Iron-catalyzed oxidative 1,2-carboacylation of activated alkenes with alcohols: A tandem route to 3-(2-oxoethyl)indolin-2-ones

Article abstract of DOI:10.1002/ejoc.201400043

Oxindoles are important heterocyclic compounds that are found in a wide range of pharmaceutical agents and natural products. A new oxidative tandem route to the assembly of 3-(2-oxoethyl)indolin-2-ones from N-arylacrylamides and alcohols has been established by using inexpensive and environmentally benign iron catalysts and peroxides. In the presence of Fe(OAc)₂ and tert-butyl hydroperoxide, a variety of arylacrylamides underwent the oxidative 1,2-carboacylation reaction with alcohols to give the corresponding 3-(2-oxoethyl)indolin-2-ones in moderate to good yields. Copyright

Full text of DOI:10.1002/ejoc.201400043

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DOI: 10.1002/ejoc.201400043
Iron-Catalyzed Oxidative 1,2-Carboacylation of Activated Alkenes with
Alcohols: A Tandem Route to 3-(2-Oxoethyl)indolin-2-ones
Xuan-Hui Ouyang,[a] Ren-Jie Song,*[a] and Jin-Heng Li*[a]
Keywords: Domino reactions / Cyclization / Iron / Oxidation / Alkenes / Alcohols
Oxindoles are important heterocyclic compounds that are
found in a wide range of pharmaceutical agents and natural
products. A new oxidative tandem route to the assembly of
3-(2-oxoethyl)indolin-2-ones from N-arylacrylamides and
alcohols has been established by using inexpensive and en-
vironmentally benign iron catalysts and peroxides. In the
presence of Fe(OAc)2 and tert-butyl hydroperoxide, a variety
of arylacrylamides underwent the oxidative 1,2-carboacyl-
ation reaction with alcohols to give the corresponding 3-(2-
oxoethyl)indolin-2-ones in moderate to good yields.
Introduction
Oxidative difunctionalization of alkenes through C–H
functionalization has emerged as a direct and highly atom-
economical synthetic approach to a diverse range of prod-
ucts with important chemical, biological, and medicinal
properties.[1] In this field, the oxidative C–H functionaliza-
tion/carbocyclization of alkenes with two C–H bonds lead-
ing to the simultaneous formation of two carbon–carbon
bonds is an elegant finding because their cyclic products are
important skeletal units in natural products and bioactive
molecules.[2–5] However, the oxidative C–H functionaliza-
tion/carbocyclization of alkenes has not been much investi-
gated (Scheme 1).[2–5] Liu and co-workers first reported oxi-
dative difunctionalization of alkenes in N-arylacrylamides
with the α-C(sp3)–H bonds of alkyl nitriles using the
Pd(OAc)2/PhI(OPiv)2 catalytic system, which provides a
useful route to oxindoles.[2] Recently, our group,[3] the Li
group,[3i] and the group of Guo and Duan[4] independently
illustrated the oxidative difunctionalization of alkenes in N-
arylacrylamides with various C–H bonds, including the
C(sp3)–H bond adjacent to a heteroatom[3a,4a] or an aryl
group[3b,4b] and the carbonyl C(sp2)–H bond[3c] using a
transition metal and/or peroxide system.
Scheme 1. Oxidative difunctionalization of alkenes with two C–H
bonds.
Tu[8a–d] and Liu[8e] have reported transition metal (Rh, Ru,
Pd, Fe or Cu) catalyzed C–H functionalization/cross-cou-
pling of alcohols with alkenes. Recently, Guo and Duan
developed metal-free tert-butyl hydroperoxide (TBHP) me-
diated oxidative hydroxyalkylarylation of activated alkenes
by direct C(sp3)–H functionalization of alcohols, providing
hydroxy-containing oxindoles in high yields.[4a] As part of
our continuing interest in the oxidative C–H functionaliza-
tion/carbocyclization of alkenes, we report here a tandem
route to 3-(2-oxoethyl)indolin-2-ones by iron-catalyzed oxi-
dative 1,2-carboacylation of activated alkenes with alcohols
(Scheme 1). Carbonyl-containing oxindoles are fundamen-
tal structural motifs in pharmaceutical agents and natural
products as well as versatile intermediates in organic syn-
thesis.[9]
Alcohols, which are fundamental bulk chemicals, are
widely used as solvents and building blocks in organic syn-
thesis and industry.[6] Direct functionalization of the C–H
bond adjacent to a hydroxyl group still belongs to an im-
portant and challenging area of organic chemistry.[7,8]
[a] State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan
University,
Changsha 410082, China
E-mail: jhli@hnu.edu.cn
srj0731@hnu.edu.cn
http://cc.hnu.cn/index.php?option=com_content&task=
view&id=1054&Itemid=228
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201400043.
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X.-H. Ouyang, R.-J. Song, J.-H. Li
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the reaction, with other solvents such as MeCN, dioxane,
and DMF, suppressing the reaction.
Results and Discussion
As shown in Table 1, we chose the reaction between N-
methyl-N-phenylmethacrylamide (1a) and benzyl alcohol
(2a) as a model with which to optimize the reaction condi-
tions. Treatment of amide 1a with alcohol 2a, Fe(OAc)2,
and TBHP in EtOAc afforded the expected product 3 in
77% yield (entry 1). Therefore, a series of other Fe catalysts,
including FeCl2, Fe(OTf)2, FeCl3, Fe(OTf)3, Fe(acac)3, were
examined (entries 2–6), however, these catalysts were less
effective than Fe(OAc)2. Interestingly, the reaction gave
product 3 in the presence of TBHP without Fe catalysts,
albeit in low yield (entry 7). Screening revealed that the
amount of Fe(OAc)2 affected the reaction, and 10 mol-%
Fe(OAc)2 was viable (entry 1 vs. entries 8–9). Subsequently,
several oxidants, such as aqueous TBHP, di-tert-butyl per-
oxide (DTBP), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ), and O2, were investigated (entries 10–13). Whereas
both hydrous TBHP and DTBP displayed high activity for
the reaction, DDQ and O2 had no effect on the reaction.
The effect of reaction temperature was also investigated,
and it was found that conducting the reaction at 110 °C
gave the best results (entries 1, 14 and 15). A number of
other solvents, including nBuOAc, MeCN, dioxane and
N,N-dimethylformamide (DMF), were also tested (entries
16–19). We found that nBuOAc was a suitable solvent for
After determining the optimal conditions, we turned our
attention to exploring the scope of this oxidative 1,2-
carboacylation reaction (Table 2 and Table 3). As illustrated
in Table 2, a variety of primary alcohols 2, including benzyl
alcohols, were compatible with the optimal conditions with
respect to N-methyl-N-phenylmethacrylamide (1a), giving
products 4–14. Initially, a number of benzyl alcohols were
investigated (products 4–11). The results demonstrated that
several substituents, including Me, CN, Cl and MeO
groups, on the aromatic ring of the benzyl moiety were well-
tolerated, and the reactive order of the substituents was
para, metaϾ ortho (products 4–10). For example, the reac-
tion of p-tolylmethanol with amide 1a, Fe(OAc)2, and
TBHP gave the desired product 4 in 66% yield. 4-CN- or
4-Cl-substituted benzyl alcohols were also viable for the re-
action, giving the corresponding products 5 and 6 in good
yields. Whereas (p-methoxyphenyl)methanol and (m-meth-
oxyphenyl)methanol afforded products 7 and 8 in 76 and
74% yield, respectively, (o-methoxyphenyl)methanol gave a
lower yield of the corresponding product 9 (47%). Notably,
the optimized conditions were compatible with a heteroaryl
methanol, furan-2-ylmethanol, resulting in the formation of
11 in 63% yield. In light of these results, other alkyl
alcohols were examined and all were found to be suitable
substrates, providing the desired products 12 and 14–16 in
moderate yield. It is noteworthy that the reaction with eth-
anol offered another hydroxy-containing product, 13, in
31% yield. Unfortunately, secondary alcohols were inert
under these conditions.
Table 1. Screening optimal conditions.[a]
We next set out to apply the iron-catalyzed oxidative tan-
dem reaction to N-arylacrylamides 1 in the presence of (p-
methoxyphenyl)methanol, Fe(OAc)2, and TBHP (Table 3).
N-Phenylmethacrylamides with a N–Bn group or a N–Ac
group were found to be suitable substrates for the reaction
(products 17 and 18), but substrates with an N–H group
did not react (product 19). Gratifyingly, N-arylacrylamides
1, bearing either electron-donating or electron-withdrawing
substituents on the aromatic ring of the N-aryl moiety, were
compatible with the optimized conditions, and the electron-
donating groups displayed higher activity than electron-
withdrawing groups (products 20–26). Importantly, ortho-
halo groups were perfectly tolerated, affording the corre-
sponding products 23 and 24 in moderate yields. Using sub-
strate amides with a meta-methyl group, gave a mixture of
products 25 and 26. It was noted that N-arylacrylamides
with a phenyl group at the 2-position was also viable in the
reaction with (p-methoxyphenyl)methanol, Fe(OAc)2 and
TBHP, providing the desired product 27 in 58% yield.
To understand the mechanism followed in the oxidative
1,2-carboacylation reaction, a number of control experi-
ments were performed (Scheme 2).[10] These experiment
showed that (p-methoxyphenyl)methanol could be readily
converted into aldehyde 28 in the presence of Fe(OAc)2 and
TBHP [Equation (1)]. However, dodecan-1-ol display lower
reactivity under the same conditions [Equation (2)]. Inter-
estingly, substrate 13, which was synthesized by a reported
Entry [M] (mol-%)
[O]
Solvent
T (°C)
Isolated
yield [%]
1
2
Fe(OAc)2 (10)
FeCl2 (10)
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP EtOAc
DTBP EtOAc
DDQ EtOAc
110
110
110
110
110
110
110
110
110
110
110
110
110
80
77
65
51
15
59
58
28
41
75
61
58
trace
trace
32
67
76
49
trace
trace
3
4
Fe(OTf)2 (10)
FeCl3 (10)
5
6
7
Fe(OTf)3 (10)
Fe(acac)3 (10)
–
8
9
Fe(OAc)2 (5)
Fe(OAc)2 (15)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
Fe(OAc)2 (10)
10[b]
11
12
13[c]
14
15
16
17
18
19
–
EtOAc
TBHP EtOAc
TBHP EtOAc
TBHP nBuOAc
TBHP MeCN
TBHP dioxane
TBHP DMF
130
110
110
110
110
[a] Reaction conditions: 1a (0.2 mmol), 2a (3 equiv.), [Fe], [O]
(2 equiv.), solvent (2 mL), 110 °C, 24 h. Unless specified otherwise,
TBHP was used as a 5 m solution in decane. Some byproducts,
including C–N decomposition products, were observed by GC–MS
analysis, and the rest of alcohol 2a was converted into the corre-
sponding acid. [b] TBHP (70% in water). [c] O2 (1 atm).
2
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A Tandem Route to 3-(2-Oxoethyl)indolin-2-ones
Table 2. Screening scope of alcohols 2.[a]
[a] Reaction conditions: 1a (0.3 mmol), 2 (2 equiv.), Fe(OAc)2 (10 mol-%), TBHP (3 equiv; 5 m in decane), EtOAc (2 mL), 110 °C, 24 h.
[b] A mixture of 12 and byproduct 13 [3-(2-hydroxypropyl)-1,3-dimethylindolin-2-one] was isolated in 75% total yield with 1.4:1 ratio.
Table 3. Screening scope of N-arylacrylamides (1).[a]
[a] Reaction conditions: 1 (0.3 mmol), 2 (2 equiv.), Fe(OAc)2 (10 mol-%), TBHP (3 equiv; 5 m in decane), EtOAc (2 mL), 110 °C, 24 h.
method,[4a] could be transformed into ketone 12 in 54%
Consequently, possible mechanisms as outlined in
yield [Equation (3)]. These results suggest that the oxidative Scheme 3 were proposed on the basis of the present re-
1,2-carboacylation reaction may proceed through two dif- sults.[5,6] Initially, TBHP is easily split by Fe2+ into a tert-
ferent mechanisms.
butoxy radical and Fe3+(OH) (Pathway I). The reaction of
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X.-H. Ouyang, R.-J. Song, J.-H. Li
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by using inexpensive and environmentally benign iron cata-
lysts; moreover, it provides a shortcut to carbonyl-contain-
ing oxindoles from alcohols.
Experimental Section
General Methods: All the materials and solvents were purchased
from commercial suppliers and used without additional purifica-
tion. IR measurements were performed with a FTIR Shimadzu
DR-8000 spectrometer fitted with a Pike Technologies MIRacle
Single Reflection ATR adapter. 1H and 13C NMR spectra were
recorded with a Bruker DRX-500 spectrometer (1H at 500 MHz
and 13C at 125 MHz) or a Bruker DRX-400 spectrometer (1H at
400 MHz and 13C at 100 MHz). NMR spectroscopic data were ob-
tained in CDCl3 unless otherwise noted. High-resolution mass
spectra were recorded with a Bruker microTOF-QII (ESI) spec-
trometer. Preparative thin-layer chromatography was performed on
silica gel plates with PF254 indicator. Flash column chromatog-
raphy was performed with silica gel 60N unless otherwise noted.
Scheme 2. Control experiments.
a tert-butoxy radical with an alcohol affords radical inter-
mediate A by abstracting the C(sp3)–H bonds adjacent to
an oxygen atom. Addition of radical intermediate A to the
carbon–carbon double bond of substrate 1a gave radical
intermediate B, followed by intramolecular carbocyclization
of radical intermediate B to furnish radical intermediate C.
Typical Experimental Procedure for the Fe-Catalyzed Synthesis of
3-(2-Oxoethyl)indolin-2-ones: To a Schlenk tube were added N-aryl-
acrylamide 1 (0.3 mmol), alcohol 2 (2 equiv.), Fe(OAc)2 (10 mol-
%), TBHP (5 m in decane, 3 equiv), and EtOAc (2 mL). The tube
was charged with argon and the mixture was stirred at 110 °C for
24 h until complete consumption of starting material was observed
(reaction monitored by TLC and/or GC–MS analysis). When the
reaction was complete, the reaction mixture was washed with brine,
the aqueous phase was re-extracted with ethyl acetate, and the com-
bined organic extracts were dried with Na2SO4, concentrated in
vacuo, and the resulting residue was purified by silica gel column
chromatography (hexane/ethyl acetate) to afford the desired prod-
uct.
Hydrogen abstraction of radical intermediate
C by
Fe3+(OH) takes place to produce 3-(2-hydroxyethyl)indolin-
2-one D. The oxidation of D by Fe(OAc)2 and TBHP gives
the expected 3-(2-hydroxyethyl)indolin-2-one[10] and regen-
erates the active FeII species.
1,3-Dimethyl-3-(2-oxo-2-phenylethyl)indolin-2-one (3):[3c,5f] Color-
1
less liquid. H NMR (400 MHz, CDCl3): δ = 7.83 (d, J = 7.2 Hz,
2 H), 7.51 (t, J = 7.2 Hz, 1 H), 7.39 (t, J = 8.0 Hz, 2 H), 7.26 (t, J
= 8.0 Hz, 1 H), 7.14 (d, J = 7.2 Hz, 1 H), 6.98 (t, J = 7.6 Hz, 1 H),
6.90 (d, J = 8.0 Hz, 1 H), 3.72 (d, J = 18.0 Hz, 1 H), 3.65 (d, J =
18.0 Hz, 1 H), 3.31 (s, 3 H), 1.44 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 195.9, 180.4, 143.7, 136.3, 133.6, 133.0,
128.3, 127.8, 127.7, 122.0, 121.6, 108.0, 45.9, 45.1, 26.3, 24.8 ppm.
MS (EI, 70 eV): m/z (%) = 279 (87) [M+], 234 (22), 220 (8), 160
(100).
1,3-Dimethyl-3-[2-oxo-2-(p-tolyl)ethyl]indolin-2-one (4):[3c] Colorless
oil. 1H NMR (400 MHz, CDCl3): δ = 7.74 (d, J = 8.2 Hz, 2 H),
7.26 (t, J = 4.0 Hz, 1 H), 7.19 (d, J = 8.0 Hz, 1 H), 7.13 (d, J =
6.8 Hz, 1 H), 6.95 (t, J = 8.0 Hz, 1 H), 6.95 (t, J = 7.6 Hz, 1 H),
3.71 (d, J = 18.0 Hz, 1 H), 3.63 (d, J = 18.0 Hz, 1 H), 3.32 (s, 3
H), 2.37 (s, 3 H), 1.43 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 195.6, 180.6, 143.9, 143.8, 133.9, 133.8, 129.1, 128.0, 127.7,
122.0, 121.7, 108.0, 45.8, 45.2, 26.4, 24.8, 21.5 ppm. MS (EI,
70 eV): m/z (%) = 293 (78) [M+], 248 (23), 174 (30), 160 (79), 119
(100).
Scheme 3. Possible mechanisms.
Another pathway includes initial oxidation of the alcohol
to give the aldehyde, followed by a acylation–carbocycli-
zation tandem reaction to give the expected 3-(2-hydroxy-
ethyl)indolin-2-one (Pathway II). It is noteworthy that
benzyl alcohols may predominantly perform the reaction
through Pathway II.
4-[2-(1,3-Dimethyl-2-oxoindolin-3-yl)acetyl]benzonitrile (5):[3c] Col-
1
orless oil. H NMR (500 MHz, CDCl3): δ = 7.90 (d, J = 8.0 Hz, 2
Conclusions
H), 7.70 (d, J = 8.5 Hz, 2 H), 7.27 (t, J = 7.5 Hz, 1 H), 7.13 (d, J
= 7.0 Hz, 1 H), 6.99 (t, J = 7.5 Hz, 1 H), 6.91 (d, J = 8.0 Hz, 1 H),
3.67 (s, 2 H), 3.30 (s, 3 H), 1.45 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 194.9, 180.1, 143.7, 139.1, 133.1, 132.3, 128.3, 128.0,
122.3, 121.7, 117.7, 116.4, 108.2, 46.1, 45.2, 26.4, 24.8 ppm. MS
We have established an iron-catalyzed oxidative carbo-
acylation tandem route to 3-(2-oxoethyl)indolin-2-ones.
This tandem method is realized by 1,2-difunctionalization
of the C–C double bond in N-arylacrylamides with alcohols (EI, 70 eV): m/z (%) = 304 (37) [M+], 259 (13), 245 (7), 160 (100).
4
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A Tandem Route to 3-(2-Oxoethyl)indolin-2-ones
3-[2-(4-Chlorophenyl)-2-oxoethyl]-1,3-dimethylindolin-2-one (6): Yel-
low oil. H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 8.4 Hz, 2
H), 7.36 (d, J = 8.4 Hz, 2 H), 7.26 (d, J = 7.6 Hz, 1 H), 7.13 (t, J
1,3-Dimethyl-3-(2-oxopropyl)indolin-2-one (12) and 3-(2-Hy-
droxypropyl)-1,3-dimethylindolin-2-one (13):[5f] Ratio 12/13 = 1.4:1;
colorless oil. 1H NMR (500 MHz, CDCl3): δ = 7.31–7.24 (m, 2 H),
1
= 7.2 Hz, 1 H), 6.98 (d, J = 7.6 Hz, 1 H), 6.90 (d, J = 8.0 Hz, 1 7.19 (d, J = 7.2 Hz, 0.85 H), 7.14 (d, J = 7.2 Hz, 1 H), 7.09 (t, J =
H), 3.67 (d, J = 18.0 Hz, 1 H), 3.62 (d, J = 18.0 Hz, 1 H), 3.30 (s,
3 H), 1.43 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.9,
180.4, 143.7, 139.6, 134.5, 133.5, 129.3, 128.7, 127.9, 122.2, 121.6,
7.6 Hz, 0.83 H), 7.01 (t, J = 7.6 Hz, 1 H), 6.87 (d, J = 7.6 Hz, 1.78
H), 4.15–4.08 (m, 0.85 H), 3.82 (br. s, 0.73 H), 3.26 (s, 3 H), 3.23
(s, 2.5 H), 3.13 (d, J = 18.0 Hz, 1 H), 3.08 (d, J = 18.4 Hz, 1 H),
1.98 (s, 3 H), 1.97–1.93 (m, 1 H), 1.79–1.73 (m, 0.94 H), 1.35 (s,
2.5 H), 1.33 (s, 3 H), 1.15 (d, J = 6.0 Hz, 2.5 H) ppm. 13C NMR
108.1, 45.9, 45.2, 26.4, 24.8 ppm. IR (KBr): ν = 1702, 1686 cm–1.
˜
MS (EI, 70 eV): m/z (%) = 315 (14) [M+ + 2], 313 (37) [M+], 268
(20), 168 (100). HRMS (ESI): m/z calcd. for C18H17ClNO2 [M + (100 MHz, CDCl3): δ = 204.6, 181.9, 180.3, 143.6, 142.3, 134.9,
H]+ 314.0948; found 314.0957.
133.3, 128.0, 127.8, 123.0, 122.4, 122.2, 121.7, 108.4, 108.1, 64.6,
50.4, 47.3, 46.0, 45.1, 29.9, 26.3, 24.3, 23.9, 22.8 ppm. MS (EI,
70 eV) for 12: m/z (%) = 217 (82) [M+], 174 (50), 160 (100); MS
(EI, 70 eV) for 13: m/z (%) = (30) [M+] [%] 219, 174 (52), 161 (100).
3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-one
(7):[3c] Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J =
8.8 Hz, 2 H), 7.24 (t, J = 8.0 Hz, 1 H), 7.13 (d, J = 7.2 Hz, 1 H),
6.96 (t, J = 7.6 Hz, 1 H), 6.89 (d, J = 8.0 Hz, 1 H), 6.85 (d, J =
8.8 Hz, 2 H), 3.81 (s, 3 H), 3.68 (d, J = 18.0 Hz, 1 H), 3.59 (d, J =
17.6 Hz, 1 H), 3.30 (s, 3 H), 1.42 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 194.5, 180.7, 163.5, 143.8, 133.9, 130.2,
129.5, 127.7, 122.1, 121.7, 113.6, 108.1, 55.4, 45.6, 45.3, 26.4,
24.9 ppm. MS (EI, 70 eV): m/z (%) = 309 (28) [M+], 264 (10), 174
(13), 160 (28), 135 (100).
1,3-Dimethyl-3-(2-oxobutyl)indolin-2-one (14): Colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 7.25 (d, J = 7.6 Hz, 1 H), 7.13 (d,
J = 7.6 Hz, 1 H), 7.00 (t, J = 7.6 Hz, 1 H), 6.87 (d, J = 7.6 Hz, 1
H), 3.27 (s, 3 H), 3.08 (s, 2 H), 2.39–2.19 (m, 2 H), 1.33 (s, 3 H),
0.89 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
207.4, 180.4, 143.7, 133.5, 127.9, 122.2, 121.7, 108.2, 49.3, 45.1,
35.9, 26.4, 24.5, 7.3 ppm. IR (KBr): ν = 1703, 1692 cm–1. MS (EI,
˜
70 eV): m/z (%) = 231 (59) [M+], 174 (77), 160 (100). HRMS (ESI):
m/z calcd. for C14H18NO2 [M + H]+ 232.1338; found 232.1342.
3-[2-(3-Methoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-one
(8):[3c] Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.45 (d, J =
7.6 Hz, 1 H),7.32 (t, J = 4.0 Hz, 2 H), 7.28 (t, J = 6.4 Hz, 1 H),
7.13 (d, J = 8.0 Hz, 1 H), 7.06–7.05 (m, 1 H), 6.97 (t, J = 7.2 Hz,
1 H), 6.90 (d, J = 7.6 Hz, 1 H), 3.77 (s, 3 H), 3.71 (d, J = 18.0 Hz,
1 H), 3.64 (d, J = 18.0 Hz, 1 H), 3.31 (s, 3 H), 1.43 (s, 3 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 195.9, 180.5, 159.6, 143.7, 137.6,
133.6, 129.4, 127.7, 122.1, 121.6, 120.5, 119.9, 111.8, 108.0, 55.3,
46.0, 45.2, 26.3, 24.9 ppm. MS (EI, 70 eV): m/z (%) = 309 (96)
[M+], 264 (28), 250 (11), 160 (100).
1
1,3-Dimethyl-3-(2-oxopentyl)indolin-2-one (15):[3c] Colorless oil. H
NMR (500 MHz, CDCl3): δ = 7.25–7.23 (m, 1 H), 7.14 (d, J =
5 Hz, 1 H), 7.02 (t, J = 7.5 Hz, 1 H), 6.88 (d, J = 2.5 Hz, 1 H),
3.28 (s, 3 H), 3.08 (s, 2 H), 2.29–2.12 (m, 2 H), 1.46–1.41 (m, 2 H),
1.33 (s, 3 H), 0.77 (t, J = 7.5 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 206.9, 180.4, 143.7, 133.5, 127.8, 122.1, 121.7, 108.1,
49.7, 45.2, 44.7, 29.7, 24.4, 16.9, 13.5 ppm. MS (EI, 70 eV): m/z
(%) = 246 (13) [M+ + 1], 245 (70) [M+], 200 (5), 174 (100).
1,3-Dimethyl-3-(2-oxotridecyl)indolin-2-one (16): Colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 7.24 (t, J = 7.6 Hz, 1 H), 7.12 (d, J
= 7.2 Hz, 1 H), 6.99 (d, J = 7.6 Hz, 1 H), 6.85 (d, J = 7.6 Hz, 1
H), 3.26 (s, 3 H), 3.07 (s, 2 H), 2.31–2.16 (m, 2 H), 1.41–1.39 (m,
2 H), 1.33 (s, 3 H), 1.26–1.24 (m, 16 H), 0.87 (t, J = 7.2 Hz, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 207.0, 180.3, 143.6,
133.5, 127.8, 122.1, 121.6, 108.9, 49.6, 45.1, 42.8, 31.8, 29.5 (2 C),
3-[2-(2-Methoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-one
(9):[3c] Colorless oil. 1H NMR (500 MHz, CDCl3): δ = 7.42–7.37
(m, 2 H), 7.24 (t, J = 7.5 Hz, 1 H), 7.13 (d, J = 5 Hz, 1 H), 6.97
(t, J = 7.5 Hz,1 H), 6.91 (d, J = 10 Hz, 1 H), 6.88–6.85 (m, 2 H),
3.91 (s, 3 H), 3.76 (d, J = 15 Hz, 1 H), 3.67 (d, J = 20 Hz, 1 H),
3.28 (s, 3 H), 1.39 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ
= 198.0, 180.8, 158.6, 143.8, 134.0, 133.6, 130.3, 127.6, 122.6, 122.0,
121.8, 120.5, 111.3, 108.0, 55.5, 51.2, 45.7, 26.4, 25.0 ppm. MS (EI,
70 eV): m/z (%) = 309 (49) [M+], 264 (12), 160 (33), 135 (100).
29.3, 29.2, 28.9, 26.3, 24.4, 23.4, 22.6, 14.0 ppm. IR (KBr): ν =
˜
1701, 1698 cm–1. MS (EI, 70 eV): m/z (%) = 357 (26) [M+], 174
(71), 160 (100). HRMS (ESI): m/z calcd. for C23H36NO2 [M +
H]+ 358.2746; found 358.2751.
3-[2-(3,4-Dimethoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-one
(10): Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.54 (d, J =
8.4 Hz, 1 H),7.33 (d, J = 2.0 Hz, 1 H), 7.25 (t, J = 7.2 Hz, 1 H),
7.14 (d, J = 7.2 Hz, 1 H), 6.98 (t, J = 7.6 Hz, 1 H), 6.91 (t, J =
8.0 Hz, 1 H), 6.84 (d, J = 8.4 Hz, 1 H), 3.92 (s, 3 H), 3.83 (s, 3 H),
3.69 (d, J = 17.6 Hz, 1 H), 3.63 (d, J = 17.6 Hz, 1 H), 3.31 (s, 3
H), 1.43 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.7,
180.7, 153.3, 148.9, 143.7, 133.9, 129.6, 127.7, 122.6, 122.1, 121.7,
110.0, 109.8, 108.1, 56.0, 55.8, 45.5, 45.3, 26.4, 25.0 ppm. IR (KBr):
1-Benzyl-3-[2-(4-methoxyphenyl)-2-oxoethyl]-3-methylindolin-2-one
1
(17):[3c] Yellow solid; m.p. 101.2–102.3 °C (uncorrected). H NMR
(500 MHz, CDCl3): δ = 7.85 (d, J = 9.0 Hz, 2 H), 7.41 (d, J =
7.5 Hz, 2 H), 7.33 (t, J = 7.5 Hz, 2 H), 7.25 (d, J = 9.0 Hz, 1 H),
7.13 (d, J = 7.0 Hz, 1 H), 7.08 (d, J = 9.0 Hz, 1 H), 6.92 (t, J =
7.5 Hz, 1 H), 6.86 (d, J = 9.0 Hz, 2 H), 6.72 (d, J = 8.0 Hz, 1 H),
5.08 (d, J = 16.0 Hz, 1 H), 4.95 (d, J = 16.0 Hz, 1 H), 3.81 (s, 3
H), 3.71–3.69 (m, 2 H), 1.48 (s, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 194.5, 180.8, 163.6, 142.9, 136.3, 134.0, 130.4, 128.7,
127.7, 127.4, 127.3, 122.2, 121.8, 113.7, 109.3, 55.5, 45.6, 44.0,
25.6 ppm. MS (EI, 70 eV): m/z (%) = 385 (42) [M+], 250 (9), 235
(50), 135 (100).
ν = 1692, 1684 cm–1. MS (EI, 70 eV): m/z (%) = 339 (43) [M+], 294
˜
(14), 165 (100). HRMS (ESI): m/z calcd. for C20H22NO4 [M +
H]+ 340.1549; found 340.1556.
3-[2-(Furan-2-yl)-2-oxoethyl]-1,3-dimethylindolin-2-one (11):[3c] Col-
orless oil. 1H NMR (500 MHz, CDCl3): δ = 7.51 (m, 1 H), 7.24 (t, 1-Acetyl-3-[2-(4-methoxyphenyl)-2-oxoethyl]-3-methylindolin-2-one
1
J = 10 Hz, 1 H), 7.16 (d, J = 10 Hz, 1 H), 7.07 (d, J = 5 Hz, 1 H),
6.97 (t, J = 7.5 Hz, 1 H), 6.87 (d, J = 5 Hz, 1 H), 6.47 (d, J = 5 Hz,
1 H), 3.58 (d, J = 10 Hz, 1 H), 3.44 (d, J = 7.5 Hz, 1 H), 3.29 (s,
3 H), 1.43 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 185.4,
180.3, 152.4, 146.2, 143.8, 133.4, 127.9, 122.2, 122.1, 116.9, 112.3,
108.1, 45.4, 45.3, 26.4, 24.5 ppm. MS (EI, 70 eV): m/z (%) = 269
(36) [M+], 224 (15), 210 (12), 160 (100).
(18): Colorless oil. H NMR (400 MHz, CDCl3): δ = 8.32 (d, J =
8.0 Hz, 2 H), 7.82 (d, J = 8.8 Hz, 2 H), 7.31–7.27 (m, 1 H), 7.13–
7.09 (m, 2 H), 6.88 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3 H), 3.81 (d, J =
18.0 Hz, 1 H), 3.68 (d, J = 18.0 Hz, 1 H), 2.74 (s, 3 H),1.48 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.2, 181.5, 171.3,
163.8, 140.0, 132.9, 130.3, 128.8, 128.1, 124.8, 120.9, 116.7, 113.7,
55.5, 47.0, 45.7, 26.7, 26.1 ppm. IR (KBr): ν = 1723, 1691,
˜
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O40043
/KAP1
Date: 16-04-14 11:59:57
Pages: 8
X.-H. Ouyang, R.-J. Song, J.-H. Li
FULL PAPER
1685 cm–1. MS (EI, 70 eV): m/z (%) = 337 (32) [M+], 264 (4), 135
3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1-methyl-3-phenylindolin-2-one
1
(100). HRMS (ESI): m/z calcd. for C20H20NO4 [M + H]+ 338.1392; (27):[3c] Yellow oil. H NMR (500 MHz, CDCl3): δ = 7.83 (d, J =
found 338.1398.
8.5 Hz, 2 H), 7.44 (d, J = 7.5 Hz, 2 H), 7.33–7.29 (m, 3 H), 7.25
(t, J = 7.5 Hz, 2 H), 7.03 (t, J = 7.5 Hz, 1 H), 6.93 (d, J = 7.5 Hz,
1 H), 6.86 (d, J = 8.5 Hz, 2 H), 4.12 (d, J = 18.0 Hz, 1 H), 4.04 (d,
J = 18.0 Hz, 1 H), 3.83 (s, 3 H), 3.29 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 194.2, 178.7, 163.5, 144.8, 139.7, 131.7,
130.3, 129.5, 128.6, 128.3, 127.5, 126.7, 124.1, 122.1, 113.6, 108.4,
55.4, 53.2, 46.6, 26.7 ppm. MS (EI, 70 eV): m/z (%) = 371 (56)
[M+], 326 (10), 278 (15), 236 (24), 222 (75), 135 (100).
3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1,3,5-trimethylindolin-2-one
(20):[3c] Colorless oil. H NMR (400 MHz, CDCl3): δ = 7.83 (d, J
1
= 78.8 Hz, 2 H), 7.04 (d, J = 8.0 Hz, 1 H), 6.94 (s, 1 H), 6.87 (d, J
= 8.8 Hz, 2 H), 6.78 (d, J = 8.0 Hz, 1 H), 3.84 (s, 3 H), 3.65 (d, J
= 17.6 Hz, 1 H), 3.59 (d, J = 18.0 Hz, 1 H), 3.29 (s, 3 H), 2.27 (s,
3 H), 1.41 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 194.6,
180.6, 163.4, 141.4, 133.9, 131.5, 130.2, 129.5, 127.9, 122.7, 113.5,
107.8, 55.4, 45.6, 45.3, 26.4, 25.0, 21.1 ppm. MS (EI, 70 eV): m/z
(%) = 323 (87) [M+], 278 (30), 174 (88), 135 (100).
Supporting Information (see footnote on the first page of this arti-
cle): 1H and 13C NMR spectra for 3-(2-oxoethyl)indolin-2-one
products.
5-Methoxy-3-[2-(4-methoxyphenyl)-2-oxoethyl]-1,3-dimethyl-
indolin-2-one (21):[3c] Colorless oil. 1H NMR (500 MHz, CDCl3): δ
= 7.82 (d, J = 9.0 Hz, 2 H), 6.85 (d, J = 9.0 Hz, 2 H), 6.80–6.74
(m, 3 H), 3.82 (s, 3 H), 3.72 (s, 3 H), 3.64 (d, J = 18.0 Hz, 1 H),
3.59 (d, J = 17.5 Hz, 1 H), 3.28 (s, 3 H), 1.42 (s, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 194.5, 180.3, 163.4, 155.6, 137.3,
135.3, 130.2, 129.4, 113.5, 111.3, 109.8, 108.2, 55.6, 55.3, 45.7, 45.3,
26.4, 24.9 ppm. MS (EI, 70 eV): m/z (%) = 339 (94) [M+], 294 (40),
280 (12), 254 (11), 190 (100), 135 (91).
Acknowledgments
The authors thank the National Natural Science Foundation of
China (NSFC) (grant number 21172060), the Specialized Research
Fund for the Doctoral Program of Higher Education (grant
number 20120161110041), and the Hunan Provincial Natural Sci-
ence Foundation of China (grant number 13JJ2018) for financial
support. Dr. R.-J. S. also thanks the China Postdoctoral Science
Foundation (grant number 2012M511716) and Hunan Province
Science and Technology Project (grant number 2013RS4026).
3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1,3-dimethyl-5-nitroindolin-2-
one (22):[3c] Yellow oil. H NMR (400 MHz, CDCl3): δ = 8.26 (d,
1
J = 8.8 Hz, 1 H), 7.99 (d, J = 2.4 Hz, 1 H), 7.81 (d, J = 9.2 Hz, 2
H), 6.98 (d, J = 8.4 Hz, 1 H), 6.88 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3
H), 3.78 (d, J = 18.0 Hz, 1 H), 3.73 (d, J = 18.0 Hz, 1 H), 3.39 (s,
3 H), 1.46 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 194.2,
180.8, 163.9, 149.8, 143.1, 135.0, 130.3, 128.8, 125.3, 117.3, 113.8,
107.6, 55.5, 46.0, 45.1, 26.9, 24.7 ppm. MS (EI, 70 eV): m/z (%) =
354 (13) [M+], 306 (10), 219 (30), 205 (39), 135 (100).
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7-Iodo-3-[2-(4-methoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-
one (23):[3c] Red oil. 1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J =
8.8 Hz, 2 H), 7.63 (d, J = 8.8 Hz, 1 H), 7.04 (d, J = 7.2 Hz, 1 H),
6.87 (d, J = 8.8 Hz, 2 H), 6.66 (t, J = 7.6 Hz, 1 H), 3.84 (s, 3 H),
3.69 (s, 3 H), 3.64 (s, 2 H), 1.39 (s, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 194.3, 181.5, 163.6, 144.2, 140.2, 137.1, 130.2, 129.2,
123.8, 121.2, 113.6, 71.9, 55.4, 45.9, 44.8, 30.3, 25.3 ppm. MS (EI,
70 eV): m/z (%) = 435 (43) [M+], 300 (6), 286 (13), 135 (100).
7-Bromo-3-[2-(4-methoxyphenyl)-2-oxoethyl]-1,3-dimethylindolin-2-
one (24):[3c] Yellow oil. H NMR (400 MHz, CDCl3): δ = 7.82 (d,
1
[2] T. Wu, X. Mu, G.-S. Liu, Angew. Chem. Int. Ed. 2011, 50,
12578; Angew. Chem. 2011, 123, 12786.
J = 8.8 Hz, 2 H), 7.34 (d, J = 8.4 Hz, 1 H), 7.01 (d, J = 7.2 Hz, 1
H), 6.87 (d, J = 8.8 Hz, 2 H), 6.80 (t, J = 7.6 Hz, 1 H), 3.84 (s, 3
H), 3.69 (s, 3 H), 3.65 (s, 2 H), 1.40 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 194.3, 181.2, 163.6, 141.2, 137.2, 133.3,
130.2, 129.2, 123.2, 120.5, 113.6, 102.6, 55.4, 46.0, 45.0, 30.0,
25.3 ppm. MS (EI, 70 eV): m/z (%) = 389 (12) [M+ + 2], 387 (12)
[M+], 240 (6), 238 (6), 135 (100).
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3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1,3,6-trimethylindolin-2-one
(25) and 3-[2-(4-Methoxyphenyl)-2-oxoethyl]-1,3,4-trimethylindolin-
2-one (26):[3c] Ratio 25/26 = 1.5:1; Colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 7.84–7.80 (m, 3.2 H), 7.15 (t, J = 8.0 Hz,
1 H), 7.01 (d, J = 7.6 Hz, 0.7 H), 6.86 (d, J = 8.80 Hz, 3.3 H),
6.79–6.72 (m, 2.5 H), 3.92 (d, J = 17.6 Hz, 1 H), 3.81 (s, 5 H),
3.68–3.55 (m, 2.4 H), 3.29 (s, 2 H), 3.28 (s, 3 H), 2.36 (s, 2 H), 2.29
(s, 3 H), 1.48 (s, 3 H), 1.41 (s, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 194.7, 181.0, 180.6, 163.4, 144.0, 143.8, 137.7, 132.7,
130.9, 130.5, 130.2, 130.1, 129.5, 129.2, 128.6, 127.5, 124.7 (2 C),
122.5, 121.4, 113.6, 113.5, 109.1, 105.9, 55.3, 46.1, 45.6, 45.1, 44.5,
29.6, 26.4, 26.3, 24.9, 22.8, 21.7, 18.1 ppm. MS (EI, 70 eV) for 25:
m/z (%) = 323 (79) [M+], 308 (6), 174 (77), 173 (83), 135 (100); MS
(EI, 70 eV) for 26: m/z [%] = 323 (60) [M+], 264 (4), 174 (68), 135
(100).
6
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O40043
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Date: 16-04-14 11:59:57
Pages: 8
A Tandem Route to 3-(2-Oxoethyl)indolin-2-ones
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Published Online: ᭿
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Job/Unit: O40043
/KAP1
Date: 16-04-14 11:59:57
Pages: 8
X.-H. Ouyang, R.-J. Song, J.-H. Li
FULL PAPER
Iron-Catalyzed Cyclization
X.-H. Ouyang, R.-J. Song,*
J.-H. Li* ........................................... 1–8
Iron-Catalyzed Oxidative 1,2-Carboacyl-
ation of Activated Alkenes with Alcohols:
A Tandem Route to 3-(2-Oxoethyl)indolin-
2-ones
A route to 3-(2-oxoethyl)indolin-2-ones is
presented that involves iron-catalyzed oxi-
dative tandem reaction of N-arylacryl-
amides with alcohols. This method re-
presents a new 1,2-difunctionalization of
activated alkenes with alcohols, and pro-
vides a shortcut to carbonyl-containing ox-
indoles from alcohols.
Keywords: Domino reactions / Cyclization /
Iron / Oxidation / Alkenes / Alcohols
8
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Eur. J. Org. Chem. 0000, 0–0