Hydrogen and Sulfonyl Radical Generation for the Hydrogenation and Arylsulfonylation of Alkenes Driven by Photochemical Activity of Hydrogen Bond Donor-Acceptor Complexes

Article abstract of DOI:10.1002/adsc.201801521

An efficient photoinduced strategy for the hydrogenation and arylsulfonylation of alkenes has been developed. The reaction afforded a range of hydrogenated products and sulfonated oxindoles in high yields under external photocatalyst-free, oxidant- and reductant-free conditions. Mechanistic investigations suggested this transformation is driven by the photochemical activity of hydrogen bond donor-acceptor complex, generated from the substrates of arylsulfinic acids and C6-(vinyl sulfone)phenanthridines or N-arylacrylamides via hydrogen bond interaction. (Figure presented.).

Full text of DOI:10.1002/adsc.201801521

Title: Hydrogen and Sulfonyl Radical Generation for the Hydrogenation
and Arylsulfonylation of Alkenes Driven by Photochemical Activity
of Hydrogen Bond Donor–Acceptor Complexes
Authors: Yang Li, Fang Ma, Pinhua Li, Tao Miao, and Lei Wang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801521
Link to VoR: http://dx.doi.org/10.1002/adsc.201801521

10.1002/adsc.201801521
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.200((will be filled in by the editorial staff))
Hydrogen and Sulfonyl Radical Generation for the
Hydrogenation and Arylsulfonylation of Alkenes Driven by
Photochemical Activity of Hydrogen Bond Donor–Acceptor
Complexes
Yang Li,a Fang Ma,a Pinhua Li,a Tao Miao,*a and Lei Wang*a,b
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, People’s Republic of China
Fax: (+86)-561-309-0518; phone: (+86)-561-380-2069; e-mail: taomiao@chnu.edu.cn; leiwang@chnu.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032,
b
People’s Republic of China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.200######.((Please
delete if not appropriate))
hydrogen bond donor-acceptor complex, generated from
the substrates of arylsulfinic acids and C6-(vinyl
sulfone)phenanthridines or N-arylacrylamides via hydrogen
bond interaction.
Abstract: An efficient photoinduced strategy for the
hydrogenation and arylsulfonylation of alkenes has been
developed. The reaction afforded a range of hydrogenated
products and sulfonated oxindoles in high yields under
external photocatalyst-free, oxidant- and reductant-free
conditions. Mechanistic investigations suggested this
transformation is driven by the photochemical activity of
Keywords: photochemisty; arylsulfinic acids; alkenes;
hydrogen bond interaction; radical transformation
The acquirement of energy from light is a highly
economical and environmentally benign strategy of
promoting chemical transformations because light is
regarded as an inexpensive, abundant and infinitely
available energy source.[4] Therefore, radical process
only employed light as an initiator under
photocatalyst and external oxidant-free conditions is
undoubtedly the ideal and promising route to
achieving aforementioned goal. However, due to the
incapablity of most common organic compounds to
absorb visible light, photocatalysts such as metal
ruthenium or iridium complexes and organic dyes
were often employed through their visible light-
driven electron/energy transfer to sensitize organic
molecules in photoredox catalysis.[5] Recently, the
photochemical activity of electron donor-acceptor
(EDA) complex, provides a viable alternative for
photo-induced radical transformations without the
need for an external photocatalyst.[6] It should be
noted that EDA complex is the transient combination
of an electron-rich and an electron-accepting
substrate by the appearance of a weak absorption
band or a charge-transfer band.[7] On the other hand,
hydrogen bonding, a bond between a donor hydrogen
atom and an electronegative acceptor atom, is one of
the most important molecular interactions, playing a
crucial role in chemical, physical and biochemical
processes.[8] During the past few decades, the
Introduction
Radical transformations are fundamental and widely
utilized synthetic tools in modern organic chemistry,
which are often compatible with a broad range of
functional groups and have great potential to enable
unconventional bond cleavages and constructions.[1]
To date, much effort has focused on the discovery and
design of synthetically useful and selective radical
reactions from readily available substrates, and
significant achievements have been made in this
field.[2] Among of these, direct transformation of
alkenes with free radical has offered a straightforward
means for the synthesis of the target organics,
especially for the simultaneous introduction of two
functional groups to the carbon-carbon double
bonds.[3] Nevertheless, most of the these radical
strategies are carried out by utilizing precious and/or
toxic metal complexes and unfriendly radical
initiators as catalysts or oxidants, leading to the
difficult purification of the desired products from a
large amount of unwanted by-products and residual
metal catalysts. These disadvantages seriously restrict
the application of radical reactions in the areas of
pharmaceutical and materials industries. Therefore,
the development of green and sustainable radical
reaction is highly appealing.
1
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10.1002/adsc.201801521
Advanced Synthesis & Catalysis
physical and chemical properties of hydrogen bonds
inferior yields of products (Table 1, entries 4–9).
have been widely investigated both experimentally THF, and 1,4-dioxane were not suitable solvents
and theoretically, while their application in and the reaction was prohibited completely
photochemical reactions was undeveloped. Herein, (Table 1, entries 10 and 11). Furthermore, the role
we report our progress on photo-induced hydrogen
and sulfonyl radical generation by hydrogen bond
donor-acceptor complexes generated from substrates,
which provided a novel, efficient, and atom-economic
approach for selective hydrogenation of C6-(vinyl
sulfone)phenanthridines and coupling of N-
arylacrylamides with arylsulfinic acids in one-pot
under photocatalyst-free, external oxidant-free and
reductant-free conditions (Scheme 1). It is important
to note that this protocol was carried out in
exceptionally facile and mild manners by simply
mixing substrates and arylsulfinic acids in acetonitrile
as solvent under UV light (380±5 nm) irradiation,
providing hydrogenated products and sulfonated
oxindoles in good to excellent yields.
of atmospheric nitrogen (N2) was also found to an
essential parameter in the formation of 4a and 5a
because there was no reaction under air atmosphere
(Table 1, entry 12). It should be noted that no
product was detected in the absence of light even the
Table 1. Optimization of the reaction conditions.[a]
Yield (%)[b]
Entry
Solvent
4a
38
0
5a
1[c]
2[d]
3
CH3CN
CH3CN
CH3CN
CH2Cl2
DCE
0
70 (94[e])
92
76
68
83
53
78
39
0
95
85
80
87
74
87
7
4
5
6
CHCl3
Toluene
DMSO
DMF
7
8
9
10
11
12[f]
13[g]
14[h]
15[i]
16[j]
THF
0
Dioxane
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
0
0
Scheme
1.
Photoinduced
hydrogenation
and
0
0
arylsulfonylation of alkenes.
0
0
0
0
Results and Discussion
0
0
0
0
Initially, we found that (Z)-6-(1-tosylhept-1-en-2-
yl)phenanthridine (1a) was hydrogenated to generate
the 6-(1-tosylheptan-2- yl)phenanthridine (4a) in 38%
yield in presence of p-toluenesulfinic acid under N2
atmosphere with 3 W UV (380±5 nm) irradiation for
24 h (Table 1, entry 1). On the same conditions,
sulfonated oxindole (5a) was formed in 70% yield
[a]
Reaction conditions: (Z)-6-(1-tosylhept-1-en-2-yl)phenan-
thridine (1a, 0.25 mmol), N-methyl-N-phenylmethacrylamide (2a,
0.25 mmol), p-toluene-sulfinic acid (3a, 0.75 mmol), solvent (4.0
mL), UV (380±5 nm, 3 W), N2, r.t., 24 h.
[b] Isolated yield based on 1a and 2a.
[c] 1a (0.25 mmol) with 3a (0.375 mmol),
[d] 2a (0.25 mmol) with 3a (0.375 mmol).
[e] 3a (0.75 mmol) was used.
when
N-methyl-N-phenyl-methacrylamide
(2a)
[f] In the air.
reacted with p-toluenesulfinic acid (Table 1, entry
2). Increasing the amount of p-toluenesulfinic acid,
5a with 94% yield was obtained. These results
suggested arylsulfinic acids were used as hydrogen
and sulfonyl sources, respectively. To increase the
reaction efficiency and reduce synthesis steps, we
wondered whether two transformations were carried
out in one-pot, in which p-toluenesulfinic acid was
employed as hydrogen and sulfonyl sources for
hydrogenation of 1a and arylsulfonylation of 2a. To
our delighted, the hydrogenation product (4a) and
sulfonated oxindole (5a) were obtained in excellent
yield of 92% and 95% when 1a, 2a reacted with 3a in
one-pot without any photocatalyst, external oxidant
and reductant (Table 1, entry 3). Next, the effect of
the solvent on the model reaction was examined.
Other solvents including CH2Cl2, DCE, CHCl3,
toluene, DMSO (dimethyl sulfoxide) and DMF (N,N-
dimethylformamide) were less effective and gave the
[g] Darkness, 24 h.
[h] Darkness, 80 °C, 24 h
[i] Blue LED (450±5 nm, 3 W).
[j] Green LED (530±5 nm, 3 W).
o
reaction was heated to 80 C for 24 h (Table 1,
entries 13 and 14). Similarly, the reaction also did
not proceed under the irradiation with blue LED
(450±5 nm) or green LED (530±5 nm) (Table 1,
entries 15 and 16). All these features demonstrate
that this radical tandem reaction is a photoinduced
process.
To gain
a
better understanding of this
photoinduced radical process, a series of optical
absorption spectra of the solution were recorded. As
depicted in Figure 1a, the optical absorption spectrum
of the solution showed a clear bathochromic
displacement above 380 nm after mixing 1a and 3a or
2a and 3a in CH3CN, where none of the substrates
2
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10.1002/adsc.201801521
Advanced Synthesis & Catalysis
absorbed. The solution of 1a and 3a showed stronger
red-shifts compared to 2a and 3a. When mixed with
1a, 2a and 3a, the UV/vis absorption spectrometry
indicated no obvious signal change from 1a and 3a.
However, since color change was not observed in the
reaction mixture, the EDA association in the ground
state might not be involved. In addition, nuclear
sulfone)phenanthridines (1) was investigated in
presence of 2a and 3a.[10] As shown in Scheme 2, the
reduction worked very well with a diverse set of (Z)-
C6-(vinyl sulfone)phenanthridines including aliphatic
and aromatic substituted ones, leading to the
hydrogenation
products
C6-(alkyl
sulfone)phenanthridines (4a–u) in good to excellent
yields, and the structure of 4m was unambiguously
confirmed by X-ray crystal structure analysis.
Importantly, the reaction was not sensitive to the
electronic nature of the substituents on either
phenanthridine ring or phenyl ring, and both electron-
withdrawing and electron-donating substituted
substrates ran smoothly to deliver the hydrogenation
products in 80–95% yields. A number of functional
groups, including Me, MeO, F, Cl, Br, CF3, and
CO2Et can tolerate the standard conditions.
Meanwhile, sulfonated oxindole 5a was also obtained
magnetic
resonance
(NMR)
spectroscopy
experiments showed that 1H-NMR signal of p-
toluenesulfinic acid (3a) shifted downfield with the
addition of 1a or 2a, suggesting the formation of the
hydrogen bond donor-acceptor complex from 3a and
1a or 2a via hydrogen bonding interaction (Figure S1,
SI). Geometry structures of the hydrogen bond donor-
acceptor complexes were obtained using the
Minnesota density functional M06-2X with 6-31G
(d,p) basis set, and the PCM using the Integral
Equation Formalism model (IEFPCM) was adopted to
simulate the solvation effect (solvent = acetonitrile).[9] via cascade CS/CC bond formation process during
As shown in Figure 1b, the hydrogen bond extended
the framework of the single substrate, which was the
reason of the bathochromic displacement.
Furthermore, water has multiple H-bonding
capabilities in biological and organic synthetic
systems. When deuterium oxide was added to the
reaction of 1a and 3a under the optimized conditions,
the product 4a (H/D = 7:3) was obtained with 62%
yield, indicating that H2O could be involved in the
reaction as hydrogen bond donor via a hydronium
ion, generated from H2O and sulfinic acid (Figure S2,
SI).
the formation of the products 4 using 2a and 3a, and
the yields of 5a exceed 90% in all cases. Survival of
ethoxy carbonyl and sulfonyl groups and selective
formation of sulfonated oxindole illustrated the
Scheme 2. Scope of C6-(vinyl sulfone)phenanthridines.[a]
[a]Reaction conditions: (Z)-C6-(vinyl sulfone)phenanthridine (1,
0.25 mmol), N-methyl-N-phenyl-methacrylamide (2a, 0.25
mmol), p-toluenesulfinic acid (3a, 0.75 mmol), CH3CN (4.0 mL),
3 W UV (380±5 nm), N2, r.t., 24 h; isolated yield based on 1 and
2a.]
Figure 1. (a) Optical absorption spectra of the reaction
components. (b) Hydrogen bond extends the framework of the
single substrate.
remarkable chemoselectivity of this photoinduced
hydrogenation reaction. Moreover, when (Z)-6-(1-
((4-chlorophenyl)-sulfonyl)hept-1-en-2-yl)phenanth-
ridine was employed as the substrate under the
optimized conditions, the reaction gave a mixture of
hydrogenated products 4v and 4a in isolated yields of
With optimized reaction conditions in hand, the
scope of this photoinduced hydrogenation process
with
a
variety
of
(Z)-C6-(vinyl
3
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10.1002/adsc.201801521
Advanced Synthesis & Catalysis
51% and 32%, accompanied with sulfonated
oxindoles 5b and 5a in 15% and 80% yields,
respectively. The similar results were also observed
when (Z)-6-(2-((4-chlorophenyl)sulfonyl)-1-phenyl-
vinyl)phenanthridine reacted with 2a and 3a. These
provided important information to understand the
hydrogenation process.
We then turned our attention to explore the scope
of the arylacrylamides (2) and arylsulfinic acids (3) in
absence of 1, as shown in Scheme 3. A lot of
substituted arylsulfinic acids bearing methyl, tert-
butyl, methoxy, fluoro and chloro on the aromatic
rings reacted with 2a effectively, and afforded the
corresponding sulfonated oxindoles 5a–m in 70–97%
yields. Notably, functional groups such as cyano,
trifluoromethyl and halogen groups are tolerated. A
little steric effect was observed during the reaction of
detected when 2a reacted with 3a in the presence of a
radical
inhibitor
TEMPO
(2,2,6,6-
tetramethylpiperidinoxy), and TEMPO adduct III
from hydrogen radical was detected by ESI-MS
(Electrospray ionization mass spectrometry)[11]
(Scheme 4a). However, product 5a and adduct III
were not detected when a cut-off filter below 400 nm
was used. Furthermore, when TEMPO was employed
under the standard conditions, the desired reaction of
1a, 2a and 3a was completely inhibited, and TEMPO
adduct III and intermediate 6 were also detected.
However, we failed to isolate intermediate 6 due to a
trace amount (Scheme 4b). To further confirm the
existence of intermediates, the reaction of p-
chorophenylsulfinic acid, 1a with TEMPO was
carried out under the optimized conditions for 16 h.
The ESI-MS analysis of the reaction mixture showed
the existence of hydrogen and alkyl radical addition
intermediates III, IV and V (Scheme 4c).
ortho-methylbenzenesulfinic
acids
with
2a,
generating 71% yield of 5g. 2-Naphthyl and 2-
thienylsulfinic acids were also successful in this
transformation with 61 and 70% yields of the
products (5l–m). n-Butylsulfinic acid was also a
suitable reaction partner, giving product 5n in 64%
yield. Subsequently, the scope of the arylacrylamides
was evaluated. As expected, both electron-rich and
electron-deficient arylacrylamides afforded the
desired oxindoles (5o–t) in good to excellent yields.
However, this reaction was extremely sensitive to
steric hindrance. For example, arylacrylamide bearing
an ortho-substitutent reacted with p-toluenesulfinic
acid, only trace amount of product 5u was obtained.
Furthermore, N-free arylacrylamide was also not
suitable substrate, and no product (5v) was formed.
Scheme 3. Scope of arylacrylamides and sulfinic acids.[a]
Scheme 4. The radical-trapping experiments.
Based on the results of these studies and previous
related reports,[6,8] a plausible mechanism is proposed
in Scheme 5. Initially, hydrogen bond donor-acceptor
complexes are formed from substrates 1, 2a and 3a
via hydrogen bonding interaction. The complexes are
excited by LED (380 nm) irradiation to generate the
excited species, which make 3a homolytic cleavage
to produce highly reactive hydrogen radical and O-
centered radical A, which resonate with sulfonyl
radical B. Subsequently, an addition of sulfonyl
radical B to activated alkene 2a affords the alkyl
radical C, followed by intramolecular cyclization
with an aryl ring. This leads to the formation of
radical intermediate D, which is oxidized by O-
centered radical A to form a cationic intermediate E
process. Finally, intermediate E loses a proton to
produce the final product sulfonated oxindole 5a,
along with 3a. On the other hand, sulfonyl radical B
can also add to double-double bond of 1 to generate
the alkyl radical intermediate F, which abstracts a
hydrogen radical to deliver the compound of G. Then,
C-S bond homolytic cleavage of G produces the
[a]Reaction conditions: arylacrylamide (2, 0.25 mmol) and
arylsulfinic acid (3, 0.75 mmol), CH3CN (4.0 mL), 3 W UV
(380±5 nm), N2, r.t, 24 h; isolated yield based on 2.
To gain insights into the reaction mechanism,
radical-trapping experiments were conducted
(Scheme 4). It was found that no product 5a was
4
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10.1002/adsc.201801521
Advanced Synthesis & Catalysis
radicals H and J, which can be captured by TEMPO.
Finally, radicals H and J react with hydrogen radical
to generate hydrogenated products 4a and 4v.
collected on an Agilent Technologies 6540 UHD
Accurate-Mass Q-TOF LC/MS using ESI.
Unless otherwise stated, all reactions were carried
out under N2 atmosphere. The chemicals and solvents
were purchased from commercial suppliers either
from Aldrich (USA) or Shanghai Chemical Company
(China) without further purification. Products were
purified by flash chromatography on 100–200 mesh
silica gels, SiO2.
Typical procedure for for synthesis of 4a and 5a
(Z)-6-(1-tosylhept-1-en-2-yl)phenanthridine (1a,
0.25 mmol), N-methyl-N- phenylmethacrylamide (2a,
0.25 mmol), p-toluenesulfinic acid (3a, 0.75 mmol)
were added into an air-tight reaction tube (10 mL)
with 4.0 mL of CH3CN. The tube containing the
reactants and solvent was evacuated by pump and
back-filled with nitrogen. Then, the reaction was
stirred at room temperature under photo-irradiation
with UV LED (380 ± 5 nm, 3 W) for 24 h. After the
reaction was completed, the resulting crude mixture
was purified by flash chromatography on silica gel
(petroleum ether/EtOAc = 7:1 to 3:1) to provide the
desired products 4a and 5a in 92% and 95% yields.
Scheme 5. Proposed mechanism for the formation of 4 and
5
Conclusion
Characterization Data for the Products
In summary, we have developed a straightforward
6-(1-Tosylheptan-2-yl)phenanthridine (4a): Colorless
oil, 99.1 mg, 92% yield. H NMR (400 MHz, CDCl3) δ:
1
method
for
hydrogenation
of
C6-(vinyl
8.56 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 7.6 Hz, 1H), 8.23 (d,
J = 8.0 Hz, 1H), 7.847.80 (m, 2H), 7.70 (td, J = 7.6, 0.8
Hz, 1H), 7.63 (td, J = 7.4, 1.2 Hz, 1H), 7.56 (td, J = 7.5,
1.3 Hz, 1H), 7.21 (d, J = 8.4 Hz, 2H), 6.49 (d, J = 8.0 Hz,
2H), 4.704.64 (m, 1H), 4.384.32 (m, 1H), 3.53 (dd, J =
14.2, 2.6 Hz, 1H), 1.941.88 (m, 4H), 1.831.75 (m, 1H),
1.401.34 (m, 1H), 1.20 (br, 5H), 0.79 (t, J = 7.0 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ: 160.32, 143.36, 142.98,
136.19, 132.74, 130.30, 129.61, 128.17, 127.48, 127.34,
126.48, 125.14, 123.17, 122.18, 121.49, 59.67, 37.07,
36.15, 31.62, 26.59, 22.32, 21.03, 13.87. HRMS (ESI)
([M+H]+) calculated for C27H30NO2S: 432.1992, found:
432.1993.
sulfone)phenanthridines and coupling of N-
arylacrylamides with arylsulfinic acids in one-pot.
These reactions proceeded at room temperature in
good to excellent yields with broad substrate scope
and under external photocatalyst-free, oxidant-free
and reductant-free, and mild reaction conditions. A
preliminary mechanism indicated that this reaction
process is driven by the photochemical activity of
hydrogen bond donor-acceptor complexes, generated
upon association of readily available arylsulfinic
acids and C6-(vinyl sulfone)phenanthridines or/and
N-arylacrylamides via hydrogen bond interaction.
Further efforts are being carried out to investigate the
potential application of this hydrogen bond donor-
acceptor complex in organic synthesis.
6-(1-Tosylpentan-2-yl)phenanthridine (4b): Colorless
1
oil, 93.7 mg, 93% yield. H NMR (400 MHz, CDCl3) δ:
8.56 (d, J = 8.0 Hz, 1H), 8.44 (dd, J = 8.4, 0.6 Hz, 1H),
8.24 (d, J = 8.4 Hz, 1H), 7.857.81 (m, 2H), 7.70 (td, J =
7.6, 1.2 Hz, 1H), 7.64 (td, J = 7.5, 1.3 Hz, 1H), 7.57 (td, J
= 7.6, 1.5 Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 6.49 (d, J =
8.0 Hz, 2H), 4.704.64 (m, 1H), 4.414.34 (m, 1H), 3.52
(dd, J = 14.4, 2.8 Hz, 1H), 1.931.88 (m, 4H), 1.831.75
(m, 1H), 1.421.31 (m, 1H), 1.251.16 (m, 1H), 0.85 (t, J
= 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 160.30,
143.37, 142.96, 136.14, 132.71, 130.31, 129.58, 128.55,
128.18, 127.46, 127.34, 126.49, 125.16, 125.14, 123.15,
122.18, 121.49, 59.70, 38.37, 36.83, 21.03, 20.17, 13.93.
HRMS (ESI) ([M+H]+) calculated for C25H26NO2S:
404.1679, found: 404.1675.
Experimental Section
General Considerations
All 1H NMR and 13C NMR spectra were
measured on a Bruker Avance NMR spectrometer
(400 MHz or 100 MHz, respectively) in CDCl3 as
solvent and recorded in ppm relative to internal
standard tetramethylsilane. 1H NMR data are reported
as follows: δ, chemical shift; coupling constants (J
are given in Hertz, Hz) and integration. Abbreviations
to denote the multiplicity of a particular signal were s
(singlet), d (doublet), t (triplet), q (quartet), m
(multiplet), and br (broad singlet). High resolution
mass spectroscopic data of the products were
6-(1-Tosylhexan-2-yl)phenanthridine (4c): Colorless oil,
1
93.8 mg, 90% yield. H NMR (400 MHz, CDCl3) δ: 8.56
(d, J = 8.4 Hz, 1H), 8.44 (d, J = 8.0 Hz, 1H), 8.23 (d, J =
5
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10.1002/adsc.201801521
Advanced Synthesis & Catalysis
8.0 Hz, 1H), 7.857.82 (m, 2H), 7.71 (td, J = 7.6, 1.2 Hz,
1H), 7.64 (td, J = 7.5, 1.3 Hz, 1H), 7.57 (td, J = 7.5, 1.3
Hz, 1H), 7.21 (d, J = 8.4 Hz, 2H), 6.49 (d, J = 8.0 Hz, 2H),
4.704.64 (m, 1H), 4.394.32 (m, 1H), 3.53 (dd, J = 14.2,
2.6 Hz, 1H), 1.971.88 (m, 4H), 1.831.75 (m, 1H),
1.361.17 (m, 4H), 0.79 (t, J = 7.0 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 160.31, 143.36, 142.96, 136.15, 132.72,
130.30, 129.59, 128.55, 128.17, 127.46, 127.34, 126.48,
125.13, 123.16, 122.18, 121.49, 59.69, 37.02, 35.93, 29.06,
22.56, 21.03, 13.78. HRMS (ESI) ([M+H]+) calculated for
C26H28NO2S: 418.1835, found: 418.1831.
Hz, 1H), 7.62 (td, J = 7.6, 1.2 Hz, 1H), 7.587.52 (m, 2H),
7.35 (d, J = 8.0 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 6.98 (d,
J = 8.0 Hz, 2H), 6.61 (d, J = 8.0 Hz, 2H), 5.58 (dd, J = 9.6,
3.2 Hz, 1H), 5.255.19 (m, 1H), 3.72 (dd, J = 14.0, 3.2 Hz,
1H), 2.18 (s, 3H), 1.90 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 157.36, 143.49, 142.54, 137.66, 136.84, 136.43,
132.93, 130.19, 129.85, 129.47, 128.75, 128.06, 127.73,
127.64, 127.34, 126.66, 125.35, 124.64, 123.33, 122.14,
121.53, 61.15, 43.55, 20.99, 20.83. HRMS (ESI) ([M+H]+)
calculated for C29H25NO2S: 452.1679, found: 452.1675.
6-(1-(m-Tolyl)-2-tosylethyl)phenanthridine (4h): White
solid, 107.2 mg, 95% yield. 1H NMR (400 MHz, CDCl3) δ:
8.53 (d, J = 8.4 Hz, 1H), 8.44 (d, J = 7.6 Hz, 1H), 8.25 (d,
J = 8.0 Hz, 1H), 7.88 (dd, J = 8.2, 1.0 Hz, 1H), 7.75 (td, J
= 7.6, 1.2 Hz, 1H), 7.687.57 (m, 3H), 7.35 (d, J = 8.4 Hz,
2H), 7.17 (br, 2H), 7.107.06 (m, 1H), 6.94 (d, J = 7.2 Hz,
1H), 6.62 (d, J = 8.0 Hz, 2H), 5.56 (dd, J = 9.4, 3.0 Hz,
1H), 5.265.21 (m, 1H), 3.71 (dd, J = 14.2, 3.0 Hz, 1H),
2.22 (s, 3H), 1.93 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
157.26, 143.54, 142.64, 140.65, 138.58, 136.47, 133.02,
130.28, 130.02, 128.81, 128.76, 128.58, 128.13, 128.06,
127.74, 127.46, 126.74, 125.51, 125.03, 124.83, 123.45,
122.21, 121.60, 61.17, 44.04, 21.34, 21.09. HRMS (ESI)
([M+H]+) calculated for C29H25NO2S: 452.1679, found:
452.1675.
6-(1-Tosyloctan-2-yl)phenanthridine (4d): Colorless oil,
1
102.4 mg, 92% yield. H NMR (400 MHz, CDCl3) δ: 8.56
(d, J = 8.0 Hz, 1H), 8.44 (d, J = 8.0 Hz, 1H), 8.23 (d, J =
8.0 Hz, 1H), 7.857.81 (m, 2H), 7.70 (td, J = 7.6, 0.8 Hz,
1H), 7.64 (td, J = 7.5, 1.3 Hz, 1H), 7.57 (td, J = 7.5, 1.2
Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 6.49 (d, J = 8.0 Hz, 2H),
4.704.64 (m, 1H), 4.384.32 (m, 1H), 3.52 (dd, J = 14.2,
2.6 Hz, 1H), 1.941.88 (m, 4H), 1.831.75 (m, 1H),
1.381.33 (m, 1H), 1.241.14 (m, 7H), 0.80 (t, J = 6.8 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ: 160.34, 143.37,
142.99, 136.19, 132.75, 130.31, 129.63, 128.57, 128.19,
127.49, 127.36, 126.49, 125.17, 123.18, 122.19, 121.50,
59.70, 37.08, 36.22, 31.51, 29.14, 26.91, 22.47, 21.05,
13.94. HRMS (ESI) ([M+H]+) calculated for C28H32NO2S:
446.2148, found: 446.2144.
6-(1-(4-Methoxyphenyl)-2-tosylethyl)phenanthridine
1
(4i): White solid, 108.6 mg, 93% yield. H NMR (400
6-(1-Tosylnonan-2-yl)phenanthridine (4e): Colorless oil,
1
MHz, CDCl3) δ: 8.51 (d, J = 8.4 Hz, 1H), 8.42 (d, J = 7.6
Hz, 1H), 8.24 (d, J = 8.0 Hz, 1H), 7.87 (dd, J = 8.2, 1.0 Hz,
1H), 7.73 (td, J = 7.6, 0.8 Hz, 1H), 7.667.55 (m, 3H),
7.35 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 6.72 (d,
J = 8.8 Hz, 2H), 6.63 (d, J = 8.0 Hz, 2H), 5.57 (dd, J = 9.2,
3.2 Hz, 1H), 5.215.15 (m, 1H), 3.72 (dd, J = 14.0, 3.2 Hz,
1H), 3.66 (s, 3H), 1.93 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 158.67, 157.56, 143.52, 142.62, 136.51, 133.01,
132.74, 130.25, 129.92, 128.98, 128.81, 128.13, 127.69,
127.40, 126.71, 125.43, 124.67, 123.39, 122.22, 121.58,
114.21, 61.27, 55.09, 43.16, 21.06. HRMS (ESI) ([M+H]+)
calculated for C29H25NO3S: 468.1628, found: 468.1624.
102.2 mg, 89% yield. H NMR (400 MHz, CDCl3) δ: 8.55
(d, J = 8.0 Hz, 1H), 8.43 (dd, J = 8.2, 1.0 Hz, 1H), 8.23 (d,
J = 8.4 Hz, 1H), 7.837.79 (m, 2H), 7.69 (td, J = 7.7, 1.0
Hz, 1H), 7.63 (td, J = 7.6, 1.2 Hz, 1H), 7.55 (td, J = 7.5,
1.3 Hz, 1H), 7.21 (d, J = 8.4 Hz, 2H), 6.49 (d, J = 8.0 Hz,
2H), 4.704.64 (m, 1H), 4.384.32 (m, 1H), 3.53 (dd, J =
7.1, 2.6 Hz, 1H), 1.941.87 (m, 4H), 1.821.77 (m, 1H),
1.361.32 (m, 1H), 1.231.16 (m, 9H), 0.81 (t, J = 7.0 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ: 160.35, 143.36,
143.00, 136.24, 132.76, 130.30, 129.62, 128.57, 128.17,
127.49, 127.34, 126.48, 125.16, 123.19, 122.19, 121.50,
59.71, 37.08, 36.19, 31.65, 29.42, 28.94, 26.93, 22.50,
21.03, 13.96. HRMS (ESI) ([M+H]+) calculated for
C29H34NO2S: 460.2305, found: 460.2302.
6-(1-(4-Fluorophenyl)-2-tosylethyl)phenanthridine (4j):
1
White solid, 100.1 mg, 88% yield. H NMR (400 MHz,
CDCl3) δ: 8.53 (d, J = 8.4 Hz, 1H), 8.44 (d, J = 7.6 Hz,
1H), 8.22 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H),
7.76 (t, J = 7.6 Hz, 1H), 7.687.57 (m, 3H), 7.397.35 (m,
4H), 6.906.86 (m, 2H), 6.66 (d, J = 8.0 Hz, 2H), 5.61 (dd,
J = 9.2, 3.6 Hz, 1H), 5.175.11 (m, 1H), 3.74 (dd, J = 14.4,
3.6 Hz, 1H), 1.95 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
161.89 (d, J = 244.9 Hz), 157.26, 143.72, 142.60, 136.38
(d, J = 3.3 Hz), 133.09, 130.42, 129.94, 129.60 (d, J = 8.0
Hz), 128.91, 128.27, 127.70, 127.51, 126.91, 125.27,
124.00 (d, J = 113.7 Hz), 122.35, 121.64, 115.73 (d, J =
21.3 Hz), 61.22, 43.12, 21.11. HRMS (ESI) ([M+H]+)
calculated for C28H22FNO2S: 456.1428, found: 456.1425.
6-(1-Phenyl-2-tosylethyl)phenanthridine (4f): White
solid, 101.6 mg, 93% yield. 1H NMR (400 MHz, CDCl3) δ:
8.52 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 8.0 Hz, 1H), 8.25 (d,
J = 8.4 Hz, 1H), 7.88 (dd, J = 8.2, 1.0 Hz, 1H), 7.75 (td, J
= 7.7, 1.0 Hz, 1H), 7.677.56 (m, 3H), 7.407.35 (m, 4H),
7.227.18 (m, 2H), 7.13 (t, J = 7.2 Hz, 1H), 6.63 (d, J =
8.0 Hz, 2H), 5.61 (dd, J = 9.6, 3.2 Hz, 1H), 5.275.21 (m,
1H), 3.72 (dd, J = 14.4, 3.2 Hz, 1H), 1.93 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 157.29, 143.60, 142.65,
140.75, 136.51, 133.07, 130.32, 130.00, 128.89, 128.86,
128.18, 127.98, 127.76, 127.46, 127.28, 126.80, 125.46,
124.80, 123.46, 122.25, 121.61, 61.20, 44.01, 21.09.
HRMS (ESI) ([M+H]+) calculated for C28H24NO2S:
438.1522, found: 438.1517.
6-(1-(4-Bromophenyl)-2-tosylethyl)phenanthridine
1
(4k): White solid, 108.2 mg, 84% yield. H NMR (400
MHz, CDCl3) δ: 8.56 (d, J = 8.4 Hz, 1H), 8.46 (d, J = 7.6
Hz, 1H), 8.20 (d, J = 8.0 Hz, 1H), 7.90 (dd, J = 8.0, 1.2 Hz,
1H), 7.79 (td, J = 7.6, 0.8 Hz, 1H), 7.707.59 (m, 3H),
7.36 (d, J = 8.4 Hz, 2H), 7.327.26 (m, 4H), 6.70 (d, J =
8.0 Hz, 2H), 5.58 (dd, J = 8.8, 4.0 Hz, 1H), 5.125.06 (m,
6-(1-(p-Tolyl)-2-tosylethyl)phenanthridine (4g): White
solid, 106.0 mg, 94% yield. 1H NMR (400 MHz, CDCl3) δ:
8.46 (d, J = 8.0 Hz, 1H), 8.38 (d, J = 7.6 Hz, 1H), 8.23 (d,
J = 8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.69 (t, J = 7.2
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801521
Advanced Synthesis & Catalysis
1H), 3.77 (dd, J = 14.0, 4.0 Hz, 1H), 2.00 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 157.02, 143.82, 142.63,
139.57, 136.42, 133.13, 131.97, 130.50, 129.99, 129.77,
128.97, 128.34, 127.72, 127.58, 127.00, 125.25, 124.55,
123.49, 122.41, 121.69, 121.40, 60.99, 43.38, 21.17.
HRMS (ESI) ([M+H]+) calculated for C28H22BrNO2S:
516.0627, found: 516.0623.
8.0 Hz, 2H), 5.58 (dd, J = 9.4, 3.2 Hz, 1H), 5.265.20 (m,
1H), 3.77 (dd, J = 14.4, 3.2 Hz, 1H), 1.99 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 157.36, 143.83, 143.22,
140.09, 136.55, 135.25, 130.11, 129.47, 129.05, 129.02,
127.81, 127.75, 127.54, 127.44, 126.16 (q, J = 3.1 Hz),
123.92, 123.79 (q, J = 270.7 Hz)，123.47, 122.79 (q, J =
4.2 Hz), 122.45, 122.00, 60.94, 44.10, 21.09. HRMS (ESI)
([M+H]+) calculated for C29H22F3NO2S: 506.1396, found:
506.1398.
8-Chloro-6-(1-tosylheptan-2-yl)phenanthridine
(4l):
1
Colorless oil, 107.0 mg, 92% yield. H NMR (400 MHz,
CDCl3) δ: 8.49 (d, J = 8.8 Hz, 1H), 8.39 (d, J = 8.0 Hz,
1H), 8.15 (d, J = 2.0 Hz, 1H), 7.84 (dd, J = 8.0, 0.8 Hz,
1H), 7.77 (dd, J = 8.8, 2.0 Hz, 1H), 7.66 (td, J = 7.6, 1.2
Hz, 1H), 7.59 (td, J = 7.5, 1.0 Hz, 1H), 7.27 (d, J = 8.0 Hz,
2H), 6.59 (d, J = 8.0 Hz, 2H), 4.674.61 (m, 1H),
4.244.18 (m, 1H), 3.53 (dd, J = 7.2, 2.4 Hz, 1H),
1.931.87 (m, 4H), 1.821.74 (m, 1H), 1.351.32 (m, 1H),
1.21 (br, 5H), 0.80 (t, J = 6.6 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 159.43, 143.56, 142.95, 136.26, 133.46,
131.16, 130.86, 129.79, 128.75, 128.58, 127.58, 126.99,
126.06, 124.52, 124.03, 122.61, 121.43, 59.61, 37.19,
36.09, 31.59, 26.50, 22.30, 21.09, 13.86. HRMS (ESI)
([M+H]+) calculated for C27H29ClNO2S: 466.1602, found:
466.1599.
Methyl
6-(1-phenyl-2-tosylethyl)phenanthridine-8-
1
carboxylate (4p): White solid, 99.0 mg, 80% yield. H
NMR (400 MHz, CDCl3) δ: 9.00 (d, J = 1.2 Hz, 1H), 8.56
(d, J = 8.4 Hz, 1H), 8.45 (d, J = 8.0 Hz, 1H), 8.35 (dd, J =
8.6, 1.4 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.73 (td, J = 7.6,
1.2 Hz, 1H), 7.63 (td, J = 7.6, 1.2 Hz, 1H), 7.447.38 (m,
4H), 7.247.21 (m, 2H), 7.15 (t, J = 7.2 Hz, 1H), 6.68 (d, J
= 8.0 Hz, 2H), 5.67 (dd, J = 9.2, 3.2 Hz, 1H), 5.265.20
(m, 1H), 4.04 (s, 3H), 3.76 (dd, J = 14.4, 3.2 Hz, 1H), 1.97
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 166.20, 157.90,
143.70, 143.41, 140.41, 136.52, 136.03, 130.15, 130.12,
129.37, 128.99, 128.95, 128.75, 127.92, 127.80, 127.69,
127.43, 127.20, 124.18, 122.76, 122.62, 122.22, 60.98,
52.52, 44.01, 21.12. HRMS (ESI) ([M+H]+) calculated for
C30H25NO4S: 496.1577, found: 496.1579.
6-(1-Tosylheptan-2-yl)-8-(trifluoromethyl)phenanthri-
1
dine (4m): White solid, 112.3 mg, 90% yield. H NMR
2-Methyl-6-(1-tosylheptan-2-yl)phenanthridine
(4q):
1
(400 MHz, CDCl3) δ: 8.69 (d, J = 8.4 Hz, 1H), 8.498.45
(m, 2H), 8.02 (dd, J = 8.6, 1.4 Hz, 1H), 7.92 (dd, J = 8.0,
0.8 Hz, 1H), 7.74 (td, J = 7.6, 1.5 Hz, 1H), 7.65 (td, J =
7.6, 1.5 Hz, 1H), 7.297.26 (m, 2H), 6.61 (d, J = 8.0 Hz,
2H), 4.724.66 (m, 1H), 4.314.25 (m, 1H), 3.55 (dd, J =
14.4, 2.8 Hz, 1H), 1.961.87 (m, 4H), 1.841.77 (m, 1H),
1.341.14 (m, 6H), 0.79 (t, J = 7.0 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 160.49, 143.71, 143.65, 136.16, 134.97,
129.91, 129.53, 129.12 (q, J = 32.7 Hz), 128.82, 127.60,
127.21, 126.14 (q, J = 3.2 Hz), 124.43, 123.79 (q, J =
270.7 Hz), 123.44, 122.60 (q, J = 3.6 Hz), 122.28, 121.94,
59.65, 37.12, 36.25, 31.51, 26.49, 22.29, 21.11, 13.81.
HRMS (ESI) ([M+H]+) calculated for C28H29F3NO2S:
500.1866, found: 500.1862.
Colorless oil, 105.7 mg, 95% yield. H NMR (400 MHz,
CDCl3) δ: 8.54 (d, J = 8.4 Hz, 1H), 8.20 (d, J = 7.6 Hz,
2H), 7.80 (td, J = 7.6, 0.8 Hz, 1H), 7.717.66 (m, 2H),
7.45 (dd, J = 8.4, 1.6 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H),
6.50 (d, J = 8.4 Hz, 2H), 4.674.61 (m, 1H), 4.364.29 (m,
1H), 3.52 (dd, J = 14.4, 2.8 Hz, 1H), 2.59 (s, 3H),
1.941.86 (m, 4H), 1.821.75 (m, 1H), 1.371.34 (m, 1H),
1.20 (br, 5H), 0.79 (t, J = 6.8 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 159.24, 143.20, 141.32, 136.24, 132.50,
130.06, 129.84, 129.40, 128.58, 127.46, 127.18, 125.23,
125.10, 123.03, 122.15, 121.09, 59.75, 36.97, 36.12, 31.64,
26.61, 22.34, 21.86, 21.00, 13.89. HRMS (ESI) ([M+H]+)
calculated for C28H32NO2S: 446.2148, found: 446.2149.
2-Fluoro-6-(1-tosylheptan-2-yl)phenanthridine
(4r):
1
8-Chloro-6-(1-phenyl-2-tosylethyl)phenanthridine (4n):
Colorless oil, 105.6 mg, 94% yield. H NMR (400 MHz,
CDCl3) δ: 8.43 (d, J = 8.0 Hz, 1H), 8.25 (d, J = 8.0 Hz,
1H), 8.04 (dd, J = 10.2, 2.6 Hz, 1H), 7.867.79 (m, 2H),
7.74 (td, J = 7.7, 1.0 Hz, 1H), 7.37 (td, J = 8.4, 2.8 Hz,
1H), 7.21 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H),
4.664.60 (m, 1H), 4.374.31 (m, 1H), 3.52 (dd, J = 7.1,
2.6 Hz, 1H), 1.94 (s, 3H), 1.931.85 (m, 1H), 1.821.74
(m, 1H) 1.371.34 (m, 1H), 1.20 (br, 5H), 0.79 (t, J = 7.0
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 161.00 (d, J =
244.9 Hz), 159.64 (d, J = 2.7 Hz), 143.33, 139.81, 136.29,
132.19 (d, J = 4.2 Hz), 131.80 (d, J = 9.2 Hz), 130.41,
128.60, 128.05, 127.50, 125.26, 125.17, 124.48 (d, J = 8.8
Hz), 122.39, 117.00 (d, J = 24.2 Hz), 106.40 (d, J = 2.3
Hz), 59.66, 37.01, 36.11, 31.60, 26.58, 22.32, 21.05, 13.87.
HRMS (ESI) ([M+H]+) calculated for C27H29FNO2S:
450.1898, found: 450.1894.
1
White solid, 107.2 mg, 91% yield. H NMR (400 MHz,
CDCl3) δ: 8.43 (d, J = 8.8 Hz, 1H), 8.36 (d, J = 7.6 Hz,
1H), 8.19 (d, J = 2.0 Hz, 1H), 7.89 (dd, J = 8.0, 1.2 Hz,
1H), 7.697.65 (m, 2H), 7.59 (td, J = 7.6, 1.2 Hz, 1H),
7.407.37 (m, 4H), 7.257.20 (m, 2H), 7.16 (t, J = 7.4 Hz,
1H), 6.70 (d, J = 8.0 Hz, 2H), 5.50 (dd, J = 9.4, 3.0 Hz,
1H), 5.235.17 (m, 1H), 3.72 (dd, J = 14.0, 3.2 Hz, 1H),
1.97 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 156.35,
143.77, 142.60, 140.28, 136.59, 133.52, 131.50, 130.96,
130.15, 129.09, 129.01, 128.60, 127.93, 127.81, 127.53,
127.31, 125.74, 124.88, 124.10, 122.89, 121.57, 61.15,
44.09, 21.17. HRMS (ESI) ([M+H]+) calculated for
C28H22ClNO2S: 472.1133, found: 472.1134.
6-(1-Phenyl-2-tosylethyl)-8-(trifluoromethyl)phenan-
1
thridine (4o): White solid, 108.6 mg, 86% yield. H NMR
(400 MHz, CDCl3) δ: 8.57 (d, J = 8.4 Hz, 1H), 8.52 (s,
1H), 8.39 (d, J = 8.0 Hz, 1H), 7.94 (dd, J = 8.2, 0.6 Hz,
1H), 7.89 (d, J = 8.8 Hz, 1H), 7.72 (td, J = 7.6, 0.8 Hz,
1H), 7.60 (t, J = 7.6 Hz, 1H), 7.437.38 (m, 4H),
7.247.19 (m, 2H), 7.14 (t, J = 7.2 Hz, 1H), 6.73 (d, J =
2-Chloro-6-(1-tosylheptan-2-yl)phenanthridine
(4s):
1
Colorless oil, 105.8 mg, 91% yield. H NMR (400 MHz,
CDCl3) δ: 8.47 (d, J = 8.0 Hz, 1H), 8.39 (d, J = 2.4 Hz,
1H), 8.25 (d, J = 8.4 Hz, 1H), 7.85 (td, J = 7.6, 1.2 Hz,
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801521
Advanced Synthesis & Catalysis
1H), 7.767.73 (m, 2H), 7.56 (dd, J = 8.6, 2.2 Hz, 1H),
7.19 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0 Hz, 2H),
4.654.59 (m, 1H), 4.384.31 (m, 1H), 3.52 (dd, J = 14.2,
2.6 Hz, 1H), 1.94 (s, 3H), 1.911.86 (m, 1H), 1.821.74
(m, 1H), 1.371.33 (m, 1H), 1.20 (br, 5H), 0.79 (t, J = 7.0
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 160.75, 143.33,
141.33, 136.26, 132.33, 131.72, 131.08, 130.65, 128.62,
128.09, 127.45, 125.30, 125.25, 124.26, 122.23, 121.14,
59.63, 37.12, 36.07, 31.58, 26.56, 22.31, 21.02, 13.86.
HRMS (ESI) ([M+H]+) calculated for C27H29ClNO2S:
466.1602, found: 466.1601.
7.237.20 (m, 2H), 7.15 (t, J = 7.2 Hz, 1H), 6.81 (d, J =
8.8 Hz, 2H), 5.61 (dd, J = 9.6, 3.2 Hz, 1H), 5.265.20 (m,
1H), 3.78 (dd, J = 14.4, 3.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ: 157.06, 142.50, 140.34, 139.36, 138.11, 133.14,
130.51, 129.70, 129.15, 128.99, 128.51, 128.49, 127.99,
127.56, 127.46, 127.16, 125.38, 124.73, 123.44, 122.48,
121.83, 61.31, 44.12. HRMS (ESI) ([M+H]+) calculated
for C26H27ClNO2S: 458.0976, found: 458.0971.
1,3-Dimethyl-3-(tosylmethyl)indolin-2-one
(5a):[5l]
1
White solid, 78.2 mg, 95% yield. H NMR (400 MHz,
CDCl3) δ: 7.36 (d, J = 8.0 Hz, 2H), 7.27 (td, J = 7.6, 1.2
Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.06 (d, J = 7.6 Hz, 1H),
6.90 (td, J = 7.6, 0.8 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H),
3.85 (d, J = 14.8 Hz, 1H), 3.67 (d, J = 14.8 Hz, 1H), 3.15
(s, 3H), 2.38 (s, 3H), 1.38 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 177.55, 144.20, 143.18, 137.00, 129.54, 129.38,
128.45, 127.73, 124.04, 122.34, 108.25, 61.83, 45.54,
26.40, 25.37, 21.43.
2-Methyl-6-(1-phenyl-2-tosylethyl)phenanthridine (4t):
1
White solid, 104.9 mg, 93% yield. H NMR (400 MHz,
CDCl3) δ: 8.49 (d, J = 8.0 Hz, 1H), 8.228.20 (m, 2H),
7.75 (d, J = 8.4 Hz, 1H), 7.71 (t, J = 7.6 Hz, 1H), 7.57 (t, J
= 7.4 Hz, 1H), 7.46 (dd, J = 8.2, 1.4 Hz, 1H), 7.397.33
(m, 4H), 7.217.17 (m, 2H), 7.12 (t, J = 7.2 Hz, 1H), 6.63
(d, J = 8.0 Hz, 2H), 5.59 (dd, J = 9.6, 3.2 Hz, 1H),
5.245.19 (m, 1H), 3.72 (dd, J = 14.0, 3.2 Hz, 1H), 2.58 (s,
3H), 1.93 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 156.18,
143.41, 140.92, 140.83, 136.56, 136.47, 132.76, 130.04,
129.79, 129.73, 128.82, 127.94, 127.68, 127.25, 127.19,
125.33, 124.81, 123.26, 122.18, 121.18, 61.22, 43.89,
21.85, 21.02. HRMS (ESI) ([M+H]+) calculated for
C29H25NO2S: 452.1679, found: 452.1674.
3-(((4-Chlorophenyl)sulfonyl)methyl)-1,3-dimethyl-
indolin-2-one (5b):[5l] White solid, 80.3 mg, 92% yield. 1H
NMR (400 MHz, CDCl3) δ: 7.387.36 (m, 2H), 7.337.27
(m, 3H), 6.98 (dd, J = 7.2, 0.4 Hz, 1H), 6.916.84 (m, 2H),
3.91 (d, J = 14.8 Hz, 1H), 3.70 (d, J = 14.8 Hz, 1H), 3.17
(s, 3H), 1.38 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.37, 143.23, 140.02, 138.19, 129.23, 129.05, 128.67,
123.87, 122.45, 108.40, 61.87, 45.47, 26.47, 25.46.
2-Chloro-6-(1-phenyl-2-tosylethyl)phenanthridine (4u):
1
White solid, 104.8 mg, 89% yield. H NMR (400 MHz,
1,3-Dimethyl-3-((phenylsulfonyl)methyl)indolin-2-one
1
(5c):[5l] White solid, 72.5 mg, 92% yield. H NMR (400
CDCl3) δ: 8.338.31 (m, 2H), 8.24 (d, J = 8.4 Hz, 1H),
7.77 (d, J = 8.4 Hz, 1H), 7.68 (t, J = 7.4 Hz, 1H),
7.617.54 (m, 2H), 7.39 (d, J = 7.6 Hz, 2H), 7.34 (d, J =
8.0 Hz, 2H), 7.247.19 (m, 2H), 7.14 (t, J = 7.2 Hz, 1H),
6.65 (d, J = 8.0 Hz, 2H), 5.59 (dd, J = 9.6, 2.8 Hz, 1H),
5.215.15 (m, 1H), 3.71 (dd, J = 14.4, 2.8 Hz, 1H), 1.96 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 157.67, 143.55,
140.93, 140.41, 136.53, 132.62, 131.95, 131.39, 130.62,
128.93, 128.88, 128.60, 128.14, 127.89, 127.68, 127.37,
125.47, 124.86, 124.49, 122.25, 121.23, 61.10, 43.98,
21.06. HRMS (ESI) ([M+H]+) calculated for
C28H22ClNO2S: 472.1133, found: 472.1131.
MHz, CDCl3) δ: 7.557.48 (m, 3H), 7.397.35 (m, 2H),
7.28 (td, J = 7.8, 1.1 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H),
6.916.84 (m, 2H), 3.89 (d, J = 14.8 Hz, 1H), 3.70 (d, J =
14.4 Hz, 1H), 3.17 (s, 3H), 1.39 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 177.55, 143.21, 139.87, 133.29, 129.40,
128.84, 128.57, 127.70, 123.99, 122.48, 108.34, 61.77,
45.55, 26.49, 25.39.
3-(((4-(tert-Butyl)phenyl)sulfonyl)methyl)-1,3-dimethy-
lindolin-2-one (5d):[5l] Colorless oil, 82.6 mg, 89% yield.
1H NMR (400 MHz, CDCl3) δ: 7.417.35 (m, 4H),
7.287.23 (m, 1H), 7.02 (d, J = 7.2 Hz, 1H), 6.876.83 (m,
2H), 3.86 (d, J = 14.8 Hz, 1H), 3.69 (d, J = 14.8 Hz, 1H),
3.16 (s, 3H), 1.38 (s, 3H), 1.31 (s, 9H); 13C NMR (100
MHz, CDCl3) δ: 177.55, 157.05, 143.17, 136.85, 129.48,
128.43, 127.49, 125.79, 123.95, 122.35, 108.24, 61.79,
45.51, 35.04, 30.94, 26.43, 25.35.
6-(1-((4-Chlorophenyl)sulfonyl)heptan-2-yl)phenan-
1
thridine (4v): Colorless oil, 57.5 mg, 51% yield. H NMR
(400 MHz, CDCl3) δ: 8.58 (d, J = 8.4 Hz, 1H), 8.46 (d, J =
8.0 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 7.867.79 (m, 2H),
7.737.64 (m, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.19 (d, J =
8.4 Hz, 2H), 6.60 (d, J = 8.4 Hz, 2H), 4.754.69 (m, 1H),
4.374.32 (m, 1H), 3.55 (dd, J = 14.2, 2.2 Hz, 1H),
1.971.88 (m, 1H), 1.811.79 (m, 1H), 1.391.37 (m, 1H),
1.22 (br, 5H), 0.80 (t, J = 6.8 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ: 160.01, 142.84, 139.07, 137.65, 132.77,
130.48, 129.34, 128.81, 128.48, 128.10, 127.43, 126.85,
125.13, 124.97, 123.13, 122.47, 121.74, 59.82, 37.17,
36.21, 31.62, 26.62, 22.33, 13.86. HRMS (ESI) ([M+H]+)
calculated for C26H27ClNO2S: 452.1446, found: 452.1442.
3-(((4-Methoxyphenyl)sulfonyl)methyl)-1,3-dimethyl-
1
indolin-2-one (5e):[5l] White solid, 82.8 mg, 96% yield. H
NMR (400 MHz, CDCl3) δ: 7.38 (d, J = 8.8 Hz, 2H),
7.297.25 (m, 1H), 7.05 (d, J = 7.6 Hz, 1H), 6.91 (t, J =
7.6 Hz, 1H), 6.856.79 (m, 3H), 3.883.83 (m, 4H), 3.67
(d, J = 14.4 Hz, 1H), 3.15 (s, 3H), 1.37 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 177.53, 163.34, 143.11, 131.35,
129.87, 129.48, 128.42, 123.98, 122.34, 113.93, 108.23,
61.92, 55.54, 45.51, 26.39, 25.41.
6-(2-((4-Chlorophenyl)sulfonyl)-1-phenylethyl)phen-
anthridine (4w): White solid, 44.5 mg, 39% yield. 1H
NMR (400 MHz, CDCl3) δ: 8.56 (d, J = 8.0 Hz, 1H), 8.47
(dd, J = 8.2, 1.0 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 7.85 (d,
J = 8.0 Hz, 1H), 7.78 (td, J = 7.6, 0.8 Hz, 1H), 7.69 (td, J =
7.4, 1.2 Hz, 1H), 7.647.61 (m, 2H), 7.417.36 (m, 4H),
3-(((4-Fluorophenyl)sulfonyl)methyl)-1,3-dimethyl-
1
indolin-2-one (5f):[5l] White solid, 77.4 mg, 93% yield. H
NMR (400 MHz, CDCl3) δ: 7.487.45 (m, 2H), 7.317.27
(m, 1H), 7.056.98 (m, 3H), 6.926.85 (m, 2H), 3.90 (d, J
= 14.4 Hz, 1H), 3.70 (d, J = 14.4 Hz, 1H), 3.18 (s, 3H),
1.38 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 177.43,
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801521
Advanced Synthesis & Catalysis
165.43 (d, J = 254.6 Hz), 143.23, 135.89 (d, J = 3.0 Hz),
130.61 (d, J = 9.7 Hz), 129.27, 128.64, 123.84, 122.43,
116.03, 108.39, 61.93, 45.50, 26.46, 25.41.
1H), 7.76 (d, J = 8.0 Hz, 1H), 7.64 (td, J = 7.6, 1.2 Hz,
1H), 7.617.56 (m, 2H), 7.21 (td, J = 7.7, 1.1 Hz, 1H),
7.02 (d, J = 7.6 Hz, 1H), 6.796.73 (m, 2H), 3.98 (d, J =
14.8 Hz, 1H), 3.75 (d, J = 14.4 Hz, 1H), 2.97 (s, 3H), 1.38
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 177.51, 143.18,
136.31, 135.10, 131.78, 129.93, 129.50, 129.20, 129.12,
128.64, 127.79, 127.38, 124.12, 122.53, 122.33, 108.30,
61.59, 45.57, 26.31, 25.66. HRMS (ESI) ([M+H]+)
calculated for C21H19NO3S: 366.1158, found: 366.1154.
1,3-Dimethyl-3-((o-tolylsulfonyl)methyl)indolin-2-one
1
(5g): White solid, 57.6 mg, 70% yield. H NMR (400
MHz, CDCl3) δ: 7.40 (td, J = 7.4, 1.2 Hz, 1H), 7.327.24
(m, 3H), 7.13 (d, J = 7.2 Hz, 1H), 7.08 (t, J = 7.8 Hz, 1H),
6.92 (td, J = 7.6, 0.8 Hz, 1H), 6.80 (d, J = 7.6 Hz, 1H),
3.90 (d, J = 14.8 Hz, 1H), 3.68 (d, J = 14.4 Hz, 1H), 3.09
(s, 3H), 2.66 (s, 3H), 1.39 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 177.46, 143.06, 138.08, 137.63, 133.40, 132.33,
129.78, 129.45, 128.55, 126.12, 124.14, 122.41, 108.29,
60.54, 45.47, 26.40, 25.62, 20.26. HRMS (ESI) ([M+H]+)
calculated for C18H19NO3S: 330.1158, found: 330.1155.
1,3-Dimethyl-3-((thiophen-2-ylsulfonyl)methyl)indolin-
1
2-one (5m): White solid, 56.2 mg, 70% yield. H NMR
(400 MHz, CDCl3) δ: 7.59 (dd, J = 5.2, 1.2 Hz, 1H),
7.317.27 (m, 1H), 7.15 (dd, J = 4.0, 1.2 Hz, 1H), 7.10 (d,
J = 7.2 Hz, 1H), 6.956.92 (m, 2H), 6.87 (d, J = 8.0 Hz,
1H), 3.97 (d, J = 14.4 Hz, 1H), 3.80 (d, J = 14.4 Hz, 1H),
3.21 (s, 3H), 1.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.44, 143.25, 141.11, 133.99, 133.91, 129.42, 128.62,
127.49, 123.86, 122.51, 108.40, 63.27, 45.69, 26.53, 25.26.
HRMS (ESI) ([M+H]+) calculated for C15H15NO3S2:
322.0566, found: 322.0563.
3-(((3-Chlorophenyl)sulfonyl)methyl)-1,3-dimethyl-
indolin-2-one (5h): White solid, 84.6 mg, 97% yield. H
1
NMR (400 MHz, CDCl3) δ: 7.507.47 (m, 1H), 7.43 (d, J
= 8.0 Hz, 1H), 7.367.27 (m, 3H), 6.93 (d, J = 7.2 Hz,
1H), 6.88 (d, J = 7.6 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 3.92
(d, J = 14.8 Hz, 1H), 3.20 (s, 3H), 1.38 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 177.32, 143.23, 141.43, 134.91,
133.45, 130.18, 128.86, 127.84, 125.78, 123.71, 122.32,
108.40, 61.91, 45.39, 26.48, 25.28. HRMS (ESI) ([M+H]+)
calculated for C17H16ClNO3S: 350.0612, found: 350.0610.
3-((Butylsulfonyl)methyl)-1,3-dimethylindolin-2-one
1
(5n):[5l] Colorless oil, 47.2 mg, 64% yield. H NMR (400
MHz, CDCl3) δ: 7.387.32 (m, 2H), 7.11 (td, J = 7.5, 0.6
Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 3.63 (d, J = 14.4 Hz,
1H), 3.53 (d, J = 14.8 Hz, 1H), 3.26 (s, 3H), 2.692.64 (m,
2H), 1.731.65 (m, 2H), 1.46 (s, 3H), 1.381.32 (m, 2H),
0.88 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.44, 143.25, 141.11, 133.99, 133.91, 129.42, 128.62,
127.49, 123.86, 122.51, 108.40, 63.27, 45.69, 26.53, 25.26.
4-(((1,3-Dimethyl-2-oxoindolin-3-yl)methyl)sulfonyl)-
benzonitrile (5i): White solid, 80.8 mg, 95% yield. H
1
NMR (400 MHz, CDCl3) δ: 7.55 (d, J = 8.4 Hz, 2H),
7.317.27 (m, 1H), 6.896.87 (m, 2H), 6.83 (t, J = 7.4 Hz,
1H), 3.95 (d, J = 14.8 Hz, 1H), 3.76 (d, J = 14.8 Hz, 1H),
3.22 (s, 3H), 1.39 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.19, 143.86, 143.34, 132.49, 128.98, 128.84, 128.32,
123.56, 122.40, 117.01, 116.84, 108.53, 61.79, 45.38,
26.52, 25.34. HRMS (ESI) ([M+H]+) calculated for
C18H16N2O3S: 341.0954, found: 341.0956.
1,3,5-Trimethyl-3-(tosylmethyl)indolin-2-one
(5o):[5l]
1
White solid, 81.5 mg, 95% yield. H NMR (400 MHz,
CDCl3) δ: 7.29 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.4 Hz,
2H), 7.03 (d, J = 7.6 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H),
6.64 (s, 1H), 3.87 (d, J = 14.8 Hz, 1H), 3.66 (d, J = 14.8
Hz, 1H), 3.17 (s, 3H), 2.38 (s, 3H), 2.12 (s, 3H), 1.34 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 177.50, 143.96,
140.96, 137.03, 131.75, 129.26, 128.72, 127.70, 124.69,
108.00, 61.87, 45.52, 26.49, 25.36, 21.41, 20.77.
1,3-Dimethyl-3-(((4-(trifluoromethyl)phenyl)sulfonyl)-
methyl) indolin-2-one (5j): White solid, 77.6 mg, 81%
1
yield. H NMR (400 MHz, CDCl3) δ: 7.627.56 (m, 4H),
7.27 (td, J = 7.8, 1.2 Hz, 1H), 6.90 (dd, J = 7.4, 0.6 Hz,
1H), 6.85 (d, J = 8.0 Hz, 1H), 6.81 (td, J = 7.6, 0.8 Hz,
1H), 3.95 (d, J = 14.8 Hz, 1H), 3.74 (d, J = 14.8 Hz, 1H),
3.18 (s, 3H), 1.38 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.28, 143.27 (d, J = 9.4 Hz), 134.85 (q, J = 32.9 Hz),
129.04, 128.78, 128.34, 125.89 (q, J = 3.6 Hz), 123.73,
123.03 (d, J = 271.5 Hz), 122.47, 108.45, 61.82, 45.44,
26.47, 25.41. HRMS (ESI) ([M+H]+) calculated for
C18H16F3NO3S: 384.0876, found: 384.0872.
5-Fluoro-1,3-dimethyl-3-(tosylmethyl)indolin-2-one
1
(5p):[5l] White solid, 81.6 mg, 94% yield. H NMR (400
MHz, CDCl3) δ: 7.38 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.0
Hz, 2H), 6.97 (td, J = 8.8, 2.5 Hz, 1H), 6.786.75 (m, 1H),
6.71 (dd, J = 8.0, 2.4 Hz, 1H), 3.85 (d, J = 14.4 Hz, 1H),
3.65 (d, J = 14.8 Hz, 1H), 3.18 (s, 3H), 2.40 (s, 3H), 1.37
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 177.26, 159.02 (d,
J = 239.4 Hz), 144.58, 139.21 (d, J = 1.4 Hz), 136.86,
131.10 (d, J = 8.3 Hz), 129.50, 127.63, 114.79 (d, J = 23.3
Hz), 112.19 (d, J = 25.0 Hz), 108.73 (d, J = 8.1 Hz), 61.63,
45.95 (d, J = 1.4 Hz), 26.62, 25.20, 21.43.
3-(((4-Chloro-3-(trifluoromethyl)phenyl)sulfonyl)-
methyl)-1,3-dimethylindolin-2-one (5k):[5l] White solid,
1
100.1 mg, 96% yield. H NMR (400 MHz, CDCl3) δ:
7.637.60 (m, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.307.26 (m,
1H), 6.876.81 (m, 3H), 3.99 (d, J = 14.8 Hz, 1H), 3.76 (d,
J = 15.2 Hz, 1H), 3.19 (s, 3H), 1.38 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 177.11, 143.30, 138.81, 138.12, 132.18,
132.01, 129.11 (d, J = 32.4 Hz), 129.11, 128.73, 127.29 (q,
J = 5.4 Hz), 123.60, 122.34, 121.68 (d, J = 272.4 Hz),
108.55, 61.97, 45.37, 26.46, 25.46.
5-Chloro-1,3-dimethyl-3-(tosylmethyl)indolin-2-one
1
(5q):[5l] White solid, 77.2 mg, 85% yield. H NMR (400
MHz, CDCl3) δ: 7.29 (d, J = 8.4 Hz, 2H), 7.20 (dd, J = 8.4,
2.0 Hz, 1H), 7.15 (d, J = 8.4 Hz, 2H), 6.78 (d, J = 8.4 Hz,
1H), 6.70 (d, J = 2.0 Hz, 1H), 3.88 (d, J = 14.8 Hz, 1H),
3.67 (d, J = 14.8 Hz, 1H), 3.22 (s, 3H), 2.41 (s, 3H), 1.35
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 177.12, 144.63,
141.94, 136.61, 130.85, 129.53, 128.37, 127.78, 127.42,
124.26, 109.22, 61.61, 45.62, 26.63, 25.14, 21.51.
1,3-Dimethyl-3-((naphthalen-2-ylsulfonyl)methyl)-
1
indolin-2-one (5l): White solid, 73.9 mg, 81% yield. H
NMR (400 MHz, CDCl3) δ: 7.877.85 (m, 2H), 7.82 (s,
5-Iodo-1,3-dimethyl-3-(tosylmethyl)indolin-2-one
9
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801521
Advanced Synthesis & Catalysis
1
(5r):[5l] White solid, 106.9 mg, 94% yield. H NMR (400
MHz, CDCl3) δ: 7.53 (d, J = 8.4 Hz, 1H), 7.26 (d, J = 8.4
Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.94 (s, 1H), 6.64 (d, J =
8.4 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 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 176.94, 144.69, 143.29, 137.24,
136.76, 132.55, 131.64, 129.74, 127.45, 110.39, 61.81,
45.44, 26.65, 25.21, 21.87.
W.-T. Wei, M.-B. Zhou, J.-H. Fan, W. Liu, R.-J.
Song, Y. Liu, M. Hu, P. Xie, J.-H. Li, Angew. Chem.
Int. Ed. 2013, 52, 3638; e) S. Zhu, A. Das, L. Bui, H.
Zhou, D. P. Curran, M. Rueping, J. Am. Chem. Soc.
2013, 135, 1823; f) J.-M. M. Grandjean, D. A.
Nicewicz, Angew. Chem. Int. Ed. 2013, 52, 3967; g)
T. Wu, X. Mu, G. Liu, Angew. Chem. Int. Ed. 2011
,
50, 12578; h) Y.-M. Li, M. Sun, H.-L. Wang, Q.-P.
Tian, S.-D. Yang, Angew. Chem. Int. Ed. 2013, 52,
3972; i) W. Wei, J.-W. Wen, D.-S. Yang, J. Du, J.-M.
You, H. Wang, Green Chem. 2014, 16, 2988; j) T.
Shen, Y.-Z. Yuan, S. Song, N. Jiao, Chem. Commun.
2014, 50, 4115.
5-Methoxy-1,3-dimethyl-3-(tosylmethyl)indolin-2-one
1
(5s):[5l] White solid, 62.8 mg, 70% yield. H NMR (400
MHz, CDCl3) δ: 7.31 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.4
Hz, 2H), 6.796.73 (m, 2H), 6.48 (d, J = 2.4 Hz, 1H), 3.86
(d, J = 14.8 Hz, 1H), 3.673.63 (m, 4H), 3.16 (s, 3H), 2.38
(s, 3H), 1.36 (s, 3H); 13C NMR (100 MHz, CDCl3) δ:
177.18, 155.70, 144.11, 136.97, 136.68, 130.49, 129.29,
127.68, 113.11, 110.83, 108.58, 61.79, 55.28, 45.91, 26.51,
25.29, 21.37.
5-(tert-Butyl)-1,3-dimethyl-3-(tosylmethyl)indolin-2-one
(5t): White solid, 93.4 mg, 97% yield. 1H NMR (400 MHz,
CDCl3) δ: 7.35 (d, J = 8.4 Hz, 2H), 7.30 (dd, J = 8.0, 2.0
Hz, 1H), 7.157.12 (m, 3H), 6.77 (d, J = 8.0 Hz, 1H), 3.86
(d, J = 14.8 Hz, 1H), 3.71 (d, J = 14.4 Hz, 1H), 3.14 (s,
3H), 2.36 (s, 3H), 1.40 (s, 3H), 1.23 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ: 177.71, 145.46, 144.09, 140.79,
137.14, 129.36, 129.13, 127.76, 125.15, 121.40, 107.65,
61.95, 45.82, 34.37, 31.38, 26.41, 25.43, 21.46. HRMS
(ESI) ([M+H]+) calculated for C22H27NO3S: 386.1784,
found: 386.1780.
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Acknowledgements
This work was financially supported by the National
Science Foundation of China (21772062, 21602072,
21572078), the National Science Foundation of Anhui
Education Department (KJ2016A643), and the
Scientific Research Project of Anhui Provincial
Education Department (KJ2015TD002).
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FULL PAPER
Hydrogen and Sulfonyl Radical Generation for the
Hydrogenation and Arylsulfonylation of Alkenes
Driven by Photochemical Activity of Hydrogen
Bond Donor–Acceptor Complexes
Adv. Synth. Catal. 2018, Volume, Page – Page
Yang Li,a Fang Ma,a Pinhua Li,a Tao Miao,*a and
Lei Wang*a,b
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