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CRITICAL REVIEW
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2. Green Chemistry
ARTICLE
This journal is © The Royal Society of Chemistry 2016 Green Chem., 2016, 00, 1-3 | 1
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a.
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P.
R. China; E-mail: leiwang@chnu.edu.cn,taomiaochem@163.com.
Tel.: +86-561-380-2069; fax: +86-561-309-0518
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China
† Footnotes relaƟng to the Ɵtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Visible-light-induced dual C–C bond formation via selective
C(sp3
)–H bond cleavage: an efficient access to alkylated
oxindoles from activated alkenes and simple ethers under metal-
free conditions
Dong Xia,a
Yang Li,a
Tao Miao*a
Pinhua Li,a
and Lei Wang*a,b
A vsible-light-induced oxidative difunctionalization of activated alkenes with simple ethers via selective C(sp3
)−H bond
cleavage and dual C−C bond formation was developed. The reaction provides a mild, efficient and atom economical access
to alkylated oxindoles at room temperature under metal-free conditions.
Introduction
Direct cleavage and functionalization of C–H bond has evolved to be
one of the most efficient and straightforward synthetic approach to
carbon-carbon and carbon-heteroatom bond formations,1
and it does
not require substrate prefunctionalization, and minimize the number
of synthetic steps. Oxidative cross-dehydrogenative-coupling (CDC)
of C(sp3
)−H adjacent to heteroatom, double bond, phenyl group or
cycloalkane is the ideal version of this process.2
Among C(sp3
)−H
functionalization via oxidative CDC, ethers including
tetrahydrofuran (THF) are found to be easy-to-handle, stable, and
commercially available chemical feedstocks, and are the most
widely used as solvents in both academia and industry. So direct
functionalization α-C(sp3
)−H of simple ethers remains more
attractive, and great progress has been achieved in the past few
years.3
However, the oxidative coupling between two reaction
partners involving a sequential C(sp3
)−H/C(sp2
)–H bond
functionalization of ethers has gained less attention.4
In 2013, the
difunctionalization of activated alkenes with ethers and arenes
through a Fe-catalyzed dual C−H bond cleavage was developed by
Li.4a
Similarly, Cheng established a facile route to 6-alkyl
phenanthridine via the sequential ether C(sp3
)–H and aryl C(sp2
)−H
bond functionalizations.4b
Undoubtedly, this dual C−H bond
cleavage along with the dual C−C bond formation is more useful for
the synthesis of structurally complex and diverse organic molecules,
yet they still face the utilization of transition-metal catalyst and high
reaction temperature, which extremely limits its application in
organic synthesis. Therefore, the development of more mild and
Scheme 1. Visible-light-induced direct synthesis of alkylated oxindoles.
efficient strategy for dual C−C bond formation by direct
functionalization of unactived C−H bond is highly desirable.
Visible-light photoredox catalysis has become a valuable platform
for the design and development of a variety of radical reactions
under remarkably mild reaction conditions.5
However, the directly
use of visible light in organic reactions suffers from high energy UV
light and inability of many organic molecules to absorb photons in
the visible region. Recently, there has been a renaissance of
photochemical reactions by application of photoredox catalysts, such
as Eosin Y and Ru(bpy)3Cl2, which can absorb visible light to
sensitize organic molecules through their visible light-driven single-
electron transfer (SET).6
Since the pioneering work from MacMillan
and co-workers employed the photoredox catalysts in organic
transformations,7
this field has already demonstrated remarkable
accomplishments. Of particular note is visible-light-induced C–H
bond functionalization, which has attracted a surge of interest from
academic and industrial chemists due to the atom/step economical
features as well as the overall sustainability. As a result, a
combination of visible-light catalysis and C(sp3
)–H
functionalization, which is benzylic or adjacent to a tertiary amine
has been developed.8
However, to the best of our knowledge, only
isolated examples of the oxidative functionalization of C(sp3
)–H
bonds adjacent to oxygen atoms (ethers) by visible-light photoredox
catalysis have been reported to date.9
On the other hand, the
oxidative difunctionalization of carbon-carbon double bonds in N-
arylacrylamides has been proved to be a powerful strategy in the
construction of functionalized oxindoles, which have been widely
found in the structure of natural products, pharmaceuticals and
biologically active molecules.10
Considerable efforts were directed
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3. ARTICLE Green Chemistry
2 | Green Chem., 2016, 00, 1-3 This journal is © The Royal Society of Chemistry 2016
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toward the development of efficient protocols for the synthesis of
these motifs with transition metal-catalyzed cyclizations as well as
radical initiated processes.11
Based on our exploration in photoredox
catalysis and inspired by reported results,12
we herein disclose a
visible-light-induced dual C−C bond formation for the synthesis of
alkylated oxindoles from alkenes and simple ethers via a selective
C(sp3
)–H bond cleavage at room temperature under metal-free
conditions (Scheme 1).
Results and discussion
Initially, Eosin Y was chosen as a photocatalyst for the model
reaction of N-methyl-N-phenylmethacrylamide (1a) with THF
(tetrahydrofuran, 2a) to optimize the reaction conditions, and the
results are shown in Table 1. Under a blue light emitting diode
(LED, 25 W) irradiation for 12 h at room temperature, the model
Table 1. Optimization of the reaction conditions.a
Entry Oxidant Solvent Yield (%)b
1 DTBP Neat 35
2 TBHP Neat 78
3 DCP Neat 42
4 CHP Neat 40
5 TBPB Neat 55
6 H2O2 Neat 11
7 O2 Neat 0
8 BQ Neat 0
9 K2S2O8 Neat 0
10 PhI(OAc)2 Neat 0
11 TBHP CH3CN/THF (1:1) 38
12 TBHP DMF/THF (1:1) 31
13 TBHP C2H5OH/THF (1:1) 28
14 TBHP DCE/THF (1:1) 34
15 TBHP Toluene/THF (1:1) 15
16 TBHP H2O/THF (1:1) 11
17 TBHP Neat 52c
18 TBHP Neat 62d
19 TBHP Neat 55e
20 TBHP Neat 0f
21 TBHP Neat 0g
22 / Neat 0
a
Reaction conditions: 1a (0.25 mmol), THF (2a, 3.0 mL), Eosin Y (3 mol%)
and oxidant (3.0 equiv) at room temperature for 12 h. b
Isolated yield based on
1a. c
2.0 equiv TBHP was used. d
In absence of 4 Å molecular sieves.
e
Ru(bpy)2Cl2 (3 mol%) was used. f
In absence of Eosin Y. g
In the darkness.
DTBP = di-tert-butyl peroxide; TBHP = tert-butyl hydroperoxide (70%
solution in water); DCP = dicumyl peroxide; CHP = cumene hydroperoxide;
BQ = 1,4-benzoquinone; TBPB = tert-butyl peroxybenzoate; H2O2 = 30%
aqueous solution.
reaction provided product 3a in 35% yield using di-tert-butyl
peroxide (DTBP) as an oxidant (Table 1, entry 1). To our
delight, the yield of 3a was enhanced to 78% when tert-butyl
hydroperoxide (TBHP, 70% aqueous solution) was used as an
oxidant (entry 2). Other oxidants including DCP, CHP, TBPB and
H2O2 gave the inferior results and led to the formation of 3a in 11–
55% yields (entries 3–6). However, O2, BQ, K2S2O8 and PhI(OAc)2
as oxidants exhibited no any efficiency to the model reaction (Table
1, entries 7–10). The influence of solvents was also investigated. The
reaction carried out in THF (as both substrate and solvent) without
additional solvent was the best of choice, and the mixed solvent of
3a, 78%
3n, 66%
N
Me
O
Me
N
Me
O
Me
Me
Me
3m+3m', (1.9:1), 71%
N
R2
O
H
Me
R1
Eosin Y (3 mol %)
TBHP (3.0 equiv)
+
25 W blue LED
4 A MS, rt, 12 h1 2a
OH
N
Me
O
Me
3
O
N
R2
O
Me
O
R1
3b, 75%
N
Me
O
Me
O
3c, 65%
N
Me
O
Me
O
Me
Me
3d, 70%
N
Me
O
Me
O
3e, 64%
N
Me
O
Me
O
Et
Et
3f, 67%
N
Me
O
Me
O
MeO
3g, 65%
N
Me
O
Me
O
OMe
3h, 68%
N
Me
O
Me
O
EtO
3i, 63%
N
Me
O
Me
O
F
3j, 64%
N
Me
O
Me
O
Cl
3k, 72%
N
Me
O
Me
O
Br
3l, 74%
N
Me
O
Me
O
I
O O
N
O
Me
O
3o, 61%
N
Me
O
Me
O
3p, 63%
N
Me
O
Me
O
Me
Me
Me
Me
3q, 64%
N
Me
O
Me
OCl
Cl
3r, 70%
N
Et
O
Me
O
3s, R2
= H, 0%
3t, R2
= Ac, 0%
N
R2
O
Me
O
3u, trace
N
Me
O
OMe
Scheme 2. Reaction of acrylamides with THF [Reaction conditions: 1 (0.25
mmol), THF (2a, 3.0 mL), Eosin Y (3 mol%), TBHP (3.0 equiv), blue LED
(25 W) irradiation at room temperature for 12 h; isolated yield of the product
based on 1].
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THF with CH3CN, DMF (N,N-dimethylformamide), ethanol, DCE
(1,2-dichloroethane), toluene or H2O in 1:1 volume ratio showed
poor performance to model reaction, providing product 3a in 11–
38% yields (Table 1, entries 11–16). Changing the amount of
oxidant TBHP from 3.0 equiv to 2.0 equiv brought a decreased
yield of 3a (52%, entry 17). Interestingly, the addition of 4 Å
molecular sieves was found to be advantageous to the reaction. The
reaction afforded the desired product in 62% yield when no 4 Å
molecular sieves was added (entry 18). Furthermore, when
Ru(bpy)3Cl2 was employed as photocatalyst in the reaction, the yield
of 3a was decreased from 78 to 55% (entry 2 vs 19). Finally, the
experiments also revealed that no reaction occurred in the absence of
photocatalyst, visible light or oxidant (Table 1, entries 20–22).
With the optimized conditions in hand, the scope of acrylamides
with substituents on the phenyl rings was investigated, as shown in
Scheme 2. A variety of acrylamides (1) reacted with THF (2a)
smoothly under the standard reaction conditions, affording the
desired oxindoles in moderate to good yields. Importantly, the
reactions tolerated a number of functional groups, such as methyl,
ethyl, methoxyl, and fluoro, chloro, bromo and iodo, which were
suitable for further functionalization. Moreover, the position of the
substituents on the aromatic rings has no significant influence on the
efficiency. To investigate the regioselectivity of this tandem
cyclization process, a reaction of THF with acrylamide bearing a
meta-substituent on the benzene ring was conducted, generating a
Scheme 3. Reaction of ethers with acrylamides [Reaction conditions: 1 (0.25
mmol), 2 (3.0 mL), Eosin Y (3 mol%), TBHP (3.0 equiv), blue LED (25 W)
irradiation at room temperature for 12 h; isolated yield of the product based
on 1].
mixture of two regioselective isomers 3m and 3m' in a ratio of 1.9:1
with 71% total yield. In addition, the tetrahydroquinoline derivative
of acrylamide also afforded the corresponding oxindole 3n in 66%
yield. On the other hand, multi-substituted arylacrylamides were also
well tolerated in this transformation, affording the alkylated
oxindoles (3o–q) with moderate yields (61–64%). N-Arylacrylamide
with an ethyl group on the nitrogen atom also reacted with THF
smoothly to give the desired product 3r in 70% yield. However, N-
H and Ac N-arylacrylamide failed to react with 2a under the present
reaction conditions (3s, 3t). Furthermore, β-methyl acrylamides was
also tested, but only trace amount of desired product was obtained
(3u).
Subsequently, other ethers were examined to extend the
application scope. As shown in Scheme 3, it was gratifying to find
that a variety of ethers including cyclic and linear ethers could
couple with diverse acrylamides to give the desired alkylated
oxindoles in good yields. The C–H bond at 2-position of 1,3-
dioxolane was found to be highly effective and preferential to react
with different kinds of acrylamides, affording the corresponding
products (3v–3ae) in higher yields (61–83%). Meanwhile, aniline
moieties of acrylamides attached the sensitive functional groups,
such as trifluoromethyl, cyano and ester groups were tolerated in the
reactions. For a N-arylacrylamide bearing an ethyl group on the N-
atom proceeded the reaction with 1,3-dioxolane smoothly to give the
anticipated product 3ae in 75% yield. Notably, tetrahydrothiophene
was a proper reaction partner, providing the oxindoles 3af in 61%
yield. Importantly, the ether scope could be extended to chain ether.
For example, diethyl ether afforded the two diasteromers (d.r.= 30:1,
ESI for detail), and major product 3ag was obtained in 49 %
separated yield.
To clarify the reaction mechanism, some control experiments
were conducted, shown in Scheme 4. When a radical-trapping
reagent 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was
added to the system, the reaction was completely inhibited.
Meanwhile, α-oxy radical of THF formed in situ was trapped
by TEMPO to form a radical adduct (4), which was determined
by HPLC-HRMS analysis (ESI for detail). These results
revealed that the initial step of the transformation probably was
caused by a radical process. Furthermore, an isotopic effect
(kH/kD = 4.0) was observed when equivalent THF (2a) and D8-
THF (D8-2a) were used to react with 1a under the standard
reaction conditions. This significant isotopic effect indicated
that cleavage of α-C(sp3
)−H in THF should be involved in the
rate-determining step (For detail see ESI).
Scheme 4. The control experiments.
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On the basis of the above results and the literature,4a,11,12b,c
a
plausible mechanism for this reaction is proposed in Scheme 5.
Initially, the excited-state Eosin Y* formed under blue LED
irradiation donates an electron to TBHP, giving tert-butyloxy
radical. The formed tert-butyloxy radical then abstracts a hydrogen
from α-C(sp3
)−H of THF (1a) to generate alkoxyalkyl radical
intermediate (A), which was trapped by TEMPO to form a radical
adduct (4), determined by HPLC-HRMS analysis. Subsequently, an
addition of alkoxyalkyl radical A to the C=C bond of amide 2a
produces an alkyl radical B, followed by intramolecular cyclization
with an aryl ring to afford a radical intermediate C. The generated C
is oxidized by a cation radical of Eosin Y•+
to deliver a cationic
intermediate D through a SET process. Finally, D is deprotonated to
afford alkylated oxindole 3a via an aromatization process along with
the formation of water.
Scheme 5. The possible reaction mechanism.
Conclusions
In summary, we have developed a novel visible-light-induced direct
difunctionalization of activated alkenes with readily available ethers,
in which two new C–C bonds were formed via selective C(sp3
)–H
bond cleavage. This tandem radical reaction represents a mild, facile
and environmental friendly route to a variety of alkylated oxindoles
in good yields at room temperature under metal-free condition.
Further investigation of the detailed mechanism and applications of
this protocol in organic synthesis are currently underway in our
laboratory.
Experimental section
General remarks
All reactions were carried out under air. 1
H NMR and 13
C 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. 1
H 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 collected on
an Agilent Technologies 6540 UHD Accurate-Mass Q-TOF LC/MS
using ESI.
Unless otherwise stated, all reactions were carried out under air
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.
General experimental procedure
A reaction tube was charged with N-methyl-N-
phenylmethacryl-amide (1a, 0.25 mmol), THF (2a, 3.0 mL),
TBHP (3.0 equiv), 4Å molecular sieve (60 mg), Eosin-Y (3.0
mol%). The mixture was stirred under the irradiation of 25 W
blue LED for 12 h. Then it was concentrated in vacuo to yield
the crude product, which was further purified by column
chromatography on silica gel (petroleum ether/EtOAc=2:1) to
give the desired product 3a.
Characterization data for all products
1,3-Dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-one
(3a):4a
White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.27 (t, J = 7.8
Hz, 1H), 7.19 (d, J = 7.2 Hz, 1H), 7.05 (t, J = 7.4 Hz, 1H), 6.85 (d, J
= 7.6 Hz, 1H), 3.73–3.67 (m, 1H), 3.56–3.48 (m, 2H), 3.21 (s, 3H),
2.27–2.21 (m, 1H), 1.88–1.84 (m, 1H), 1.81–1.70 (m, 2H), 1.69–
1.62 (m, 2H), 1.36 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 180.9,
143.7, 133.6, 127.7, 122.8, 121.9, 108.0, 75.6, 67.1, 46.8, 43.7, 31.7,
26.3, 25.3, 24.8.
1,3,5-Trimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-one
(3b):4a
White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.06 (d, J = 7.6
Hz, 1H), 7.00 (s, 1H), 6.73 (d, J = 8.0 Hz, 1H), 3.73–3.67 (m, 1H),
3.57–3.48 (m, 2H), 3.18 (s, 3H), 2.35 (s, 3H), 2.26–2.20 (m, 1H),
1.85–1.77 (m, 3H), 1.72–1.63 (m, 2H), 1.34 (s, 3H); 13
C NMR (100
MHz, CDCl3) δ: 180.8, 141.3, 133.7, 131.3, 127.9, 123.6, 107.7,
75.6, 67.1, 46.9, 43.7, 31.7, 26.3, 25.3, 24.8, 21.1.
1,3,7-Trimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-one
(3c): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.02–6.98 (m, 2H),
6.92 (t, J = 7.2 Hz, 1H), 3.73–3.68 (m, 1H), 3.55–3.51 (m, 2H), 3.48
(s, 3H), 2.59 (s, 3H), 2.27–2.21 (m, 1H), 1.84–1.78 (m, 3H), 1.72–
1.63 (m, 2H), 1.32 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 181.7,
141.5, 134.2, 131.4, 121.9, 120.6, 119.6, 75.5, 67.0, 46.1, 44.0, 31.7,
29.7, 25.3, 25.2, 19.1. HRMS (ESI) ([M+H]+
) Calcd. for C16H21NO3:
276.1600, Found: 276.1596.
5-Ethyl-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-
one (3d): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.09 (d, J =
7.6 Hz, 1H), 7.03 (s, 1H), 6.76 (d, J = 8.0 Hz, 1H), 3.73–3.67 (m,
1H), 3.58–3.49 (m, 2H), 3.19 (s, 3H), 2.67–2.62 (m, 2H), 2.26–2.21
(m, 1H), 1.87–1.79 (m, 3H), 1.71–1.63 (m, 2H), 1.35 (s, 3H), 1.24 (t,
J = 7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ: 180.9, 141.5,
138.1, 133.7, 126.8, 122.5, 107.7, 75.6, 67.0, 46.9, 43.7, 31.7, 28.6,
26.3, 25.3, 24.8, 16.0. HRMS (ESI) ([M+H]+
) Calcd. for C17H23NO2:
274.1807, Found: 274.1805.
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7-Ethyl-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-
one (3e): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.05 (d, J =
7.6 Hz, 1H), 7.02 (d, J = 6.0 Hz, 1H), 6.97 (t, J = 7.4 Hz, 1H), 3.73–
3.65 (m, 2H), 3.53–3.48 (m, 5H), 3.02–2.84 (m, 2H), 2.27–2.21 (m,
1H), 1.84–1.80 (m, 2H), 1.70–1.62 (m, 2H), 1.34 (s, 3H), 1.28 (t, J =
7.6 Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ: 181.8, 140.8, 134.5,
129.7, 126.3, 122.0, 120.5, 75.6, 67.0, 46.0, 44.1, 31.7, 29.5, 25.3,
25.2, 24.9, 16.7. HRMS (ESI) ([M+H]+
) Calcd. for C17H23NO2:
274.1807, Found: 274.1805.
5-Methoxy-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin
-2-one (3f):4a
White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.83–6.82
(m, 1H), 6.81–6.78 (m, 1H), 6.74 (d, J = 8.4 Hz, 1H), 3.81 (s, 3H),
3.73–3.68 (m, 1H), 3.59–3.51 (m, 2H), 3.18 (s, 3H), 2.25–2.20 (m,
1H), 1.85–1.78 (m, 3H), 1.71–1.67 (m, 2H), 1.34 (s, 3H); 13
C NMR
(100 MHz, CDCl3) δ: 180.6, 155.7, 137.3, 135.1, 111.6, 110.8,
108.1, 75.5, 67.1, 55.8, 47.3, 43.6, 31.7, 26.3, 25.3, 24.8.
5-Methoxy-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin
-2-one (3g):4a
White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.99 (t, J
= 8.0 Hz, 1H), 6.84–6.80 (m, 2H), 3.86 (s, 3H), 3.75–3.65 (m, 1H),
3.58–3.52 (m, 2H), 3.48 (s, 3H), 2.27–2.21 (m, 1H), 1.84–1.78 (m,
2H), 1.71–1.63 (m, 3H), 1.33 (s, 3H); 13
C NMR (100 MHz, CDCl3)
δ: 181.1, 145.3, 135.3, 131.5, 122.4, 115.5, 111.6, 75.6, 67.0, 55.8,
46.8, 43.9, 31.7, 29.5, 25.3, 25.1.
5-Ethoxy-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-
2-one (3h): White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.83–6.82
(m, 1H), 6.80–6.77 (m, 1H), 6.73 (d, J = 8.4 Hz, 1H), 4.04–3.99 (m,
2H), 3.73–3.67 (m, 1H), 3.59–3.48 (m, 2H), 3.17 (s, 3H), 2.25–2.19
(m, 1H), 1.84–1.79 (m, 3H), 1.72–1.63 (m, 2H), 1.41 (t, J = 7.0 Hz,
3H), 1.34 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 180.6, 155.0,
137.3, 135.0, 112.4, 111.4, 108.1, 75.6, 67.1, 64.1, 47.2, 43.6, 31.7,
26.3, 25.3, 24.8, 14.9. HRMS (ESI) ([M+H]+
) Calcd. for C17H23NO3:
290.1756, Found: 290.1752.
7-Methoxy-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin
-2-one (3i): White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.98–6.94
(m, 2H), 6.77–6.73 (m, 1H), 3.73–3.67 (m, 1H), 3.59–3.49 (m, 2H),
3.19 (s, 3H), 2.24–2.18 (m, 1H), 1.86–1.82 (m, 2H), 1.78–1.66 (m,
3H), 1.35 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 180.6, 159.1 (d, J
= 238.2 Hz), 139.6 (d, J = 1.9 Hz), 135.3 (d, J = 7.8 Hz), 113.8 (d, J
= 23.3 Hz), 111.0 (d, J = 24.4 Hz), 108.3 (d, J = 8.1 Hz), 75.4, 67.2,
47.4 (d, J = 1.7 Hz), 43.5, 31.7, 26.4, 25.2, 24.6. HRMS (ESI)
([M+H]+
) Calcd. for C15H18FNO2: 264.1400, Found: 264.1403.
5-Chloro-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-
2-one (3j): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.25–7.23
(m, 1H), 7.173–7.169 (m, 1H), 6.76 (d, J =8.4 Hz, 1H), 3.72–3.66
(m, 1H), 3.56–3.47 (m, 2H), 3.18 (s, 3H), 2.24–2.18 (m, 1H), 1.86–
1.79 (m, 2H), 1.77–1.66 (m, 3H), 1.34 (s, 3H); 13
C NMR (100 MHz,
CDCl3) δ: 180.4, 142.4, 135.3, 127.6, 127.3, 123.3, 108.9, 75.4,
67.2, 47.1, 43.6, 31.7, 26.4, 25.2, 24.7. HRMS (ESI) ([M+H]+
)
Calcd. for C15H18ClNO2: 280.1104, Found: 280.1099.
5-Bromo-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-
2-one (3k): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.40–7.37
(m, 1H), 7.31–7.30 (m, 1H), 6.72 (d, J = 8.4 Hz, 1H), 3.71–3.66 (m,
1H), 3.58–3.47 (m, 2H), 3.18 (s, 3H), 2.24–2.18 (m, 1H), 1.86–1.76
(m, 3H), 1.75–1.68 (m, 2H), 1.34 (s, 3H); 13
C NMR (100 MHz,
CDCl3) δ: 180.3, 142.9, 135.7, 130.5, 126.1, 114.6, 109.4, 75.4,
67.2, 47.1, 43.6, 31.7, 26.4, 25.2, 24.7. HRMS (ESI) ([M+H]+
)
Calcd. for C15H18BrNO2: 323.0521, Found: 323.0518.
5-Iodo-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-
one (3l): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.59–7.57 (m,
1H), 7.473–7.469 (m, 1H), 6.63 (d, J =8.0 Hz, 1H), 3.71–3.66 (m,
1H), 3.58–3.47 (m, 2H), 3.17 (s, 3H), 2.23–2.17 (m, 1H), 1.85–1.81
(m, 2H), 1.78–1.67 (m, 3H), 1.33 (s, 3H); 13
C NMR (100 MHz,
CDCl3) δ: 180.2, 143.6, 136.6, 136.1, 131.6, 110.1, 84.4, 75.4, 67.2,
46.9, 43.6, 31.7, 26.3, 25.2, 24.7. HRMS (ESI) ([M+H]+
) Calcd. for
C15H18INO2: 372.0460, Found: 372.0458.
1,3,4-Trimethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-one
(3m) compound with 1,3,6-Trimethyl-3-((tetrahydrofuran-2-
yl)methyl)indolin-2-one (3m’) (1.9:1) (3m+3m’): White solid. 1
H
NMR (400 MHz, CDCl3) δ: 7.17 (t, J = 7.8 Hz, 0.65H), 7.06 (d, J =
7.2 Hz, 0.35H), 6.85 (d, J = 7.2 Hz, 0.35H), 6.80 (d, J = 7.6 Hz,
0.64H), 6.70 (s, 0.35H), 6.68 (d, J = 3.6 Hz, 0.65H), 3.71–3.63 (m,
1H), 3.56–3.41 (m, 2H), 3.18 (s, 3H), 2.38 (s, 1H), 2.35 (s, 2H),
2.31–2.27 (m, 0.65H), 2.26–2.24 (m, 0.35H), 2.22–2.17 (m, 0.36H),
2.08–2.04 (m, 0.64H), 1.85–1.77 (m, 2H), 1.71–1.63 (m, 2H), 1.40
(s, 2H), 1.33 (s, 1H); 13
C NMR (100 MHz, CDCl3) δ: 181.4, 181.0,
144.0, 143.7, 137.7, 133.8, 130.6, 130.3, 127.7, 124.4, 122.5, 122.4,
109.0, 105.8, 75.9, 75.6, 67.1, 67.0, 47.7, 46.6, 43.7, 42.1, 31.7,
31.4, 26.4, 26.2, 25.3, 24.9, 22.8, 21.8, 18.3. HRMS (ESI) ([M+H]+
)
Calcd. for C16H21NO2: 259.1572, Found: 259.1570.
1-Methyl-1-((tetrahydrofuran-2-yl)methyl)-5,6-dihydro-1H-
pyrrolo[3,2,1-ij]quinolin-2(4H)-one (3n): White solid. 1
H NMR
(400 MHz, CDCl3) δ: 7.04–7.00 (m, 2H), 6.93 (t, J = 7.4 Hz, 1H),
3.78–3.64 (m, 3H), 3.61–3.50 (m, 2H), 2.80–2.78 (m, 2H), 2.25–
2.19 (m, 1H), 2.03–1.97 (m, 2H), 1.88–1.83 (m, 2H), 1.75–1.69 (m,
3H), 1.37 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 179.8, 139.5,
132.1, 126.5, 121.4, 120.7, 120.0, 75.7, 67.1, 48.2, 43.5, 38.8, 31.7,
25.3, 24.7, 24.4, 21.2. HRMS (ESI) ([M+H]+
) Calcd. for C17H21NO2:
272.1651, Found: 272.1648.
1,3,5,7-Tetramethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-
one (3o): White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.82 (s, 1H),
6.80 (s, 1H), 3.73–3.68 (m, 1H), 3.58–3.52 (m, 2H), 3.46 (s, 3H),
2.54 (s, 3H), 2.29 (s, 3H), 2.25–2.19 (m, 1H), 1.84–1.76 (m, 3H),
1.72–1.64 (m, 2H), 1.31 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ:
181.6, 139.1, 134.4, 131.9, 131.2, 121.3, 119.2, 75.6, 67.0, 46.2,
44.0, 31.7, 29.6, 25.3, 20.8, 18.9. HRMS (ESI) ([M+H]+
) Calcd. for
C17H23NO2: 274.1807, Found: 274.1807.
1,3,4,6-Tetramethyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-
one (3p): White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.63 (s, 1H),
6.53 (s, 1H), 3.69–3.64 (m, 1H), 3.51–3.46 (m, 2H), 3.18 (s, 3H),
2.34 (s, 3H), 2.31 (s, 3H), 2.30–2.24 (m, 1H), 2.05–2.01 (m, 1H),
1.86–1.78 (m, 2H), 1.70–1.64 (m, 2H), 1.39 (s, 3H); 13
C NMR (100
MHz, CDCl3) δ: 181.3, 144.1, 137.6, 133.5, 127.4, 125.0, 106.8,
75.9, 66.9, 47.4, 42.2, 31.4, 26.3, 25.3, 23.0, 21.6, 18.2. HRMS
(ESI) ([M+H]+
) Calcd. for C17H23NO2: 274.1807, Found: 274.1802.
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4,6-Dichloro-1,3-dimethyl-3-((tetrahydrofuran-2-yl)methyl)-
indolin-2-one (3q): White solid. 1
H NMR (400 MHz, CDCl3) δ:
7.01–7.00 (m, 1H), 6.752–6.749 (m, 1H), 3.63–3.57 (m, 1H), 3.51–
3.41 (m, 2H), 3.21 (s, 3H), 2.67–2.62 (m, 1H), 2.08–2.03 (m, 1H),
1.88–1.71 (m, 2H), 1.69–1.58 (m, 2H), 1.47 (s, 3H); 13
C NMR (100
MHz, CDCl3) δ: 179.8, 145.3, 134.0, 131.2, 128.7, 123.0, 107.3,
76.0, 67.3, 48.4, 40.7, 31.3, 26.5, 25.6, 22.5. HRMS (ESI) ([M+H]+
)
Calcd. for C15H17Cl2NO2: 313.0636, Found: 313.0632.
1-Ethyl-3-methyl-3-((tetrahydrofuran-2-yl)methyl)indolin-2-one
(3r): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.25 (t, J = 7.6 Hz,
1H), 7.19 (d, J = 7.2 Hz, 1H), 7.03 (t, J = 7.4 Hz, 1H), 6.86 (d, J =
8.0 Hz, 1H), 3.93–3.82 (m, 1H), 3.73–3.62 (m, 2H), 3.55–3.45 (m,
2H), 2.28–2.22 (m, 1H), 1.88–1.84 (m, 1H), 1.82–1.72 (m, 2H),
1.70–1.63 (m, 2H), 1.34 (s, 3H), 1.25 (t, J = 7.2 Hz, 3H); 13
C NMR
(100 MHz, CDCl3) δ: 180.4, 142.8, 133.8, 127.6, 123.3, 122.9,
121.6, 108.1, 75.6, 66.9, 46.7, 43.6, 34.5, 31.7, 25.2, 25.0, 12.2.
HRMS (ESI) ([M+H]+
) Calcd. for C16H21NO2: 260.1651, Found:
260.1646.
3-((1,3-Dioxolan-2-yl)methyl)-1,3-dimethylindolin-2-one (3v):
White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.27 (t, J = 7.6 Hz,1H),
7.23 (d, J = 7.2 Hz, 1H), 7.06 (t, J = 7.6 Hz, 1H), 6.85 (d, J = 7.6 Hz,
1H), 4.63–4.61 (m, 1H), 3.80–3.60 (m, 4H), 3.22 (s, 3H), 2.32–2.27
(m, 1H), 2.19–2.15 (m, 1H), 1.38 (s, 3H); 13
C NMR (100 MHz,
CDCl3) δ: 180.4, 143.3, 133.1, 127.8, 123.0, 122.2, 108.0, 101.8,
64.6, 64.5, 45.6, 41.4, 26.3, 24.9. HRMS (ESI) ([M+H]+
) Calcd. for
C14H17NO3: 248.1287, Found: 248.1285
3-((1,3-Dioxolan-2-yl)methyl)-1,3,5-trimethylindolin-2-one (3w):
White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.07 (d, J = 8.4 Hz, 1H),
7.04 (s, 1H), 6.73 (d, J = 7.6 Hz, 1H), 4.63–4.60 (m, 1H), 3.82–3.72
(m, 2H), 3.68–3.63 (m, 2H), 3.20 (s, 3H), 2.35 (s, 3H), 2.30–2.25
(m, 1H), 2.16–2.12 (m, 1H), 1.36 (s, 3H); 13
C NMR (100 MHz,
CDCl3) δ: 180.3, 140.9, 133.1, 131.7, 128.1, 123.8, 107.7, 101.8,
64.57, 64.55, 45.6, 41.5, 26.3, 24.9, 21.1. HRMS (ESI) ([M+H]+
)
Calcd. for C15H19NO3: 262.1443, Found: 262.1440.
3-((1,3-Dioxolan-2-yl)methyl)-5-ethyl-1,3-dimethylindolin-2-one
(3x): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.10 (d, J = 8.0
Hz, 1H), 7.07 (s,1H), 4.64–4.62 (m, 1H), 3.82–3.71 (m, 2H), 3.68–
3.63 (m, 2H), 3.21 (s, 3H), 2.67–2.62 (m, 2H), 2.31–2.25 (m, 1H),
2.18–2.13 (m, 1H), 1.37 (s, 3H), 1.24 (t, J = 7.6 Hz, 3H); 13
C NMR
(100 MHz, CDCl3) δ: 180.4, 141.1, 138.4, 133.1, 126.9, 122.7,
107.7, 101.8, 64.9, 64.5, 45.7, 41.4, 28.6, 26.3, 24.9, 16.0. HRMS
(ESI) ([M+H]+
) Calcd. for C16H21NO3: 276.1600, Found: 276.1596.
3-((1,3-Dioxolan-2-yl)methyl)-5-ethoxy-1,3-dimethylindolin-2-
one (3y): White solid. 1
H NMR (400 MHz, CDCl3) δ: 6.86–6.85 (m,
1H), 6.80–6.78 (m, 1H), 6.73 (d, J = 8.4 Hz, 1H), 4.65–4.63 (m, 1H),
4.04–3.99 (m, 2H), 3.82–3.72 (m, 2H), 3.68–3.61 (m, 2H), 3.19 (s,
3H), 2.30–2.24 (m, 1H), 2.15–2.10 (m, 1H), 1.41 (t, J = 7.0 Hz, 3H),
1.36 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 180.0, 155.1, 136.8,
134.4, 112.8, 111.4, 108.2, 101.8, 64.58, 64.55, 64.2, 46.0, 41.4,
26.3, 24.9, 14.9. HRMS (ESI) ([M+H]+
) Calcd. for C16H21NO4:
292.1549, Found: 292.1549.
3-((1,3-Dioxolan-2-yl)methyl)-5-chloro-1,3-dimethylindolin-2-
one (3z): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.26–7.23 (m,
1H), 7.22–7.21 (m, 1H), 6.76 (d, J = 8.4 Hz, 1H), 4.65–4.62 (m, 1H),
3.79–3.74 (m, 1H), 3.71–3.62 (m, 3H), 3.21 (s, 3H), 2.32–2.27 (m,
1H), 2.17–2.13 (m, 1H), 1.37 (s, 3H); 13
C NMR (100 MHz, CDCl3)
δ: 179.8, 141.9, 134.9, 127.7, 127.6, 123.7, 108.8, 101.6, 64.7, 64.5,
45.8, 41.2, 26.4, 24.8. HRMS (ESI) ([M+H]+
) Calcd. for
C14H16ClNO3: 282.0897, Found: 282.0895.
3-((1,3-Dioxolan-2-yl)methyl)-1,3-dimethyl-5-(trifluoromethyl)
indolin-2-one (3aa): White solid. 1
H NMR (400 MHz, CDCl3) δ:
7.55 (d, J = 8.4 Hz, 1H), 7.47 (s, 1H), 6.91 (d, J = 8.4 Hz, 1H), 4.63–
4.61(m, 1H), 3.75–3.69 (m, 1H), 3.68–3.60 (m, 3H), 3.25 (s, 3H),
2.36–2.31 (m, 1H), 2.23–2.19 (m, 1H), 1.39 (s, 3H); 13
C NMR (100
MHz, CDCl3) δ: 180.3, 146.3 (q, J = 1.3 Hz), 133.7, 129.0 (q, J =
97.8 Hz), 125.8, 125.6 (q, J = 4.1 Hz), 124.4 (q, J = 32.3 Hz), 123.1,
120.2 (q, J = 3.7 Hz), 107.6, 101.5, 64.7, 64.5, 45.5, 41.1, 26.5, 24.8.
HRMS (ESI) ([M+H]+
) Calcd. for C15H16F3NO3: 315.1082, Found:
315.1078.
3-((1,3-Dioxolan-2-yl)methyl)-1,3-dimethyl-2-oxoindoline-5-
carbonitrile (3ab): White solid. 1
H NMR (400 MHz, CDCl3) δ:
7.59–7.57 (m, 1H), 7.479–7.477 (m, 1H), 6.89 (d, J = 8.4 Hz, 1H),
4.60–4.58 (m, 1H), 3.72–3.68 (m, 1H), 3.65–3.57 (m, 3H), 3.22 (s,
3H), 2.33–2.27 (m, 1H), 2.21–2.17 (m, 1H), 1.35 (s, 3H); 13
C NMR
(100 MHz, CDCl3) δ: 180.0, 147.1, 134.2, 133.2, 126.7, 119.3,
108.3, 105.1, 101.3, 64.8, 64.5, 45.3, 41.0, 26.5, 24.7. HRMS (ESI)
([M+H]+
) Calcd. for C15H16N2O3: 272.1161, Found: 272.1160.
Ethyl 3-((1,3-dioxolan-2-yl)methyl)-1,3-dimethyl-2-oxoindoline-
5-carboxylate (3ac): White solid. 1
H NMR (400 MHz, CDCl3) δ:
8.03–8.01 (m, 1H), 7.89–7.88 (m, 1H), 6.86 (d, J = 8.4 Hz, 1H),
4.59–4.57 (m, 1H), 4.39–4.34 (m, 2H), 3.78–3.71 (m, 1H), 3.69–
3.57 (m, 3H), 3.24 (s, 3H), 2.33–2.28 (m, 1H), 2.23–2.19 (m, 1H),
1.41–1.38 (m, 6H); 13
C NMR (100 MHz, CDCl3) δ: 180.6, 166.5,
147.4, 133.0, 130.6, 124.5, 124.2, 107.4, 101.5, 64.6, 64.5, 60.8,
45.4, 41.3, 26.5, 24.8, 14.4. HRMS (ESI) ([M+H]+
) Calcd. for
C17H21NO5: 319.1420, Found: 319.1416.
1-((1,3-Dioxolan-2-yl)methyl)-1-methyl-5,6-dihydro-1H-pyrrolo
[3,2,1-ij]quinolin-2(4H)-one (3ad): White solid. 1
H NMR (400
MHz, CDCl3) δ: 7.07 (d, J = 7.2 Hz, 1H), 7.02 (d, J = 7.2 Hz, 1H),
6.94 (t, J = 7.4 Hz, 1H), 4.68–4.66 (m, 1H), 3.82–3.64 (m, 6H),
2.81–2.78 (m, 2H), 2.30–2.24 (m, 1H), 2.18–2.14 (m, 1H), 2.04–
1.98 (m, 2H), 1.39 (s, 3H); 13
C NMR (100 MHz, CDCl3) δ: 179.2,
139.1, 131.6, 126.6, 121.6, 120.9, 120.0, 101.9, 64.6, 64.5, 46.9,
41.2, 38.9, 24.7, 24.5, 21.3. HRMS (ESI) ([M+H]+
) Calcd. for
C16H19NO3: 274.1443, Found: 274.1443.
3-((1,3-Dioxolan-2-yl)methyl)-1-ethyl-3-methylindolin-2-one
(3ae): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.27–7.22 (m,
2H), 7.04 (t, J = 7.4 Hz, 1H), 6.86 (d, J = 7.6 Hz, 1H), 4.61–4.59 (m,
1H), 3.93–3.84 (m, 1H), 3.80–3.76 (m, 1H), 3.71–3.59 (m, 4H),
2.33–2.28 (m, 1H), 2.19–2.15 (m, 1H), 1.36 (s, 3H), 1.26 (t, J = 7.2
Hz, 3H); 13
C NMR (100 MHz, CDCl3) δ: 179.9, 142.4, 133.3, 127.7,
123.2, 121.9, 108.1, 101.8, 64.6, 64.3, 45.4, 41.3, 34.5, 25.0, 12.3.
HRMS (ESI) ([M+H]+
) Calcd. for C15H19NO3: 262.1443, Found:
262.1440.
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8. Green Chemistry ARTICLE
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1,3-Dimethyl-3-((tetrahydrothiophen-2-yl)methyl)indolin-2-one
(3af): White solid. 1
H NMR (400 MHz, CDCl3) δ: 7.31 (t, J = 7.8
Hz, 1H), 7.27 (d, J = 5.6 Hz, 1H), 7.08 (t, J = 7.6 Hz, 1H), 6.88 (d, J
= 7.6 Hz, 1H), 3.25 (s, 3H), 3.03–2.91 (m, 2H), 2.46–2.42 (m, 2H),
2.40–2.36 (m, 2H), 1.82–1.75 (m, 2H), 1.43 (s, 3H); 13
C NMR (100
MHz, CDCl3) δ: 179.4, 143.6, 132.8, 128.3, 122.9, 122.5, 108.1,
49.2, 42.4, 39.9, 32.9, 26.2, 23.0, 21.9. HRMS (ESI) ([M+H]+
)
Calcd. for C15H19NOS: 262.1266, Found: 262.1260.
3-(2-Ethoxypropyl)-1,3-dimethylindolin-2-one (3ag):4a
White
solid. 1
H NMR (400 MHz, CDCl3) δ: 7.27–7.22 (m, 2H), 7.07 (t, J =
7.6 Hz, 1H), 6.83 (d, J = 7.6 Hz, 1H), 3.23–3.18 (m, 4H), 3.09–3.05
(m, 1H), 2.77–2.71 (m, 1H), 2.15–2.09 (m, 1H), 2.04–2.00 (m, 1H),
1.36 (s, 3H), 0.99 (d, J = 6.0 Hz, 3H), 0.72 (t, J = 7.0 Hz, 3H); 13
C
NMR (100 MHz, CDCl3) δ: 180.6, 142.7, 134.7, 127.2, 123.0, 122.4,
107.7, 72.9, 63.4, 47.3, 44.9, 26.1, 25.4, 20.2, 15.0.
Acknowledgements
This work was financially supported by the National Science
Foundation of China (21572078, 21602072), the Anhui
Provincial Natural Science Foundation (1508085QB42), the
National Science Foundation of Anhui Education Department
(KJ2016A643) and Huaibei Normal University Foundation
(2014xq014).
Notes and references
1 (a) H. Chen, S. Schlecht, T. C. Semple and J. F. Hartwig, Science,
2000, 287, 1995; (b) R. G. Bergman, Nature, 2007, 446, 391; (c) M.
S. Chen and M. C. White, Science, 2007, 318, 783; (d) W. Shi, C. Liu
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DOI: 10.1039/C6GC03323G