Room-temperature palladium-catalyzed intramolecular oxidative aminocarbonylation of vinylic C(sp2)-H bonds with amines and CO

Article abstract of DOI:10.1002/ejoc.201301284

A new, mild route to access 3-methyleneindolin-2-ones is presented that proceeds through a room-temperature, palladium-catalyzed intramolecular oxidative aminocarbonylation of alkenes with amines and CO. This method represents a new aminocarbonylation str

Full text of DOI:10.1002/ejoc.201301284

Job/Unit: O31284
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Date: 13-11-13 18:45:19
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FULL PAPER
DOI: 10.1002/ejoc.201301284
Room-Temperature Palladium-Catalyzed Intramolecular Oxidative
Aminocarbonylation of Vinylic C(sp2)–H Bonds with Amines and CO
Xu-Heng Yang,[a] Kai Li,[a] Ren-Jie Song,[a] and Jin-Heng Li*[a]
Keywords: Nitrogen heterocycles / Palladium / Carbonylation / Amines / Reaction mechanisms
A new, mild route to access 3-methyleneindolin-2-ones is
presented that proceeds through a room-temperature, palla-
dium-catalyzed intramolecular oxidative aminocarbonylation
of alkenes with amines and CO. This method represents a
new aminocarbonylation strategy by employing an oxidative
functionalization of a vinyl C(sp2)–H bond.
the amine prior to this insertion of CO. We reasoned that
vinylic C(sp2)–PdIIǟN complexation might readily form
under similar conditions, as a vinylic C(sp2)–H bond is
more reactive than an aryl C(sp2)–H bond. This complex
would then be treated with CO to access the aminocarb-
onylation product. Herein, we report a room-temperature,
palladium-catalyzed intramolecular oxidative aminocarb-
onylation of alkenes with amines and CO by using Ag2CO3
as the oxidant and PivOH (Piv = pivaloyl) as the promoter
(see Scheme 1, b). This method represents both a new ex-
ample of the direct oxidative aminocarbonylation of vinylic
C(sp2)–H bonds and a straightforward way to prepare 3-
methyleneindolin-2-ones,[8] which are motifs that are found
in many natural products and bioactive compounds.[9]
Introduction
Carbonylation is an important reaction because of its
broad applications in organic synthesis and industry and
for incorporating carbonyl groups into organic mo-
lecules.[1–7] Of its numerous applications, the transition-
metal-catalyzed carbonylation of organic molecules,[1–6]
which include organohalides,[2] alkynes,[3] and alkenes[4–6] as
well as some special compounds with C(sp2)–H bonds,[7]
with amines and CO has proven extremely effective for the
synthesis of amides. However, methods for the transition-
metal-catalyzed (often by Pd) aminocarbonylation of alk-
enes with amines and CO still face a huge challenge because
of the dicarbonylation of amines and the amination of alk-
enes with amines prior to aminocarbonylation, and thus
successful examples of aminocarbonylation are quite
rare.[4–6] To the best of our knowledge, the only reported
approach of an intramolecular aminocarbonylation of alk-
enes with amines and CO involves a Pd0-catalyzed pro-
cess,[6] which is achieved by cleavage of the carbon–carbon
π bond of the alkenes and transformation of the carbon–
carbon double bond into a carbon–carbon σ bond.[6]
Therefore, it would be a highly desirable synthetic technique
to develop new, mild routes for the aminocarbonylation of
alkenes.
Recently, elegant methods were established for the palla-
dium-catalyzed intramolecular oxidative aminocarb-
onylation of aryl C(sp2)–H bonds with amines and CO (see
Scheme 1, a).[7] During the process, the C(sp2)–PdIIǟN
complexation occurred through the insertion of PdII into
the aryl C(sp2)–H bond followed by the coordination with
Scheme 1. Pd-catalyzed C–H aminocarbonylation.
Results and Discussion
[a] State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan
University,
To test our hypothesis, (E)-N-methyl-2-styrylaniline (1a)
was employed for the reaction with CO, Pd(OAc)2, and the
oxidants (see Table 1). Gratifyingly, treatment of substrate
1a with CO, Pd(OAc)2, and Cu(OAc)2 in HOAc at 100 °C
afforded the desired product 2a in 72% yield (see Table 1,
Entry 1). Screening the amount of Pd(OAc)2 revealed that
Changsha 410082, China
E-mail: jhli@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.201301284.
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FULL PAPER
Table 1. Screening optimal conditions.[a]
Entry
[Pd]
Oxidant [equiv.]
Additive [equiv.]
Solvent
% Yield[b]
1
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
Cu(OAc)2 (2)
CuCl2 (2)
–
–
–
–
–
–
–
HOAc
HOAc
HOAc
HOAc
MeCN
DMF
toluene
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
72
53
73
66
34
trace
26
78
trace
80
2[c]
3[d]
4
5[e]
6[e]
7[e]
8
PivOH (5)
PivOH (5)
PivOH (5)
PivOH (5)
PivOH (5)
PivOH (0.1)
9
10
11
12[f]
13[f]
AgOAc (2)
Ag2CO3 (2)
Ag2CO3 (2)
Ag2CO3 (2)
82
85 (1:1.3)
36
[a] Reagents and conditions: 1a (0.3 mmol), CO (bubbled), [Pd] (5 mol-%), oxidant, additive, and solvent (2 mL) at 100 °C for 12 h.
[b] Isolated % yield. Z and E isomers were separated, and the Z/E ratio is given in parenthesis. [c] Pd(OAc)2 (2 mol-%). [d] Pd(OAc)2
(10 mol-%). [e] Some byproducts, as a result of the amination of the alkene with the amine, were detected by GC–MS analysis. [f] At
room temperature.
5 mol-% Pd(OAc)2 was viable for the reaction (see Table 1, substituted substrate 1g were inert under the reaction con-
Entries 1–3). PdCl2 as a catalyst was also highly reactive, ditions (i.e., products 2f and 2g). Gratifyingly, several sub-
albeit the yield was slightly lower (see Table 1, Entry 4). En- stituents that include an aryl, alkyl, ester, or CN group at
couraged by the results, the solvents MeCN, N,N-dimethyl- the terminal alkene were well tolerated to give products 2h–
formamide (DMF), and toluene were subsequently exam- 2q. For examples, (E)-N-methyl-2-vinylanilines 1h–1m,
ined, but they were less effective than HOAc. Moreover, which have either electron-rich or electron-deficient aryl
the reaction in DMF was completely sluggish (see Table 1, groups at the terminal alkene, underwent the reaction with
Entries 1 vs. 5–7). Interestingly, the addition of PivOH im- CO smoothly to afford the corresponding products 2h–2m
proved the reaction, and 5 equiv. PivOH gave the best re- in moderate yields. Significantly, some functional groups
sults (see Table 1, Entry 8). Some other oxidants, which in- such as the Br, Cl, or pyridin-2-yl groups were tolerated
clude CuCl2, AgOAc, and Ag2CO3, were investigated (see under the optimal conditions (i.e., to give products 2i, 2k
Table 1, Entries 9–11). Surprisingly, the reaction that em- and 2n), thereby making this methodology more useful to
ployed CuCl2 as the oxidant, which was previously reported organic synthesis.[9] Electron-poor alkenes 1p and 1q still
as an efficient oxidant for amination-carbonylation trans- afforded satisfactory yields (i.e., products 2p and 2q). No-
formations,[5] resulted in no detectable amount of product tably, only the (E) isomer 2q was produced from substrate
2a (see Table 1, Entry 9). Interestingly, the results showed 1q, which contained a CN group. The reason for this may
that changing the oxidant to either AgOAc or Ag2CO3 also be the interaction of the CN donor directed towards the
gave a good yield (see Table 1, Entries 10 and 11). Notably, palladium center.
substrate 1a was consumed completely at room temperature
We next set out to examine substituents on the aromatic
in 12 h to provide product 2a in 85% yield with an isolated ring of the aniline moiety, and the screening revealed that
Z/E ratio of 1:1.3 (Z and E isomers were separated by silica Me-, Cl-, and acetyl-substituted anilines 1r–1u were com-
gel column chromatography with hexane/ethyl acetate as patible under the optimal conditions to give products 2r–
the eluent, see Table 1, Entry 12).[10] However, the yield of 2u. For instance, (E)-N,4-dimethyl-2-styrylaniline (1r) pro-
2a was lowered sharply when the reaction was carried out vided the desired product 2r in 59% yield. Anilines 1s and
with 0.1 equiv. PivOH (see Table 1, Entry 13).
1t that contain a Cl group or two Cl groups, respectively,
As shown in Table 2, 2-vinylanilines 1b–1w were sub- also gave the corresponding products 2s and 2t in good
jected to the optimal reaction conditions.[10] Initially, the yields. The optimal conditions were also compatible with
effect of the substituent on the nitrogen atom of (E)-2-styr- substrates 1v and 1w that contained two substituents at the
ylanilines 1b–1g was investigated in the presence of CO, terminal alkene to provide products 2v and 2w in 51 and
Pd(OAc)2, Ag2CO3, and PivOH to give products 2b–2g. 61% yields, respectively.
Substrates 1b–1e, which contain nBu, Bn, allyl, or 2-methyl-
Interestingly, (E)-2,2Ј-(ethene-1,2-diyl)bis(N-methylanil-
allyl groups on the nitrogen atom, furnished the corre- ine) (1x) performed the aminocarbonylation twice to pro-
sponding products 2b–2e in good yields. Unfortunately, vide the two indolin-2-one rings, a unit in some bioactive
both the free NH2-substituted substrate 1f and the N-Ac- molecules and dyes,[11] of product 2x in 50% yield [see
2
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Intramolecular Oxidative Aminocarbonylation
Table 2. Scope of 2-vinylanilines (1).[a]
[a] Reagents and conditions: 1 (0.3 mmol), CO (bubbled), Pd(OAc)2 (5 mol-%), Ag2CO3 (2 equiv.), PivOH (5 equiv.), and MeCN (2 mL)
at room temperature for 12 h. The Z and E isomers were separated, and the Z/E ratio is given in parenthesis. [b] The Z/E ratio was
1
determined by H NMR analysis.
Scheme 2. Carbonylation of other substrates.
Scheme 2, Equation (1)]. However, our attempt at the changed upon the complete conversion of deuterium-substi-
aminocarbonylation of 2-(1,2-diphenylvinyl)-N-methyl- tuted substrate 1a-D2 into product 2a-D1. These results
aniline (1z) failed [see Scheme 2, Equation (2)].
suggest there is a different mechanism taking place from
To understand the mechanism, a deuterium labeling ex- the reported mechanism proposed by Alper.[6] Interestingly,
periment was performed [see Scheme 3, Equation (3)]. The the reaction of 1q with CO was carried out with 1 equiv. of
amount of deuterium at the terminal alkene remained un- Pd(OAc)2 for 4 h without the oxidant and acid to provide
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X.-H. Yang, K. Li, R.-J. Song, J.-H. Li
FULL PAPER
only the (E) isomer of 2q in 63% yield [see Scheme 3, Equa-
tion (4)]. The selectivity of the reaction with substrate 1q
was elucidated by HRMS (high resolution mass spectrome-
try) analysis after 1 h of reaction time (see Figure S1 in
Supporting Information). According to these results, the
three Pd-containing intermediates A–C were involved (see
Scheme 3), which implies that there is an interaction of the
CN donor that is directed towards the palladium center.
Scheme 4. Possible mechanism.
Conclusions
In summary, we have illustrated a new, mild protocol for
the synthesis of 3-methyleneindolin-2-ones by using a palla-
dium-catalyzed intramolecular oxidative aminocarb-
onylation of alkenes with amines and CO at room tempera-
ture. This present method was achieved by the direct
aminocarbonylation of the vinyl C(sp2)–H bond and pro-
vides a new access to bioactive 3-methyleneindolin-2-ones.
Scheme 3. Control experiments.
Although product 2a was obtained in 85% yield by using
5 equiv. of PivOH, the yield was reduced to 36% by using
0.1 equiv. of PivOH (see Table 1, Entries 12 and 13). More-
over, only 34% yield was obtained in the absence of the
acids (see Table 1, Entry 5), and 78% yield was achieved in
the presence of HOAc (see Table 1, Entry 1). These results
imply that the acidic conditions favor the reaction by help-
ing to remove the hydrogen atom of the amine and exchang-
ing –OAc from PdL2(OAc)2 with PivO– to make the Pd spe-
cies more active and enhance the yields.
Consequently, the possible mechanism outlined in
Scheme 4 is proposed on the basis of the present results and
the reported mechanisms.[1–7] Initially, Pd(OAc)2 coordi-
nates with MeCN to yield the PdL2(OAc)2 complex (L =
MeCN), and then an exchange with the acid HY (PivOH)
leads to the more active PdL2Y2 species. The nitrogen atom
in substrate 1 can readily complex with the PdL2Y2 species
to afford intermediate A.[6,7] Subsequently, two of the fol-
Experimental Section
General Methods: All materials and solvents were purchased from
commercial suppliers and used without additional purification. IR
measurements were performed with a FTIR SHIMADZU DR-
8000 spectrometer that was fitted with a Pike Technologies MIR-
acle Single Reflection ATR adapter. The 1H and 13C NMR spectro-
scopic data were recorded with a Bruker DRX-500 spectrometer
(1H NMR at 500 MHz and 13C NMR at 125 MHz) or a Bruker
DRX-400 spectrometer (1H NMR at 400 MHz and 13C NMR at
100 MHz). The NMR samples were dissolved in CDCl3 unless
otherwise noted. High resolution mass spectra were recorded with
a Bruker microTOF-QII (ESI) spectrometer. Preparative thin layer
chromatography was performed on silica gel plates with PF254 in-
dicator. Flash column chromatography was performed with silica
gel 60N unless otherwise noted.
Typical Experimental Procedure for the Room-Temperature Palla-
dium-Catalyzed Oxidative Intramolecular Aminocarbonylation: To a
lowing pathways may take place: (i) sequential reactions of flask (10 mL) were added 2-vinylaniline 1 (0.3 mmol), Pd(OAc)2
(5 mol-%), Ag2CO3 (2 equiv.), PivOH (5 equiv.), and MeCN
(2 mL). Then, CO was bubbled through a tube into the mixture,
and the reaction was stirred at room temperature for 12 h until
there was complete consumption of starting material as monitored
by TLC and/or GC–MS analysis. Upon completion, the reaction
mixture was washed with brine, and the aqueous phase was re-
extracted with ethyl acetate. The combined organic extracts were
dried with Na2SO4 and concentrated in vacuo. The resulting resi-
due was purified by silica gel column chromatography (hexane/
ethyl acetate, 5:1) to afford the desired product 2. Caution: Carbon
monoxide (CO) is a colorless, tasteless, and highly poisonous gas.
the amine with CO and the insertion of the PdL2Y2 species
into the vinyl C–H bond of intermediate A to give PdIII
intermediate D[7] or ii) sequential reactions of the amine
with CO and an oxidative Heck reaction to form intermedi-
ate E.[6c] Finally, the reductive elimination of either interme-
diate D or E affords both product 2 and the Pd0Ln species.
The deuterium labeling experiment displayed in Scheme 3,
Equation (3) does not support the latter pathway because
no exchange takes place between the hydrogen and deuter-
ium atoms.
4
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Intramolecular Oxidative Aminocarbonylation
3-Benzylidene-1-methylindolin-2-one (2a):[3l,8j] (Z/E, 1:1.3). Data for
(Z) isomer: yellow solid; m.p. 95.4–96.5 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.29 (d, J = 8.5 Hz, 2 H), 7.53 (d, J = 8.5 Hz, 2 H),
125.9, 124.4, 121.8, 119.0, 117.3, 108.6, 42.2 ppm. IR (KBr): ν =
˜
1767, 1654, 1538 cm–1. LRMS (EI, 70 eV): m/z (%) = 261 (100)
[M]+, 232 (15), 184 (27), 165 (38). HRMS (ESI): calcd. for
7.47–7.41 (m, 3 H), 7.28 (t, J = 7.5 Hz, 1 H), 7.07 (t, J = 7.5 Hz, C18H16NO [M + H]+ 262.1246; found 262.1258. Data for (E) iso-
1 H), 6.81 (d, J = 8.0 Hz, 1 H), 3.27 (s, 3 H) ppm. 13C NMR mer: yellow solid; m.p. 136.7–137.4 °C. 1H NMR (500 MHz,
(125 MHz, CDCl3): δ = 166.1, 142.4, 137.0, 133.8, 131.9, 130.4, CDCl3): δ = 7.88 (s, 1 H), 7.64 (t, J = 7.5 Hz, 3 H), 7.48–7.40 (m,
128.9, 128.2, 126.1, 124.4, 121.8, 118.9, 107.8, 25.9 ppm. IR (KBr):
3 H), 7.25–7.21 (m, 1 H), 6.88–6.82 (m, 2 H), 5.91–5.85 (m, 1 H),
5.28–5.22 (m, 2 H), 4.43–4.42 (m, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 168.1, 143.4, 137.3, 134.9, 131.6, 129.6, 129.5, 129.2,
128.6, 127.0, 122.8, 121.7, 121.2, 117.4, 109.0, 42.3 ppm. IR (KBr):
ν = 1716, 1658, 1504 cm–1. LRMS (EI, 70 eV): m/z (%) = 235 (100)
˜
[M]+, 207 (18), 159 (42), 117 (9). Data for (E) isomer: yellow solid;
m.p. 106.5–107.8 °C. 1H NMR (500 MHz, CDCl3): δ = 7.86 (s, 1
H), 7.65–7.61 (m, 3 H), 7.48–7.41 (m, 3 H), 7.26 (t, J = 8.0 Hz, 1
ν = 1767, 1654, 1538 cm–1. LRMS (EI, 70 eV): m/z (%) = 261 (100)
˜
H), 6.87 (t, J = 8.0 Hz, 1 H), 6.82 (d, J = 7.5 Hz, 1 H), 3.28 (s, 3 [M]+, 232 (18), 184 (30), 165 (41).
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.4, 144.2, 137.1,
3-Benzylidene-1-(2-methylallyl)indolin-2-one (2e): (Z/E, 2:1). Data
134.9, 129.7, 129.4, 129.3, 128.6, 127.2, 122.7, 121.7, 121.1, 108.1,
for (Z) isomer: yellow solid; m.p. 186.1–188.6 °C. 1H NMR
(500 MHz, CDCl3): δ = 8.30 (d, J = 8.0 Hz, 2 H), 7.56 (s, 1 H),
7.54 (d, J = 7.5 Hz, 1 H), 7.45–7.40 (m, 3 H), 7.23 (t, J = 7.5 Hz,
1 H), 7.04 (t, J = 7.5 Hz, 1 H), 6.80 (d, J = 7.5 Hz, 1 H), 4.92 (s,
26.1 ppm. IR (KBr): ν = 1716, 1658, 1504 cm–1. LRMS (EI, 70 eV):
˜
m/z (%) = 235 (100) [M]+, 207 (21), 159 (45), 117 (12).
3-Benzylidene-1-butylindolin-2-one (2b): (Z/E, 2:1). Data for (Z)
isomer: yellow solid; m.p. 171.6–173.2 °C. 1H NMR (500 MHz, 1 H), 4.87 (s, 1 H), 4.33 (s, 2 H), 1.75 (s, 3 H) ppm. 13C NMR
CDCl3): δ = 8.29 (d, J = 8.5 Hz, 2 H), 7.54–7.53 (m, 2 H), 7.46–
7.39 (m, 3 H), 7.29–7.26 (m, 1 H), 7.05 (t, J = 8.5 Hz, 1 H), 6.83
(125 MHz, CDCl3): δ = 165.9, 141.8, 139.4, 137.3, 133.8, 132.0,
130.5, 128.8, 128.2, 125.8, 124.3, 121.8, 118.9, 112.2, 108.8, 45.6,
(d, J = 8.0 Hz, 1 H), 3.77 (t, J = 7.5 Hz, 2 H), 1.72–1.66 (m, 2 19.9 ppm. IR (KBr): ν = 1765, 1637, 1585 cm–1. LRMS (EI, 70 eV):
˜
H), 1.45–1.39 (m, 2 H), 0.96 (t, J = 7.5 Hz, 3 H) ppm. 13C NMR
m/z (%) = 275 (100) [M]+, 258 (49), 206 (19), 165 (30). HRMS
(125 MHz, CDCl3): δ = 166.0, 141.9, 137.0, 133.8, 131.9, 130.4, (ESI): calcd. for C19H18NO [M + H]+ 276.1383; found 276.1386.
1
128.8, 128.2, 126.2, 124.5, 121.6, 119.0, 108.1, 39.7, 29.7, 20.3,
Data for (E) isomer: yellow solid; m.p. 170.3–171.6 °C. H NMR
(400 MHz, CDCl3): δ = 7.89 (s, 1 H), 7.65 (t, J = 8.0 Hz, 3 H),
13.8 ppm. IR (KBr): ν = 1763, 1629, 1546 cm–1. LRMS (EI, 70 eV):
˜
m/z (%) = 277 (82) [M]+, 234 (100), 206 (50), 178 (24). HRMS 7.48–7.42 (m, 3 H), 7.23–7.20 (m, 1 H), 6.89–6.82 (m, 2 H), 4.95
(ESI): calcd. for C19H20NO [M + H]+ 278.1556; found 278.1589.
(s, 1 H), 4.90 (s, 1 H), 4.35 (s, 2 H), 1.77 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 168.4, 143.6, 139.2, 137.4, 135.0, 129.7,
1
Data for (E) isomer: yellow solid; m.p. 158.7–159.4 °C. H NMR
(500 MHz, CDCl3): δ = 7.85 (s, 1 H), 7.65–7.61 (m, 3 H), 7.48– 129.5, 129.4, 128.6, 127.0, 122.7, 121.7, 121.1, 112.4, 109.2, 45.9,
7.40 (m, 3 H), 7.26–7.23 (m, 1 H), 6.88–6.83 (m, 2 H), 3.79 (t, J = 19.9 ppm. IR (KBr): ν = 1765, 1637, 1585 cm–1. LRMS (EI, 70 eV):
˜
7.5 Hz, 2 H), 1.73–1.67 (m, 2 H), 1.45–1.41 (m, 2 H), 0.97 (t, J =
7.5 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.4, 143.7,
137.1, 135.1, 129.7, 129.4, 129.2, 128.6, 127.3, 122.8, 121.5, 121.3,
m/z (%) = 275 (100) [M]+, 258 (52), 206 (22), 165 (32).
1-Methyl-3-(4-methylbenzylidene)indolin-2-one
(2h):[3l,8j]
(Z/E,
1
1.2:1). Data for (Z) isomer: yellow solid; m.p. 128.4–129.5 °C. H
NMR (500 MHz, CDCl3): δ = 8.23 (d, J = 8.0 Hz, 2 H), 7.53–7.51
(m, 2 H), 7.29–7.25 (m, 3 H), 7.05 (t, J = 7.5 Hz, 1 H), 6.80 (d, J =
7.5 Hz, 1 H), 3.28 (s, 3 H), 2.41 (s, 3 H) ppm. 13C NMR (125 MHz,
108.4, 39.8, 29.7, 20.2, 13.8 ppm. IR (KBr): ν = 1763, 1629,
˜
1546 cm–1. LRMS (EI, 70 eV): m/z (%) = 277 (85) [M]+, 234 (100),
206 (48), 178 (26).
1-Benzyl-3-benzylideneindolin-2-one (2c):[3l,8j] (Z/E, 1.2:1). Data for CDCl3): δ = 166.2, 142.1, 141.1, 137.2, 132.1, 131.2, 129.0, 128.5,
(Z) isomer: yellow solid; m.p. 187.3–188.4 °C. 1H NMR (500 MHz,
125.1, 124.6, 121.7, 118.7, 107.8, 25.9, 21.7 ppm. IR (KBr): ν =
˜
CDCl3): δ = 8.32 (d, J = 7.5 Hz, 2 H), 7.59 (s, 1 H), 7.54 (d, J = 1747, 1660, 1540 cm–1. LRMS (EI, 70 eV): m/z (%) = 249 (100)
7.0 Hz, 1 H), 7.48–7.42 (m, 3 H), 7.34–7.28 (m, 4 H), 7.26–7.23 (m, [M]+, 248 (79), 158 (49), 123 (17). Data for (E) isomer: yellow solid;
1 H), 7.18 (t, J = 7.0 Hz, 1 H), 7.03 (t, J = 7.5 Hz, 1 H), 6.72 (d,
J = 8.0 Hz, 1 H), 4.99 (s, 2 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 166.1, 141.5, 137.4, 136.2, 133.8, 132.0, 130.5, 128.8, 128.7,
128.3, 127.5, 127.3, 125.8, 124.4, 121.9, 119.0, 108.8, 43.6 ppm. IR
m.p. 118.6–119.4 °C. 1H NMR (500 MHz, CDCl3): δ = 7.83 (s, 1
H), 7.69 (d, J = 7.5 Hz, 1 H), 7.56 (d, J = 8.0 Hz, 2 H), 7.26 (t, J
= 8.0 Hz, 3 H), 6.89 (t, J = 8.0 Hz, 1 H), 6.82 (d, J = 7.5 Hz, 1 H),
3.28 (s, 3 H), 2.42 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ
= 168.6, 144.1, 139.9, 137.5, 132.0, 129.5, 129.4, 129.3, 126.4, 122.6,
(KBr): ν = 1759, 1644, 1576 cm–1. LRMS (EI, 70 eV): m/z (%) =
˜
311 (68) [M]+, 206 (11), 165 (24), 91 (100). Data for (E) isomer: 121.7, 121.3, 108.1, 26.1, 21.5 ppm. IR (KBr): ν = 1747, 1660,
˜
1
yellow solid; m.p. 153.6–154.3 °C. H NMR (400 MHz, CDCl3): δ
= 7.93 (s, 1 H), 7.67–7.62 (m, 3 H), 7.50–7.45 (m, 3 H), 7.35–7.30
(m, 4 H), 7.28–7.25 (m, 1 H), 7.14 (t, J = 8.0 Hz, 1 H), 6.84 (t, J
= 8.0 Hz, 1 H), 6.72 (d, J = 8.0 Hz, 1 H), 5.00 (s, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 168.6, 143.3, 137.6, 136.0, 134.9,
132.0, 129.7, 129.6, 129.3, 128.8, 128.7, 128.6, 127.5, 127.3, 122.8,
1540 cm–1. LRMS (EI, 70 eV): m/z (%) = 249 (100) [M]+, 248 (82),
158 (48), 123 (15).
3-(4-Bromobenzylidene)-1-methylindolin-2-one (2i):[12a] (Z/E, 1:1.3).
1
Data for (Z) isomer: yellow solid; m.p. 144.3–145.9 °C. H NMR
(400 MHz, CDCl3): δ = 8.18 (d, J = 8.0 Hz, 2 H), 7.56 (d, J =
8.0 Hz, 2 H), 7.51 (d, J = 8.0 Hz, 1 H), 7.43 (s, 1 H), 7.29 (t, J =
8.0 Hz, 1 H), 7.06 (t, J = 8.0 Hz, 1 H), 6.81 (d, J = 8.0 Hz, 1 H),
3.27 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.1, 142.4,
135.4, 133.4, 132.7, 131.5, 129.2, 126.7, 124.9, 124.1, 121.9, 119.0,
121.8, 109.2, 43.7 ppm. IR (KBr): ν = 1759, 1644, 1576 cm–1.
˜
LRMS (EI, 70 eV): m/z (%) = 311 (70) [M]+, 206 (14), 165 (27), 91
(100).
1-Allyl-3-benzylideneindolin-2-one (2d): (Z/E, 1:1.1). Data for (Z)
108.0, 25.9 ppm. IR (KBr): ν = 1759, 1645, 1536 cm–1. LRMS (EI,
˜
isomer: yellow solid; m.p. 157.4–158.3 °C. 1H NMR (500 MHz, 70 eV): m/z (%) = 315 (88) [M + 2]+, 313 (88) [M]+, 158 (100), 117
CDCl3): δ = 8.29 (d, J = 8.0 Hz, 2 H), 7.54 (t, J = 7.5 Hz, 2 H),
(51). Data for (E) isomer: yellow solid; m.p. 121.5–122.7 °C. 1H
7.46–7.41 (m, 3 H), 7.24 (t, J = 7.5 Hz, 1 H), 7.05 (t, J = 7.5 Hz, NMR (400 MHz, CDCl3): δ = 7.75 (s, 1 H), 7.61–7.55 (m, 3 H),
1 H), 6.81 (d, J = 7.5 Hz, 1 H), 5.91–5.83 (m, 1 H), 5.26–5.20 (m, 7.51 (d, J = 8.0 Hz, 2 H), 7.29 (t, J = 8.0 Hz, 1 H), 6.89 (d, J =
2 H), 4.41 (d, J = 4.0 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3): 8.0 Hz, 1 H), 6.83 (t, J = 8.0 Hz, 1 H), 3.28 (s, 3 H) ppm. 13C NMR
δ = 165.7, 141.5, 137.3, 133.8, 131.9, 131.6, 130.5, 128.8, 128.2,
(125 MHz, CDCl3): δ = 168.3, 144.4, 135.5, 133.9, 131.9, 130.8,
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O31284
/KAP1
Date: 13-11-13 18:45:19
Pages: 9
X.-H. Yang, K. Li, R.-J. Song, J.-H. Li
FULL PAPER
130.1, 127.8, 123.7, 122.7, 121.9, 120.9, 108.3, 26.2 ppm. IR (KBr):
H), 7.91 (d, J = 8.0 Hz, 1 H), 7.85–7.80 (m, 2 H), 7.61 (s, 1 H),
7.52–7.45 (m, 3 H), 7.25 (t, J = 7.5 Hz, 1 H), 7.04 (t, J = 7.5 Hz,
1 H), 6.76 (d, J = 7.5 Hz, 1 H), 3.24 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 166.1, 142.2, 137.0, 134.1, 133.0, 132.9,
131.5, 129.1, 128.8, 128.6, 127.6, 127.5, 127.4, 126.2, 126.0, 124.4,
ν = 1759, 1645, 1536 cm–1. LRMS (EI, 70 eV): m/z (%) = 315 (86)
˜
[M + 2]+, 313 (86) [M]+, 158 (100), 117 (55).
1-Methyl-3-(4-nitrobenzylidene)indolin-2-one (2j):[12a] (Z/E, 1.6:1).
Data for (Z) isomer: red solid; m.p. 187.6–189.1 °C. 1H NMR
(500 MHz, CDCl3): δ = 8.36 (d, J = 8.5 Hz, 2 H), 8.26 (d, J =
7.0 Hz, 2 H), 7.54 (d, J = 7.5 Hz, 1 H), 7.51 (s, 1 H), 7.35 (t, J =
7.0 Hz, 1 H), 7.09 (t, J = 7.5 Hz, 1 H), 6.83 (d, J = 8.0 Hz, 1 H),
3.27 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.6, 147.9,
143.0, 139.8, 133.0, 132.2, 130.2, 129.6, 123.4, 123.3, 122.2, 119.7,
121.8, 118.8, 107.8, 25.9 ppm. IR (KBr): ν = 1749, 1648, 1563 cm–1.
˜
LRMS (EI, 70 eV): m/z (%) = 285 (100) [M]+, 207 (16), 158 (35),
142 (15). HRMS (ESI): calcd. for C20H16NO [M + H]+ 286.1226;
found 286.1229. Data for (E) isomer: yellow solid; m.p. 178.6–
1
181.5 °C. H NMR (500 MHz, CDCl3): δ = 8.12 (s, 1 H), 8.00 (s,
1 H), 7.92–7.85 (m, 3 H), 7.72 (d, J = 8.5 Hz, 1 H), 7.68–7.66 (m,
1 H), 7.55–7.53 (m, 2 H), 7.28–7.25 (m, 1 H), 6.88–6.82 (m, 2 H),
3.30 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.5, 144.3,
137.1, 133.6, 133.0, 132.4, 129.8, 129.3, 128.4, 128.2, 127.8, 127.3,
127.2, 126.7, 126.4, 122.7, 121.8, 121.2, 108.2, 26.2 ppm. IR (KBr):
108.3, 26.0 ppm. IR (KBr): ν = 1788, 1675, 1569 cm–1. LRMS (EI,
˜
70 eV): m/z (%) = 280 (24) [M]+, 250 (41), 207 (100), 158 (26). Data
for (E) isomer: red solid; m.p. 167.6–168.5 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.33 (d, J = 9.0 Hz, 2 H), 7.80–7.78 (m, 3 H), 7.43 (d,
J = 8.0 Hz, 1 H), 7.32 (t, J = 8.0 Hz, 1 H), 6.90 (t, J = 8.0 Hz, 1
H), 6.85 (d, J = 7.5 Hz, 1 H), 3.29 (s, 3 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 167.7, 147.9, 144.8, 141.8, 133.3, 130.9,
130.0, 129.9, 124.0, 122.9, 122.1, 120.3, 108.6, 26.3 ppm. IR (KBr):
ν = 1749, 1648, 1563 cm–1. LRMS (EI, 70 eV): m/z (%) = 285 (100)
˜
[M]+, 207 (18), 158 (37), 142 (19).
(E)-1-Methyl-3-(pyridin-2-ylmethylene)indolin-2-one (2n):[12b] Yel-
ν = 1788, 1675, 1569 cm–1. LRMS (EI, 70 eV): m/z (%) = 280 (26)
low solid; m.p. 113.7–114.3 °C. H NMR (500 MHz, CDCl3): δ =
1
˜
[M]+, 250 (45), 207 (100), 158 (28).
9.00 (d, J = 7.5 Hz, 1 H), 8.85 (d, J = 4.5 Hz, 1 H), 7.76 (t, J =
8.0 Hz, 1 H), 7.72 (s, 1 H), 7.59 (d, J = 8.0 Hz, 1 H), 7.33–7.27 (m,
2 H), 7.05 (t, J = 7.5 Hz, 1 H), 6.80 (d, J = 8.0 Hz, 1 H), 3.28 (s,
3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 169.0, 153.8, 149.5,
144.8, 136.5, 134.4, 130.4, 129.1, 127.8, 123.5, 122.1 (2 C), 121.5,
3-(3-Chlorobenzylidene)-1-methylindolin-2-one (2k): (Z/E, 1.3:1).
1
Data for (Z) isomer: yellow solid; m.p. 106.9–108.4 °C. H NMR
(500 MHz, CDCl3): δ = 8.35 (s, 1 H), 8.14–8.12 (m, 1 H), 7.51 (d,
J = 7.5 Hz, 1 H), 7.44 (s, 1 H), 7.39–7.35 (m, 2 H), 7.31 (t, J =
7.5 Hz, 1 H), 7.07 (t, J = 7.5 Hz, 1 H), 6.82 (d, J = 7.5 Hz, 1 H),
3.28 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 165.9, 142.6,
135.4, 135.0, 134.1, 131.4, 130.2, 129.9, 129.4 (2 C), 127.4, 124.0,
107.6, 26.2 ppm. IR (KBr): ν = 1764, 1655, 1534 cm–1. LRMS (EI,
˜
70 eV): m/z (%) = 236 (70) [M]+, 208 (64), 158 (100), 130 (40).
3-Heptylidene-1-methylindolin-2-one (2o): (Z/E, 1:1). Data for mix-
122.0, 119.1, 108.0, 26.0 ppm. IR (KBr): ν = 1745, 1689, 1539 cm–1. ture of (Z) and (E) isomers: yellow solid. 1H NMR (500 MHz,
˜
LRMS (EI, 70 eV): m/z (%) = 271 (34) [M + 2]+, 269 (99) [M]+,
204 (21), 158 (100), 117 (23). HRMS (ESI): calcd. for C16H13ClNO 7.07–7.02 (m, 2 H), 6.83 (d, J = 8.0 Hz, 1 H), 3.24 (s, 3 H), 2.70–
CDCl3): δ = 7.54 (d, J = 4.0 Hz, 1 H), 7.28 (t, J = 8.0 Hz, 1 H),
[M + H]+ 270.0680; found 270.0681. Data for (E) isomer: yellow
solid; m.p. 80.4–81.6 °C. 1H NMR (500 MHz, CDCl3): δ = 7.76 (s,
1 H), 7.61 (s, 1 H), 7.54–7.50 (m, 2 H), 7.41–7.40 (m, 2 H), 7.29 (t,
J = 8.0 Hz, 1 H), 6.90 (t, J = 7.5 Hz, 1 H), 6.83 (d, J = 8.0 Hz, 1
H), 3.28 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.2,
144.5, 136.8, 135.0, 134.7, 130.2, 130.0, 129.4, 129.0, 128.3, 127.3,
2.65 (m, 2 H), 1.68–1.62 (m, 2 H), 1.46–1.39 (m, 2 H), 1.33–1.31
(m, 4 H), 0.89 (t, J = 4.0 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 168.0, 143.6, 142.4, 128.7, 127.5, 123.4, 122.4, 122.0,
108.0, 31.6, 29.4, 29.2, 28.6, 26.0, 22.6, 14.1 ppm. IR (KBr): ν =
˜
1749, 1648, 1563 cm–1. LRMS (EI, 70 eV): m/z (%) = 243 (91)
[M]+, 174 (90), 161 (100), 145 (62). HRMS (ESI): calcd. for
C16H22NO [M + H]+ 244.1696; found 244.1688.
122.8, 122.0, 120.7, 108.3, 26.2 ppm. IR (KBr): ν = 1745, 1689,
˜
1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (36) [M + 2]+, 269
Butyl 2-(1-Methyl-2-oxoindolin-3-ylidene)acetate (2p):[13] (Z/E,
(96) [M]+, 204 (25), 158 (100), 117 (26).
1
1:1.4). Data for (Z) isomer: yellow solid; m.p. 162.5–163.7 °C. H
3-(3-Methoxybenzylidene)-1-methylindolin-2-one (2l): (Z/E, 1.3:1).
Data for (Z) isomer: yellow solid; m.p. 106.9–108.4 °C. H NMR
NMR (500 MHz, CDCl3): δ = 7.72 (d, J = 7.5 Hz, 1 H), 7.22 (t, J
= 7.5 Hz, 1 H), 6.99 (t, J = 7.5 Hz, 1 H), 6.62 (d, J = 7.5 Hz, 1 H),
4.68 (s, 1 H), 4.17–4.13 (m, 1 H), 4.00–3.96 (m, 1 H), 3.04 (s, 3 H),
1.50–1.43 (m, 2 H), 1.22–1.19 (m, 2 H), 0.83 (t, J = 7.5 Hz, 3
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 175.2, 170.4, 144.2,
132.4, 129.4, 125.8, 125.3, 122.8, 122.5, 107.6, 64.6, 30.5, 26.0, 18.8,
1
(400 MHz, CDCl3): δ = 8.34 (s, 1 H), 8.64 (d, J = 8.0 Hz, 1 H),
7.52 (d, J = 8.0 Hz, 2 H), 7.36–7.26 (m, 2 H), 7.04 (t, J = 8.0 Hz,
1 H), 7.06 (d, J = 8.0 Hz, 1 H), 6.81 (d, J = 8.0 Hz, 1 H), 3.92 (s,
3 H), 3.28 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.2,
159.5, 142.3, 137.1, 135.2, 129.1, 128.9, 126.2, 125.2, 124.4, 121.8,
13.6 ppm. IR (KBr): ν = 1718, 1654, 1571 cm–1. LRMS (EI, 70 eV):
˜
118.9, 117.6, 115.8, 107.9, 55.5, 26.0 ppm. IR (KBr): ν = 1745,
m/z (%) = 259 (43) [M]+, 186 (55), 159 (100), 130 (54). Data for
(E) isomer: yellow solid; m.p. 184.8–185.3 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.55 (d, J = 7.5 Hz, 1 H), 7.37 (t, J = 7.5 Hz, 1 H),
7.06 (t, J = 7.5 Hz, 1 H), 6.91 (s, 1 H), 6.79 (d, J = 7.5 Hz, 1 H),
4.27 (t, J = 6.5 Hz, 2 H), 3.23 (s, 3 H), 1.75–1.69 (m, 2 H), 1.49–
1.41 (m, 2 H), 0.97 (t, J = 6.5 Hz, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 167.6, 165.8, 145.9, 137.8, 132.4, 128.7, 122.8, 122.5,
˜
1689, 1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (34) [M + 2]+,
269 (99) [M]+, 204 (21), 158 (100), 117 (23). HRMS (ESI): calcd.
for C16H13ClNO [M + H]+ 270.0680; found 270.0681. Data for
(E) isomer: yellow solid; m.p. 80.4–81.6 °C. 1H NMR (400 MHz,
CDCl3): δ = 7.75 (s, 1 H), 7.59 (d, J = 8.0 Hz, 1 H), 7.30 (t, J =
8.0 Hz, 1 H), 7.21–7.15 (m, 2 H), 7.08 (s, 1 H), 6.88 (d, J = 8.0 Hz,
1 H), 6.81 (t, J = 8.0 Hz, 1 H), 6.75 (t, J = 8.0 Hz, 1 H), 3.76 (s, 3
H), 3.20 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.4,
159.6, 144.2, 137.0, 136.2, 129.8, 129.7, 127.3, 122.9, 121.8, 121.7,
119.8, 108.1, 65.0, 30.6, 26.2, 19.1, 13.7 ppm. IR (KBr): ν = 1718,
˜
1654, 1571 cm–1. LRMS (EI, 70 eV): m/z (%) = 259 (41) [M]+, 186
(52), 159 (100), 130 (52).
121.1, 115.4, 114.2, 108.1, 55.3, 26.1 ppm. IR (KBr): ν = 1745,
˜
(E)-2-(1-Methyl-2-oxoindolin-3-ylidene)acetonitrile (2q):[14] Yellow
solid; m.p. 232.7–233.4 °C. H NMR (500 MHz, CDCl3): δ = 8.06
(d, J = 7.5 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 1 H), 7.13 (t, J = 7.5 Hz,
1 H), 6.84 (d, J = 8.0 Hz, 1 H), 6.32 (s, 1 H), 3.23 (s, 3 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 165.2, 145.6, 143.5, 133.7, 124.9,
1689, 1539 cm–1. LRMS (EI, 70 eV): m/z (%) = 271 (36) [M + 2]+,
1
269 (96) [M]+, 204 (25), 158 (100), 117 (26).
1-Methyl-3-(naphthalen-2-ylmethylene)indolin-2-one (2m): (Z/E,
1
1.8:1). Data for (Z) isomer: yellow solid; m.p. 213.4–215.2 °C. H
NMR (500 MHz, CDCl3): δ = 8.72 (s, 1 H), 8.46 (d, J = 8.0 Hz, 1
123.2, 119.2, 116.1, 108.8, 97.5, 26.3 ppm. IR (KBr): ν = 1756,
˜
6
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O31284
/KAP1
Date: 13-11-13 18:45:19
Pages: 9
Intramolecular Oxidative Aminocarbonylation
1672, 1569 cm–1. LRMS (EI, 70 eV): m/z (%) = 184 (100) [M]+, 155
(96), 130 (34), 114 (19).
26.2 ppm. IR (KBr): ν = 1787, 1608, 1512 cm–1. LRMS (EI, 70 eV):
˜
m/z (%) = 277 (62) [M]+, 262 (100), 207 (23), 165 (17). HRMS
(ESI): calcd. for C18H16NO2 [M + H]+ 278.1237; found 278.1241.
3-Benzylidene-1,5-dimethylindolin-2-one (2r): (Z/E, 1.5:1). Data for
(Z) isomer: yellow solid; m.p. 143.5–145.1 °C. 1H NMR (500 MHz,
CDCl3): δ = 8.28 (d, J = 7.5 Hz, 2 H), 7.50 (s, 1 H), 7.46–7.40 (m,
3 H), 7.34 (s, 1 H), 7.08 (d, J = 8.0 Hz, 1 H), 6.69 (d, J = 7.5 Hz,
1 H), 3.24 (s, 3 H), 2.38 (s, 3 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 166.2, 140.2, 136.6, 133.9, 131.9, 131.2, 130.3, 129.3,
(E)-1-Methyl-3-(1-Phenylethylidene)indolin-2-one (2v):.[15] Yellow
solid; m.p. 161.4–162.8 °C. 1H NMR (400 MHz, CDCl3): δ = 7.50–
7.44 (m, 3 H), 7.29–7.26 (m, 3 H), 7.13 (d, J = 8.0 Hz, 1 H), 6.75
(d, J = 7.6 Hz, 1 H), 6.63 (t, J = 7.6 Hz, 1 H), 6.13 (d, J = 7.6 Hz,
1 H), 3.28 (s, 3 H), 2.81 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 168.2, 154.9, 143.0, 142.3, 129.2, 128.3, 128.1, 126.5,
128.2, 126.3, 124.3, 119.7, 107.6, 25.9, 21.2 ppm. IR (KBr): ν =
˜
1776, 1653, 1586 cm–1. LRMS (EI, 70 eV): m/z (%) = 249 (100)
[M]+, 220 (27), 172 (64), 123 (26). HRMS (ESI): calcd. for
C17H16NO [M + H]+ 250.1226; found 250.1231. Data for (E) iso-
mer: yellow solid; m.p. 127.1–128.3 °C. 1H NMR (500 MHz,
CDCl3): δ = 7.83 (s, 1 H), 7.64 (d, J = 7.5 Hz, 2 H), 7.49–7.42 (m,
4 H), 7.07 (d, J = 7.5 Hz, 1 H), 6.71 (d, J = 8.0 Hz, 1 H), 3.26 (s,
3 H), 2.22 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 168.5,
142.1, 136.8, 135.1, 131.1, 130.1, 129.4, 129.3, 128.6, 127.4, 123.4,
˜
123.4, 122.8, 122.6, 121.3, 107.4, 25.7, 22.9 ppm. IR (KBr): ν =
1758, 1674, 1565 cm–1. LRMS (EI, 70 eV): m/z (%) = 249 (100)
[M]+, 172 (21), 132 (59), 117 (28).
3-(Diphenylmethylene)-1-methylindolin-2-one (2w):[15] Yellow solid;
1
m.p. 214.6–215.3 °C. H NMR (500 MHz, CDCl3): δ = 7.44–7.40
(m, 3 H), 7.37–7.31 (m, 7 H), 7.15 (t, J = 7.5 Hz, 1 H), 6.76 (d, J
= 8.0 Hz, 1 H), 6.68 (t, J = 7.5 Hz, 1 H), 6.42 (d, J = 7.5 Hz, 1 H),
3.20 (s, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 166.8, 154.5,
143.3, 141.3, 139.9, 129.9, 129.3, 129.1, 129.0, 128.9, 128.7, 127.8,
121.1, 107.9, 26.2, 21.1 ppm. IR (KBr): ν = 1776, 1653, 1586 cm–1.
˜
LRMS (EI, 70 eV): m/z (%) = 249 (100) [M]+, 220 (29), 172 (67),
124.2, 123.2, 123.1, 121.3, 107.6, 25.8 ppm. IR (KBr): ν = 1758,
˜
123 (28).
1674, 1565 cm–1. LRMS (EI, 70 eV): m/z (%) = 311 (98) [M]+, 310
3-Benzylidene-6-chloro-1-methylindolin-2-one (2s):[8j] (Z/E, 1.2:1).
(100), 234 (30), 165 (16).
1
Data for (Z) isomer: yellow solid; m.p. 167.3–168.8 °C. H NMR
1,1Ј-Dimethyl-[3,3Ј-biindolinylidene]-2,2Ј-dione (2x):[11a,11b] Yellow
(400 MHz, CDCl3): δ = 8.29–8.27 (m, 2 H), 7.45–7.41 (m, 5 H),
7.20 (d, J = 8.0 Hz, 1 H), 6.66 (d, J = 8.0 Hz, 1 H),3.20 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 165.6, 140.6, 138.4,
133.4, 132.1, 130.9, 128.3, 128.3, 127.2, 125.7, 125.0, 119.3, 108.7,
1
solid; m.p. 173.6–175.1 °C. H NMR (400 MHz, CDCl3): δ = 9.21
(d, J = 8.0 Hz, 2 H), 7.37 (t, J = 7.6 Hz, 2 H), 7.07 (t, J = 7.6 Hz,
2 H), 6.78 (d, J = 7.6 Hz, 2 H), 3.29 (s, 6 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 168.0, 145.2, 133.4, 132.4, 129.8, 122.4,
26.0 ppm. IR (KBr): ν = 1765, 1643, 1556 cm–1. LRMS (EI, 70 eV):
˜
121.6, 107.6, 26.1 ppm. IR (KBr): ν = 1784, 1683, 1552 cm–1.
˜
m/z (%) = 271 (34) [M + 2]+, 269 (100) [M]+, 268 (66), 192 (58),
164 (22). Data for (E) isomer: yellow solid; m.p. 152.6–153.8 °C.
1H NMR (400 MHz, CDCl3): δ = 7.89 (s, 1 H), 7.62–7.58 (m, 3
H), 7.51–7.45 (m, 3 H), 7.22 (d, J = 8.0 Hz, 1 H), 6.73 (d, J =
8.0 Hz, 1 H), 3.26 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 168.0, 142.6, 138.8, 134.4, 130.0, 129.3, 129.2, 128.8, 127.0, 126.2,
LRMS (EI, 70 eV): m/z (%) = 290 (100) [M]+, 262 (43), 233 (45),
207 (38).
Supporting Information (see footnote on the first page of this arti-
1
cle): H and 13C NMR spectra for indolin-2-one products 2.
122.7, 122.4, 108.9, 26.2 ppm. IR (KBr): ν = 1765, 1643, 1556 cm–1.
˜
Acknowledgments
LRMS (EI, 70 eV): m/z (%) = 271 (36) [M + 2]+, 269 (100) [M]+,
268 (69), 192 (55), 164 (23).
The authors thank the Specialized Research Fund for the Doctoral
Program of Higher Education (grant number 20120161110041), the
Hunan Provincial Natural Science Foundation of China (grant
number 13JJ2018), the National Natural Science Foundation of
China (grant number 21172060), and the Fundamental Research
Funds for the Central Universities (Hunan University), grant
number 2011-015) for the financial support.
(Z)-3-Benzylidene-5,7-dichloro-1-methylindolin-2-one (2t): (Z/E,
1.4:1). Data for (Z) isomer: yellow solid; m.p. 193.7–194.5 °C. H
1
NMR (400 MHz, CDCl3): δ = 8.28–8.26 (m, 2 H), 7.46–7.43 (m, 4
H), 7.31 (s, 1 H), 7.15 (s, 1 H), 3.57 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 165.7, 139.5, 136.5, 133.1, 132.4, 131.4,
129.9, 128.3, 127.9, 127.1, 123.8, 117.6, 115.6, 29.0 ppm. IR (KBr):
ν = 1787, 1608, 1512 cm–1. LRMS (EI, 70 eV): m/z (%) = 306 (19)
˜
[M + 3]+, 305 (69) [M + 2]+, 304 (68) [M + 1]+, 303 (100) [M]+,
302 (85), 226 (49), 134 (24). HRMS (ESI): calcd. for C16H12Cl2NO
[M + H]+ 304.0362; found 304.0364. Data for (E) isomer: yellow
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1
solid; m.p. 176.5–177.9 °C. H NMR (400 MHz, CDCl3): δ = 7.95
(s, 1 H), 7.58–7.56 (m, 2 H), 7.51–7.46 (m, 4 H), 7.19 (s, 1 H), 3.65
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.3, 140.2,
138.6, 134.1, 130.9, 130.2, 129.1, 128.9, 127.1, 125.4, 124.8, 121.2,
116.0, 29.7 ppm. IR (KBr): ν = 1787, 1608, 1512 cm–1. LRMS (EI,
˜
70 eV): m/z (%) = 306 (16) [M + 3]+, 305 (65) [M + 2]+, 304 (70)
[M + 1]+, 303 (100) [M]+, 302 (82), 226 (46), 134 (20).
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(500 MHz, CDCl3): δ = 8.32 (d, J = 8.0 Hz, 0.55 H), 8.27 (s, 0.71
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7.0 Hz, 1.73 H), 7.51–7.46 (m, 3 H), 6.89–6.85 (m, 1 H), 3.33 (s, 3
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Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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Job/Unit: O31284
/KAP1
Date: 13-11-13 18:45:19
Pages: 9
X.-H. Yang, K. Li, R.-J. Song, J.-H. Li
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Received: August 26, 2013
Published Online: ᭿
8
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O31284
/KAP1
Date: 13-11-13 18:45:19
Pages: 9
Intramolecular Oxidative Aminocarbonylation
Aminocarbonylation
X.-H. Yang, K. Li, R.-J. Song,
J.-H. Li* ........................................... 1–9
Room-Temperature Palladium-Catalyzed
Intramolecular Oxidative Aminocarbonyl-
ation of Vinylic C(sp2)–H Bonds with
Amines and CO
A general, room-temperature route to 3-
methyleneindolin-2-ones is presented that
is achieved by a palladium-catalyzed intra-
molecular oxidative aminocarbonylation of
vinylic C(sp2)–H bonds with amines and
CO.
Keywords: Nitrogen heterocycles
ladium / Carbonylation / Amines / Reac-
tion mechanisms
/ Pal-
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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