7.17 (d, J=8.0 Hz, 2H), 6.54 (s, 2H), 3.94 (d, J=14.6 Hz, 1H), 3.78
(d, J=14.6 Hz, 1H), 3.11 (s, 3H), 2.41 (s, 3H), 2.37 (s, 3H), 2.12 (s,
3H), 1.38 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.9, 144.2,
143.6, 138.6, 136.6, 134.9, 129.2, 128.0, 125.5, 123.8, 107.0, 60.9,
45.6, 26.4, 23.3, 21.5, 21.4, 18.1 ppm; HRMS (ESI): m/z calcd for
C20H23NO3S: 358.1477; found: 358.1475 [M+H]+.
White solid; H NMR (400 MHz, CDCl3): d=7.46 (d, J=7.8 Hz, 1H),
7.43–7.39 (m, 1H), 7.28 (d, J=7.6 Hz, 1H), 7.16 (t, J=7.7 Hz, 1H),
7.09 (t, J=7.5 Hz, 1H), 6.85–6.80 (m, 2H), 6.64 (t, J=7.5 Hz, 1H),
4.22 (d, J=15.0 Hz, 1H), 4.01 (d, J=14.9 Hz, 1H), 3.23 (s, 3H),
1.41 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.5, 143.4, 137.5,
134.2, 132.1, 131.4, 130.9, 129.2, 128.7, 127.2, 123.2, 122.3, 108.3,
59.7, 45.4, 26.6, 25.1 ppm.
5-Methoxy-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3o)[17]
1
3-({[4-Chloro-3-(trifluoromethyl)phenyl]sulfonyl}methyl)-1,3-di-
White solid; H NMR (400 MHz, CDCl3): d=7.32 (d, J=8.1 Hz, 2H),
methylindolin-2-one (3i)[18]
7.14 (d, J=8.0 Hz, 2H), 6.79–6.73 (m, 2H), 6.50–6.49 (m, 1H), 3.85
(d, J=14.6 Hz, 1H), 3.66–3.62 (m, 4H), 3.16 (s, 3H), 2.38 (s, 3H),
1.36 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.2, 155.7, 144.1,
137.0, 136.7, 130.5, 129.3, 127.7, 113.1, 110.9, 108.6, 61.8, 55.3, 45.9,
26.5, 25.3, 21.4 ppm.
1
White solid; H NMR (400 MHz, CDCl3): d=7.63–7.61 (m, 1H), 7.54
(d, J=8.4 Hz, 2H), 7.31–7.27 (m, 1H), 6.87–6.82 (m, 3H), 3.99 (d, J=
14.9 Hz, 1H), 3.75 (d, J=14.9 Hz, 1H), 3.19 (s, 3H), 1.39 ppm (s,
3H); 13C NMR (100 MHz, CDCl3): d=177.0, 143.2, 138.8, 138.1 (q, J=
1.7 Hz), 132.1, 132.0, 129.1 (q, J=32.4 Hz), 129.05, 128.7, 127.25 (q,
J=5.3 Hz), 123.6, 121.62 (q, J=272.4 Hz), 108.5, 61.9, 45.3, 26.4,
25.4 ppm.
5-Ethoxy-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3p)
1
White solid; H NMR (400 MHz, CDCl3): d=7.34 (d, J=8.1 Hz, 2H),
7.15 (d, J=8.1 Hz, 2H), 6.80–6.77 (m, 1H), 6.73 (d, J=8.5 Hz, 1H),
6.54–6.53 (m, 1H), 3.89–3.79 (m, 3H), 3.63 (d, J=14.6 Hz, 1H), 3.15
(s, 3H), 2.39 (s, 3H), 1.36 ppm (s, 3H); 13C NMR (100 MHz, CDCl3):
d=177.2, 155.1, 144.1, 137.0, 136.6, 130.5, 129.3, 127.7, 113.8,
111.6, 108.5, 63.7, 61.8, 45.9, 26.5, 25.3, 21.4, 14.8 ppm; HRMS (ESI):
m/z calcd for C20H23NO4S: 374.1426; found: 374.1424 [M+H]+.
3-{[(4-Bromophenyl)sulfonyl]methyl}-1,3-dimethylindolin-2-one
(3j)[18]
1
White solid; H NMR (400 MHz, CDCl3): d=7.49 (d, J=8.5 Hz, 2H),
7.31–7.27 (m, 3H), 7.00 (d, J=7.2 Hz, 1H), 6.91 (t, J=7.5 Hz, 1H),
6.85 (d, J=7.8 Hz, 1H), 3.90 (d, J=14.6 Hz, 1H), 3.69 (d, J=14.6 Hz,
1H), 3.17 (s, 3H), 1.38 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
177.3, 143.2, 138.7, 132.0, 129.3, 129.2, 128.63, 128.60, 123.9, 122.4,
108.3, 61.8, 45.4, 26.4, 25.4 ppm.
5-Fluoro-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3q)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.38 (d, J=7.7 Hz, 2H),
7.19 (d, J=7.8 Hz, 2H), 6.97 (t, J=8.6 Hz, 1H), 6.78–6.75 (m, 1H),
6.71 (d, J=7.7 Hz, 1H), 3.85 (d, J=14.6 Hz, 1H), 3.64 (d, J=14.6 Hz,
1H), 3.18 (s, 3H), 2.40 (s, 3H), 1.37 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.3, 159.1 (d, J=239.5 Hz), 144.7, 139.27 (d, J=
2.0 Hz), 136.9, 131.15 (d, J=8.1 Hz), 129.6, 127.7, 114.87 (d, J=
23.3 Hz), 112.27 (d, J=25.0 Hz), 108.8 (d, J=8.1 Hz), 61.7, 46.0, 46.0,
26.7, 25.3, 21.5 ppm.
1,3-Dimethyl-3-[(naphthalen-1-ylsulfonyl)methyl]indolin-2-one
(3k)[18]
1
White solid; H NMR (400 MHz, CDCl3): d=8.67 (d, J=8.6 Hz, 1H),
8.00 (d, J=8.1 Hz, 1H), 7.94 (d, J=8.2 Hz, 1H), 7.75 (t, J=7.5 Hz,
1H), 7.63 (t, J=7.2 Hz, 2H), 7.30–7.21 (m, 2H), 6.85 (d, J=7.8 Hz,
1H), 6.74 (d, J=4.2 Hz, 2H), 4.07 (d, J=14.5 Hz, 1H), 3.89 (d, J=
14.6 Hz, 1H), 3.22 (s, 3H), 1.37 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.7, 143.3, 134.9, 134.8, 134.0, 130.3, 129.5, 129.2,
128.8, 128.6, 128.4, 127.0, 124.3, 124.0, 123.6, 122.3, 108.4, 61.1,
45.6, 26.6, 25.4 ppm.
5-Chloro-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3r)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.36–7.34 (m, 1H), 7.29
(d, J=8.2 Hz, 2H), 7.16 (d, J=8.0 Hz, 2H), 6.82–6.81 (m, 1H), 6.74
(d, J=8.3 Hz, 1H), 3.89 (d, J=14.8 Hz, 1H), 3.65 (d, J=14.8 Hz, 1H),
3.22 (s, 3H), 2.43 (s, 3H), 1.35 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.0, 144.6, 142.5, 136.7, 131.2, 129.6, 127.4, 127.0,
115.1, 109.7, 61.7, 45.6, 26.6, 25.1, 21.6 ppm.
3-[(Butylsulfonyl)methyl]-1,3-dimethylindolin-2-one (3l)
1
Colorless oil; H NMR (400 MHz, CDCl3): d=7.37–7.31 (m, 2H), 7.10
(t, J=7.5 Hz, 1H), 6.90 (d, J=7.8 Hz, 1H), 3.63 (d, J=14.5 Hz, 1H),
3.53 (d, J=14.5 Hz, 1H), 3.25 (s, 3H), 2.67–2.64 (m, 2H), 1.72–1.64
(m, 2H), 1.45 (s, 3H), 1.39–1.29 ppm (m, 2H); 13C NMR (100 MHz,
CDCl3): d=178.0, 143.4, 130.4, 129.0, 123.6, 122.5, 108.8, 58.6, 54.9,
45.5, 26.6, 25.0, 23.7, 21.5, 13.4 ppm; HRMS (ESI): m/z calcd for
C15H21NO3S: 296.1320; found: 296.1319 [M+H]+.
4,6-Dichloro-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3s)
1
White solid; H NMR (400 MHz, CDCl3): d=7.36 (d, J=7.5 Hz, 2H),
7.16 (d, J=7.6 Hz, 2H), 6.78 (s, 1H), 6.71 (s, 1H), 4.07 (d, J=
14.5 Hz, 1H), 3.77 (d, J=14.5 Hz, 1H), 3.18 (s, 3H), 2.38 (s, 3H),
1.42 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.0, 146.1, 144.7,
136.3, 135.4, 131.8, 129.5, 127.8, 124.6, 122.76, 122.75, 107.9, 59.8,
46.1, 27.0, 22.0, 21.6 ppm; HRMS (ESI): m/z calcd for C18H17Cl2NO3S:
398.0384; found: 398.0388 [M+H]+.
1,3,5-Trimethyl-3-(tosylmethyl)indolin-2-one (3m)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.26 (d, J=8.0 Hz, 2H),
7.10 (d, J=7.8 Hz, 2H), 7.02 (d, J=7.8 Hz, 1H), 6.72 (d, J=7.9 Hz,
1H), 6.60 (s, 1H), 3.87 (d, J=14.7 Hz, 1H), 3.66 (d, J=14.7 Hz, 1H),
3.16 (s, 3H), 2.37 (s, 3H), 2.09 (s, 3H), 1.33 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=177.6, 144.0, 141.0, 137.0, 131.8, 129.33,
129.29, 128.8, 127.8, 124.7, 108.1, 61.9, 45.6, 26.6, 25.4, 21.5,
20.9 ppm.
5-Bromo-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3t)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.36–7.34 (m, 1H), 7.29
(d, J=8.3 Hz, 2H), 7.16 (d, J=8.0 Hz, 2H), 6.82–6.81 (m, 1H), 6.73
(d, J=8.2 Hz, 1H), 3.88 (d, J=14.8 Hz, 1H), 3.65 (d, J=14.8 Hz, 1H),
3.21 (s, 3H), 2.43 (s, 3H), 1.34 ppm (s, 3H); 13C NMR (100 MHz,
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Butyl-3-methyl-3-(tosylmethyl)indolin-2-one (3aa)[18]
CDCl3): d=177.0, 144.6, 142.5, 136.6, 131.2, 129.6, 127.4, 127.0,
115.1, 109.7, 61.7, 45.5, 26.6, 25.1, 21.6 ppm.
1
White solid; H NMR (400 MHz, CDCl3): d=7.40 (d, J=8.0 Hz, 2H),
7.28–7.24 (m, 1H), 7.17 (d, J=7.9 Hz, 2H), 7.06 (d, J=7.2 Hz, 1H),
6.88 (t, J=8.7 Hz, 2H), 3.83 (d, J=14.5 Hz, 1H), 3.71–3.59 (m, 3H),
2.40 (s, 3H), 1.75–1.65 (m, 2H), 1.46–1.39 (m, 5H), 0.97 ppm (t, J=
14.6 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=177.5, 144.3, 142.7,
137.3, 129.8, 129.5, 128.4, 127.8, 124.2, 122.2, 108.6, 61.8, 45.6, 40.1,
29.2, 25.7, 21.6, 20.2, 13.8 ppm.
5-Iodo-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3u)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.56–7.53 (m, 1H), 7.28–
7.26 (m, 2H), 7.17 (d, J=8.1 Hz, 2H), 6.96–6.95 (m, 1H), 6.65 (d, J=
8.2 Hz, 1H), 3.89 (d, J=14.8 Hz, 1H), 3.65 (d, J=14.8 Hz, 1H), 3.22
(s, 3H), 2.46 (s, 3H), 1.34 ppm (s, 3H); 13C NMR (100 MHz, CDCl3):
d=176.9, 144.6, 143.2, 137.2, 136.7, 132.5, 131.6, 129.6, 127.4,
110.3, 61.7, 45.4, 26.5, 25.1, 21.8 ppm.
1-Benzyl-3-methyl-3-(tosylmethyl)indolin-2-one (3ab)[17]
1
Colorless oil; H NMR (400 MHz, CDCl3): d=7.42 (d, J=7.9 Hz, 2H),
7.39–7.25 (m, 5H), 7.18–7.12 (m, 3H), 7.04 (d, J=7.4 Hz, 1H), 6.85
(t, J=7.5 Hz, 1H), 6.71 (d, J=7.8 Hz, 1H), 5.00 (d, J=15.7 Hz, 1H),
4.80 (d, J=15.8 Hz, 1H), 3.91 (d, J=14.5 Hz, 1H), 3.73 (d, J=
14.5 Hz, 1H), 2.40 (s, 3H), 1.45 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.9, 144.3, 142.4, 137.2, 135.8, 129.7, 129.6, 128.8,
128.4, 127.8, 127.6, 127.3, 124.0, 122.5, 109.5, 61.7, 45.8, 44.2, 26.0,
21.6 ppm.
6-Iodo-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3v)
1
White solid; H NMR (400 MHz, CDCl3): d=7.52–7.50 (m, 1H), 7.24
(d, J=8.2 Hz, 2H), 7.14 (d, J=8.0 Hz, 2H), 6.928–6.926 (m, 1H), 6.63
(d, J=8.2 Hz, 1H), 3.87 (d, J=14.8 Hz, 1H), 3.66 (d, J=14.8 Hz, 1H),
3.20 (s, 3H), 2.44 (s, 3H), 1.32 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=176.9, 144.6, 143.2, 137.1, 136.6, 132.4, 131.5, 129.7,
129.6, 127.3, 110.3, 61.7, 45.3, 26.6, 25.1, 21.8 ppm. HRMS (ESI): m/z
calcd for C18H18INO3S: 456.0130; found: 456.0133 [M+H]+.
3-Methyl-1-(4-methylbenzyl)-3-(tosylmethyl)indolin-2-one
(3ac)
1,3-Dimethyl-5-nitro-3-(tosylmethyl)indolin-2-one (3w)
1
White solid; H NMR (400 MHz, CDCl3): d=7.43 (d, J=8.1 Hz, 2H),
White solid; 1H NMR (400 MHz, CDCl3): d=8.23–8.21 (m, 1H),
7.613–7.608 (m, 1H), 7.32 (d, J=8.2 Hz, 2H), 7.14 (d, J=8.0 Hz, 2H),
6.96 (d, J=8.6 Hz, 1H), 3.94 (t, J=14.8 Hz, 1H), 3.79 (d, J=14.8 Hz,
1H), 3.33 (s, 3H), 2.35 (s, 3H), 1.41 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.8, 149.1, 144.9, 143.0, 136.7, 130.0, 129.6, 127.2,
125.6, 119.6, 107.9, 61.5, 45.3, 27.0, 24.9, 21.2 ppm; HRMS (ESI): m/z
calcd for C18H18N2O5S: 375.1015; found: 375.1015 [M+H]+.
7.26 (d, J=8.2 Hz, 2H), 7.18–7.13 (m, 5H), 7.06 (d, J=7.3 Hz, 1H),
6.85 (t, J=7.5 Hz, 1H), 6.72 (d, J=7.8 Hz, 1H), 4.97 (d, J=15.6 Hz,
1H), 4.73 (d, J=15.6 Hz, 1H), 3.90 (d, J=14.5 Hz, 1H), 3.72 (d, J=
14.5 Hz, 1H), 2.40 (s, 3H), 2.32 (s, 3H), 1.45 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=177.7, 144.2, 142.3, 137.2, 137.1, 132.7, 129.6,
129.4, 129.3, 128.3, 127.7, 127.2, 123.9, 122.3, 109.4, 61.6, 45.7, 43.9,
25.8, 21.4, 21.0 ppm; HRMS (ESI): m/z calcd for C25H25NO3S:
440.1633; found: 440.1632 [M+H]+.
5-Acetyl-1,3-dimethyl-3-(tosylmethyl)indolin-2-one (3x)
1-(4-Chlorobenzyl)-3-methyl-3-(tosylmethyl)indolin-2-one
(3ad)
1
White solid; H NMR (400 MHz, CDCl3): d=7.93 (d, J=8.1 Hz, 1H),
7.40 (s, 1H), 7.29 (d, J=8.1 Hz, 2H), 7.11 (d, J=7.8 Hz, 2H), 6.92 (d,
J=8.2 Hz, 1H), 3.92 (d, J=14.7 Hz, 1H), 3.75 (d, J=14.7 Hz, 1H),
3.28 (s, 3H), 2.45 (s, 3H), 2.34 (s, 3H), 1.39 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=196.1, 178.1, 147.8, 144.5, 137.0, 131.8, 130.3,
129.6, 129.5, 127.5, 123.8, 107.9, 61.8, 45.3, 26.9, 26.2, 25.2,
21.5 ppm; HRMS (ESI): m/z calcd for C20H21NO4S: 372.1270; found:
372.1265 [M+H]+.
1
White solid; H NMR (400 MHz, CDCl3): d=7.42 (d, J=8.2 Hz, 2H),
7.36–7.30 (m, 4H), 7.19–7.14 (m, 3H), 7.03 (d, J=7.4 Hz, 1H), 6.86
(t, J=7.5 Hz, 1H), 6.67 (d, J=7.8 Hz, 1H), 4.89 (t, J=16.7 Hz, 2H),
3.92 (d, J=14.5 Hz, 1H), 3.72 (d, J=14.6 Hz, 1H), 2.41 (s, 3H),
1.44 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=177.8, 144.3, 142.0,
137.2, 134.2, 133.4, 129.6, 129.5, 128.8, 128.7, 128.3, 127.6, 123.9,
122.5, 109.3, 61.6, 45.6, 43.5, 25.9, 21.4 ppm; HRMS (ESI): m/z calcd
for C24H22ClNO3S: 440.1087; found: 440.1089 [M+H]+.
1,3-Dimethyl-2-oxo-3-(tosylmethyl)indoline-5-carbonitrile
(3y)[17]
1-Methyl-1-(tosylmethyl)-5,6-dihydro-1H-pyrrolo[3,2,1-ij]qui-
nolin-2(4H)-one (3af)[17]
1
White solid; H NMR (400 MHz, CDCl3): d=7.59 (d, J=8.0 Hz, 1H),
7.34 (d, J=7.9 Hz, 2H), 7.22 (d, J=7.9 Hz, 2H), 7.03 (s, 1H), 6.95 (d,
J=8.1 Hz, 1H), 3.91 (d, J=14.7 Hz, 1H), 3.71 (d, J=14.7 Hz, 1H),
3.29 (s, 3H), 2.47 (s, 3H), 1.39 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=177.5, 147.3, 145.2, 136.8, 133.7, 130.5, 129.8, 127.4,
127.2, 118.7, 108.9, 105.6, 61.6, 45.3, 26.9, 25.1, 21.6 ppm.
1
Yellow solid; H NMR (400 MHz, CDCl3): d=7.42 (d, J=8.2 Hz, 2H),
7.18 (d, J=8.1 Hz, 2H), 7.02 (d, J=7.6 Hz, 1H), 6.96 (d, J=7.4 Hz,
1H), 6.82 (t, J=7.6 Hz, 1H), 3.81 (d, J=14.4 Hz, 1H), 3.73–3.57 (m,
3H), 2.78 (t, J=5.0 Hz, 2H), 2.39 (s, 3H), 2.04–1.98 (m, 2H),
1.40 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=176.4, 144.1, 138.9,
137.2, 129.4, 128.2, 127.7, 127.2, 122.0, 121.8, 120.3, 61.8, 46.7, 39.0,
25.0, 24.5, 21.4, 20.9 ppm.
1-Ethyl-3-methyl-3-(tosylmethyl)indolin-2-one (3z)
1
White solid; H NMR (400 MHz, CDCl3): d=7.40 (d, J=7.8 Hz, 2H),
7.29–7.25 (m, 1H), 7.17 (d, J=7.9 Hz, 2H), 7.04 (d, J=7.4 Hz, 1H),
6.89–6.86 (m, 2H), 3.85 (d, J=14.5 Hz, 1H), 3.80–3.74 (m, 1H),
3.72–3.65 (m, 2H), 2.40 (s, 3H), 1.38 (s, 3H), 1.31 ppm (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=177.3, 144.3, 142.4, 137.3,
129.9, 129.5, 128.4, 127.7, 124.2, 122.2, 108.5, 61.8, 45.6, 34.9, 25.5,
21.6, 12.3 ppm; HRMS (ESI): m/z calcd for C19H21NO3S: 344.1320;
found: 344.1316 [M+H]+.
1,3-Dimethyl-3-(tosylmethyl)-1H-benzo[de]quinolin-2(3H)-one
(3ag)
1
White solid; H NMR (400 MHz, CDCl3): d=7.68 (d, J=8.1 Hz, 1H),
7.52 (d, J=8.1 Hz, 1H), 7.45 (t, J=7.6 Hz, 1H), 7.31 (t, J=7.5 Hz,
1H), 7.27–7.22 (m, 3H), 7.02 (d, J=8.0 Hz, 2H), 6.97 (d, J=7.4 Hz,
1H), 4.61 (d, J=14.4 Hz, 1H), 3.90 (d, J=14.4 Hz, 1H), 3.51 (s, 3H),
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2.34 (s, 3H), 1.65 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=170.7,
143.8, 137.5, 136.3, 133.6, 133.3, 129.1, 127.6, 126.6, 126.4, 126.4,
123.6, 122.5, 119.2, 108.7, 66.0, 45.5, 33.6, 29.9, 21.4 ppm; HRMS
(ESI): m/z calcd for C22H21NO3S: 380.1320; found: 380.1324 [M+H]+.
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Acknowledgements
This work was financially supported by the National Science
Foundation of China (nos. 21372095, 21172092) and the Anhui
Provincial Natural Science Foundation (1508085QB42).
Keywords: domino reactions · heterocycles · photochemistry ·
radical reactions · redox
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Manuscript received: May 14, 2015
Accepted Article published: June 19, 2015
Final Article published: July 29, 2015
Chem. Asian J. 2015, 10, 1919 – 1925
www.chemasianj.org
1925
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