Ruthenium-catalyzed regioselective C2 alkenylation of indoles and pyrroles via C-H bond functionalization

Article abstract of DOI:10.1021/jo401579m

An efficient ruthenium-catalyzed oxidative coupling of indoles and pyrroles with various alkenes at the C2-position assisted by employing the N,N-dimethylcarbamoyl moiety as a directing group is reported. The catalytic reaction proceeds in an excellent regio- and stereoselective manner.

Full text of DOI:10.1021/jo401579m

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Article
Ruthenium-Catalyzed Regioselective C2 Alkenylation
of Indoles and Pyrroles via C-H Bond Functionalization
Bin Li, Jianfeng Ma, Weijia Xie, Haibin Song, Shansheng Xu, and Baiquan Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo401579m • Publication Date (Web): 28 Aug 2013
Downloaded from http://pubs.acs.org on August 29, 2013
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Ruthenium-Catalyzed Regioselective C2 Alkenylation of Indoles and
Pyrroles via C-H Bond Functionalization
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Bin Li,*,† Jianfeng Ma,†,§ Weijia Xie,†,§ Haibin Song,† Shansheng Xu,† and Baiquan
Wang*,†,‡
†State Key Laboratory of Element-Organic Chemistry, College of Chemistry, Nankai University,
Tianjin 300071
‡State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai
200032, P. R. China
Email: nklibin@nankai.edu.cn, bqwang@nankai.edu.cn
R3
R2
cat. Ru(II)
R2
R1
Me2N
H
R1
Me2N
N
N
R4
+
R3
R4
Cu(II)
dioxane
O
O
Highly regio- and stereoselective broad substrate scope
readily available and easily removable directing group
ABSTRACT: An efficient ruthenium-catalyzed oxidative coupling of indoles and pyrroles with
various alkenes at the C2-position assisted by employing the N,N-dimethylcarbamoyl moiety as a
directing group is reported. The catalytic reaction proceeds in an excellent regio- and stereoselective
manner.
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INTRODUCTION
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The catalytic functionalization of C-H bonds1 has become an increasingly efficient and reliable
approach for new carbon-carbon2 and carbon-heteroatom3 bond formations. The Fujiwara-Moritani
reaction4—a process of oxidative alkenylation of normally unreactive aryl C-H bonds—has become
an important and attractive alternative to the traditional Mizorki-Heck reaction.5 For the past
decades, various catalytic systems, mainly employing palladium6 and rhodium7 complexes as
catalysts, have been developed for oxidative Heck transformations. In these studies, a neighbouring
directing group8 was often used to obtain a regioselective C-H activation, and an easily installed and
readily removed directing group is more favoured.
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Undoubtedly, indole derivatives represent one of the most important classes of heterocyclic
compounds, because of their extensive existence in biologically active natural products and
pharmaceutical products.9 As a result, the efficient functionalization of indole derivatives has
attracted much attention. However, direct C2-alkenylation of indole via transition-metal-catalyzed
C-H bond activation is still a challenge due to the electrophilic nature of the reaction as well as the
higher C-H nucleophilic reactivity of the C3-position than that of the C2-position. Up to now, four
palladium-catalyzed protocols for intermolecular C2-alkenylation of indole were developed.10
Gaunt et al. demonstrated a selective Pd(II)-catalyzed C2- and C3- oxidative alkenylation of free
(NH) indoles by varying the nature of the solvent and additives.10d Assisted by N-2-pyridylmethyl or
N-(2-pyridyl)sulfonyl as the directing group, the groups of Ricci,10e Carretero and Arrayás10a,b
independently reported the functionalization of indole at the C2-position with excess of alkenes in
the presence of a Pd(II) catalyst. Miura, Satoh and co-workers described an exclusive
C2-alkenylation method of indoles through Pd(II)-catalyzed C–H olefination of indole-3-carboxylic
acids, in which decarboxylation of the carboxyl group occurred during the reaction process.10c In
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these cases, high catalyst loading (often 10 mol %) was required, and a limited substrate scope of
alkenes (mostly restricted to acrylates) was observed. Thus, the development of a new catalytic
system for this transformation is highly desired.
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On the other hand, the less-expensive ruthenium(II) complex has emerged into the field of
chelation-assisted oxidative olefination of arenes as a useful catalyst. In this regard, the research
groups of Satoh and Miura,11 Ackermann,12 Bruneau and Dixneuf,13 Jeganmohan,14 Lam,15
Ramana,16 and ours17 have shown that use of the [{RuL2(p-cymene)}2] (L = Cl or OAc) catalyst
allows the oxidative coupling between aromatic acids, aryl ketones, N-arylpyrazoles, anilides,
amides, aromatic aldehydes, aromatic esters, and aryl carbamates with olefins by using copper
acetate as oxidant. Moreover, we have reported the dehydrogenative alkenylation of
N-methoxybenzamides with styrene and acrylates in the presence of [{RuCl2(p-cymene)}2] as
catalyst using CONH(OMe) as an oxidizing directing group.18 Very recently, Prabhu et al. reported
the first N-benzoyl directed Ru-catalyzed regioselective C2-alkenylation of indoles. However, only
acrylates were used as coupling partners in this method.19 Based on these findings, we envisioned
that using a proper directing group, [{RuCl2(p-cymene)}2] could be a suitable catalyst for the
oxidative C2-olefination of indoles and pyrroles with broader alkene substrates scope. Herein, we
disclose our development of a ruthenium-catalyzed regioselective coupling of indoles and pyrroles
with alkenes at the C2-position via C-H activation with the use of easily removed
N,N-dimethylcarbamoyl as the directing group. 20
RESULTS AND DISCUSSION
We started our study with the oxidative coupling reaction of various N-substituted indoles (1)
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and styrene (2a). The choice of the protecting group on indole was found to be crucial, with
N,N-dimethylcarbamoyl being optimal (Table 1, entries 1-7). Treatment of
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N,N-dimethyl-1H-indole-1-carboxamide (1a) (1.0 equiv) with 2a (2.0 equiv) in the presence of 5.0
mol % of [{RuCl2(p-cymene)}2], 20.0 mol% of AgSbF6, and 2.0 equiv of Cu(OAc)2·H2O in
dioxane at 100 °C for 24 h gave the desired alkenylation product 3aa in 87% yield (entry 1). To our
delight, the reaction proceeded in excellent regio- and stereoselectivity with the formation of
exclusive C2 E-alkenylation product. Screening of the solvent indicated that THF was also suitable
for the reaction, giving 3aa in comparable yield (entry 10). But a change of solvent to t-AmOH
(t-Am = tert-amyl) and DME led to a low yield (entries 8 and 9). Later, it was found that reducing
the catalyst loading to 2.5 mol % and the amount of copper acetate to 1.0 equiv resulted in no loss
in yield of 3aa (88%, entry 14), and lowering the reaction temperature to 80 °C decreased the yield
from 88% to 67% (entry 17). The stoichiometric amount of Cu salt is used as an oxidant to
regenerate the catalyst. Note that the use of 4 equiv of AgSbF6 per molecule of
[{RuCl2(p-cymene)}2] is crucial (entry 18), which is used to remove all the chlorides to generate
cationic Ru catalyst. Moreover, no desired product was obtained in the absence of a ruthenium
catalyst (entry 19).
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We then explored the alkene scope of the ruthenium-catalyzed oxidative olefination
transformation of 1a under the optimized reaction conditions (Scheme 1). The styrene derivatives
reacted with indole 1a smoothly, and styrenes with electron-donating group (3ab-3ad) gave higher
yields than those with electron-withdrawing groups (3ae-3ag, 3ai). The molecular structure of 3af
was confirmed by X-ray diffraction analysis.21 The electrophilic alkenes were then tested for our
reaction. Various acrylates, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, and benzyl
acrylate performed well to afford the desired products in up to 95% yield (3aj-3am),22 whereas in
the reaction of 1a with tert-butyl acrylate, it furnished the product 3au in which the acrylic ester
hydrolyzed into acrylic acid under the reaction conditions (eq 1). Other alkenes bearing
electron-withdrawing groups were also tested: products 3an and 3ao could be generated from
(phenylsulfonyl)ethene and diethyl vinylphosphonate in high yields (87% and 93%, respectively);
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while acrylonitrile showed a lower reactivity with the formation of 3ap in a moderate yield.
Employment of the allyl acetate as the coupling partner resulted in the formation of nonconjugated
terminal alkene product 3av (eq 1). The formation of related terminal olefins starting from allyl
acetate has been reported.7e,23 Nevertheless, the coupling with 3,3-dimethyl-1-butene,
α-methylstyrene, norbornylene and 2,5-norbornadiene failed using our current method.
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OAc
CO2tBu
2u
CO2H
2v
N
N
1a
(1)
Me2N
O
Me2N
O
3au, 85%
3av, 31%
This protocol can also be applied to higher substituted alkenes: (E)-methyl crotonate,
(E)-methyl cinnamate, and methyl methacrylate were successfully coupled with 1a to provide the
corresponding trisubstituted alkene products 3aq, 3ar, and 3as in 90%, 55% and 44% yields,
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respectively.24 The E configuration of the double bond in these compounds was confirmed by
NOESY.21 Interestingly, the coupling of cyclic Michael acceptor cyclopent-2-enone with indole 1a
resulted in the addition product 3at in good yield.25 The molecular structure of 3at was determined
by single crystal X-ray diffraction.21
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The scope of the reaction with respect to indole reactant was explored with p-bromostyene (2g)
as the model olefin (Table 2). This coupling reaction turned out to be a versatile reaction, as the
alkenylation could tolerate various functional groups, such as OMe (entry 6), F (entry 3), Cl (entries
2, 4 and 8), Br (entry 5), and NO2 (entry 7), under the reaction conditions. The indole counterpart
with the 7-methyl group gave the desired product in low yield. This might be due to the steric
hindrance between the C7 methyl and the N,N-dimethylcarbamoyl directing group, which greatly
increased the difficulty of the carbamoyl group directed C-H bond activation at C2-position
(Scheme 2).
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We tried several times for the isolation of the Ru(II) cyclometallation organometallic species
but did not get anything. We next conducted experiments to probe the working mode of the reaction.
First, intermolecular competition experiments between indoles 1g and 1h with a single equivalent of
alkene 2g under the standard conditions revealed that electron-rich indole 1g was transformed
preferentially (eq 2), suggesting an SEAr-type mechanism of the cyclometalated step. Then,
intermolecular competition experiments between substituted styrenes 2d and 2e with a single
equivalent of indole 1a indicated that the electron rich styrene was more reactive under this
catalytic system (eq 3), which can be rationalized in terms that the electron-rich olefins are more
favorable for the coordination to Ru after the cyclometalated step.
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MeO
(1.0 equiv)
MeO
2g
O2N
+
standard
conditions
H
R
H
N
N
(2)
N
O
Me2N
O
Me2N
1h (1.5 equiv)
Me2N
1g (1.5 equiv)
O
(R = 4-BrC6H4)
3gg (52%)
OMe
1a
N
(1.0 equiv)
standard
conditions
O
+
3ad, 65%
3ae, 20%
Me2N
(3)
+
F
OMe
F
N
2e
2d
(3.0 equiv) (3.0 equiv)
O
Me2N
The reactions performed well on large scale (4.0 mmol, 80% for 3aa, Scheme 1). Moreover,
the dimethylcarbamoyl group can be easily removed under mild reaction conditions (eqs 4 and 5).
Both of these results highlight the potential synthetic utility of this method.
R
KOtBu
(6.0 equiv)
R
N
(4)
THF
25 oC, 6 h
O
N
Me2N
H
3ac
3ag
R= tBu,
R= tBu, 8a, 90%
Br, 8b, 78%
Br,
COOEt
NaOH
(10.0 equiv)
COOH
(5)
N
N
EtOH
80 oC, 24 h
O
H
Me2N
3ak
9, 72%
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Finally, we were pleased to find that the current catalytic system could be successfully applied
to pyrrole substrates (Scheme 3). By changing the ratio of reactants, pyrrole 4 successfully coupled
with acrylates to yield C2,C5-double alkenylated products 5 or C2-monoalkenylated products 6.
Furthermore, unsymmetrical C2,C5-dialkenylated products 7 could be efficiently achieved by
subsequent C5-alkenylation of 6 with a different olefin with employing our method.
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CONCLUSIONS
In summary, we have developed a Ru(II)-catalyzed oxidative C2-alkenylation of indoles and
pyrroles assisted by an easily removed directing group with a broad substrate scope. The catalytic
reaction proceeded with excellent regio- and stereoselectivity. Further studies to explore the
ruthenium-catalyzed oxidative C-H bond transformation and the detailed mechanistic investigation
are in progress in our laboratory.
Experimental Section
General Procedures. All the reactions were carried out under argon atmosphere using standard
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Schlenk technique. H NMR (400 MHz), F (376 MHz) and C NMR (100MHz) were recorded
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with CDCl3 or DMSO-d6 as solvent. Chemical shifts of H, F, and 13C NMR spectra are reported
in parts per million (ppm). The residual solvent signals were used as references and the chemical
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shifts converted to the TMS scale (CDCl3: δH = 7.26 ppm, δC = 77.00 ppm; DMSO-d6: δH = 2.50
ppm, δC = 39.52 ppm). HRMS were done on Varian 7.0 T FTICR-mass spectrometers.
[{RuCl2(p-cymene)}2] was prepared from RuCl3·xH2O following a literature procedure.[26]
General Procedure for installation of N,N-dimethylcarbamoyl moiety. A solution of indole
(10.0 mmol, 1.0 equiv) in DMF (6.0 mL) was slowly added to a suspension of NaH (20.0 mmol) in
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o
o
DMF (3.0 mL) at 0 C. The resulting solution was then stirred at 75 C for 2-3 hours. To which
o
dimethylcarbamic chloride (15.0 mmol, in 5 mL DMF) was added dropwise at 0 C. The reaction
o
was then stirred at 75 C over night. After that, the reaction was quenched with saturated NH4Cl
solution and extracted with EtOAc. The combined organic phase was dried with MgSO4 and
concentrated under reduced pressure. The residue was purified by flash chromatography.
The structure of indole substrate 1a, 1e, 1g, and 1h, which were confirmed by 1H and 13C NMR
spectroscopy, are consistent with those reported previously.[20a]
N,N,3-trimethyl-1H-indole-1-carboxamide (1b). This compound was obtained as a colorless
o
1
solid (1.76 g, 87% yield). M.p.: 115-117 C; H NMR (CDCl3, 400 MHz): δ 7.63 (d, J = 8.2 Hz,
1H), 7.53 (d, J = 7.7 Hz, 1H), 7.31-7.25 (m, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.09 (s, 1H), 3.09 (br s,
6H), 2.30 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ 155.3, 135.8, 130.2, 123.5, 123.4, 121.3, 118.9,
114.9, 113.5, 38.4, 9.6; IR (cm-1): ν 3108, 2962, 2917, 1673, 1491, 1454, 1391, 1377, 1203, 1051,
751, 547; HRMS (ESI): Calcd for C12H14N2ONa [M+Na]+ 225.0998, Found: 225.1002.
4-chloro-N,N-dimethyl-1H-indole-1-carboxamide (1c). This compound was obtained as light
yellow oil (2.08 g, 94% yield). 1H NMR (CDCl3, 400 MHz): δ 7.56 (dd, J = 5.8, 3.3 Hz, 1H), 7.35
(d, J = 3.6 Hz, 1H), 7.21 (d, J = 2.6 Hz, 1H), 7.20 (s, 1H), 6.72 (d, J = 3.5 Hz, 1H), 3.10 (s, 6H); 13C
NMR (CDCl3, 100 MHz): δ 154.5, 136.2, 128.1, 126.6, 126.1, 124.1, 121.5, 112.0, 103.9, 38.4; IR
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(cm-1): ν 3140, 1684, 1489, 1457, 1426, 1395, 1263, 1177, 1158, 891, 750; HRMS (ESI): Calcd for
C11H11ClN2ONa [M+Na]+ 245.0452, Found: 245.0455.
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5-fluoro-N,N-dimethyl-1H-indole-1-carboxamide (1d). This compound was obtained as a
light yellow solid (1.96 g, 95% yield). M.p.: 86-88 oC; 1H NMR (CDCl3, 400 MHz): δ 7.61 (dd, J =
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9.0, 4.5 Hz, 1H), 7.34 (d, J = 3.5 Hz, 1H), 7.24 (dd, J = 9.1, 2.6 Hz, 1H), 7.02 (td, J = 9.1, 2.5 Hz,
13
1H), 6.56 (dd, J = 3.5, 0.4 Hz, 1H), 3.10 (s, 6H); C NMR (CDCl3, 100 MHz): δ 158.7 (d, JC-F
=
=
237.6 Hz), 154.8, 132.0, 130.0 (d, JC-F = 10.0 Hz), 127.6, 114.4 (d, JC-F = 9.5 Hz), 111.6 (d, JC-F
25.6 Hz), 106.0 (d, JC-F = 23.8 Hz), 105.5 (d, JC-F = 4.2 Hz), 38.4; 19F NMR (CDCl3, 376 MHz): δ
-122.2 (s); IR (cm-1): ν 3309, 3138, 2972, 1683, 1676, 1653, 1471, 1475, 1398, 1027, 848, 624;
HRMS (ESI): Calcd for C11H11FN2ONa [M+Na]+ 229.0748, Found: 229.0743.
5-bromo-N,N-dimethyl-1H-indole-1-carboxamide (1f). This compound was obtained as a
o
1
colorless solid (2.45 g, 92% yield). M.p.: 139-141 C; H NMR (CDCl3, 400 MHz): δ 7.73 (d, J =
1.8 Hz, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.37 (dd, J = 8.8, 1.9 Hz, 1H), 7.31 (d, J = 3.5 Hz, 1H), 6.54
13
(dd, J = 3.5, 0.4 Hz, 1H), 3.09 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 154.6, 134.2, 131.0,
127.2, 126.4, 123.5, 115.0, 114.9, 105.0, 38.4; IR (cm-1): ν 3142, 2957, 2918, 1676, 1500, 1489,
1456, 1397, 1313, 1023, 861, 731; HRMS (ESI): Calcd for C11H11BrN2ONa [M+Na]+ 288.9947,
Found: 288.9951.
6-chloro-N,N-dimethyl-1H-indole-1-carboxamide (1i). This compound was obtained as a
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colorless solid (1.98 g, 89% yield). M.p.: 107-109 C; H NMR (CDCl3, 400 MHz): δ 7.69 (d, J =
1.6 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 7.29 (d, J = 3.5 Hz, 1H), 7.17 (dd, J = 8.4, 1.8 Hz, 1H), 6.57
(d, J = 3.5 Hz, 1H), 3.10 (s, 6H); 13C NMR (CDCl3, 100 MHz): δ 154.6, 135.9, 129.5, 127.8, 126.7,
122.4, 121.7, 113.6, 105.5, 38.4; IR (cm-1): ν 3126, 3105, 1675, 1491, 1454, 1439, 1395, 1203,
1160, 1121, 891, 679; HRMS (ESI): Calcd for C11H11ClN2ONa [M+Na]+ 245.0452, Found: 245.0450.
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N,N,7-trimethyl-1H-indole-1-carboxamide (1j). This compound was obtained as light red
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solid (1.66 g, 82% yield). M.p.: 128-130 C; H NMR (CDCl3, 400 MHz): δ 7.48 (d, J = 7.6 Hz,
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1H), 7.15 (d, J = 3.4 Hz, 1H), 7.12 (t, J = 7.6 Hz, 1H), 7.06 (d, J = 7.1 Hz, 1H), 6.61 (d, J = 3.4 Hz,
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1H), 3.04 (s, 6H), 2.45 (s, 3H); C NMR (CDCl3, 100 MHz): δ 155.0, 134.8, 129.5, 126.0, 125.5,
122.5, 121.7, 118.8, 105.4, 37.5 (br s), 18.6; IR (cm-1): ν 3100, 1683, 1653, 1490, 1456, 1391, 1300,
1194, 1020, 787, 758; HRMS (ESI): Calcd for C12H14N2ONa [M+Na]+ 225.0998, Found: 225.1003.
N,N-dimethyl-1H-pyrrole-1-carboxamide (4). This compound was obtained as a gray solid
(1.36 g, 99% yield). A. M.p.: 70-72 oC; 1H NMR (CDCl3, 400 MHz): δ 7.04 (t, J = 2.2 Hz, 2H), 6.
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23 (t, J = 2.2 Hz, 2H), 3.09 (s, 6H); C NMR (CDCl3, 100 MHz): δ 154.6, 120.4, 110.3, 38.5; IR
(cm-1): ν 3122, 3101, 2956, 2933, 1682, 1490, 1453, 1405, 1392, 1297, 1091, 1077, 963, 745, 690,
621; HRMS (ESI): Calcd for C7H10N2ONa [M+Na]+ 161.0685, Found: 161.0687.
General preparation for the product 3, 5, 6, and 7. A mixture of indole or pyrrole substrate
(1 or 4) (0.30 mmol, 1.0 equiv), [Ru(p-cymene)Cl2]2 (4.59 mg, 0.0075 mmol, 2.5 mol %),
Cu(OAc)2·H2O (60.0 mg, 0.30 mmol, 1.0 equiv.) and alkene (2) (0.60 mmol, 2.0 equiv) was
combined in a Schlenk tube followed by addition of Dioxane (2.0 mL) under Ar atmosphere. Then
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the reaction mixture was heated to 100 C with stirring for 24 hours. Afterwards, the vial was
cooled to room temperature. Silica was added to the flask and volatiles were evaporated under
reduced pressure. The purification was performed by flash column chromatography on silica gel.
(E)-N,N-dimethyl-2-styryl-1H-indole-1-carboxamide (3aa). This compound was obtained as
a light yellow oil (77 mg, 88% yield). 1H NMR (CDCl3, 400 MHz): δ 7.51 (d, J = 7.7 Hz, 1H), 7.43
(d, J = 7.3 Hz, 2H), 7.29 (t, J = 7.6 Hz, 2H), 7.23 (d, J = 8.2 Hz, 1H), 7.20-7.15 (m, 2H), 7.10 (d, J
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= 7.7 Hz, 1H), 7.07-7.06 (m, 2H), 6.79 (s, 1H), 2.94 (br s, 6H); C NMR (CDCl3, 100 MHz): δ
153.9, 137.0, 136.7, 136.1, 130.6, 128.6, 128.4, 127.9, 126.5 123.3, 121.6, 120.6, 117.3, 111.1,
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102.9, 37.6 (br s); IR (cm-1): ν 3055, 2929, 1686, 1494, 1450, 1392, 1348, 1307, 1179, 1066, 751,
693; HRMS (MALDI): Calcd for C19H19N2O [M+H]+ 291.1492, Found: 291.1500.
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(E)-N,N-dimethyl-2-(4-methylstyryl)-1H-indole-1-carboxamide (3ab). This compound was
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obtained as a light yellow oil (77 mg, 84% yield). H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 7.7
Hz, 1H), 7.41 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 7.8 Hz, 1H), 7.25 (td, J = 8.2, 1.2 Hz, 1H), 7.19-7.15
(m, 3H), 7.11 (br s, 2H), 6.84 (s, 1H), 3.02 (br s, 6H), 2.37 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ
154.0, 138.0, 137.3, 136.1, 134.0, 130.7, 129.4, 128.5, 126.5, 123.2, 121.5, 120.6, 116.4, 111.1,
102.6, 37.6 (br s), 21.3; IR (cm-1): ν 3045, 2963, 2922, 1686, 1508, 1489, 1450, 1390, 1306, 1179,
805; HRMS (ESI): Calcd for C20H21N2O [M+H]+ 305.1648, Found: 305.1653.
(E)-2-(4-tert-butylstyryl)-N,N-dimethyl-1H-indole-1-carboxamide (3ac). This compound was
obtained as a light yellow solid (92 mg, 89% yield). M.p.: 91-93 oC; 1H NMR (CDCl3, 400 MHz): δ
7.58 (d, J = 7.7 Hz, 1H), 7.45 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.2 Hz, 1H),
7.24 (td, J = 8.2, 0.8 Hz, 1H), 7.16 (td, J = 7.9, 0.8 Hz, 1H), 7.11 (br s, 2H), 6.84 (s, 1H), 3.00 (br s,
6H), 1.35 (s, 9H); 13C NMR (CDCl3, 100 MHz): δ 154.0, 151.2, 137.2, 136.1, 134.0, 130.6, 128.5,
126.3, 125.6, 123.2, 121.5, 120.5, 116.6, 111.1, 102.7, 37.7 (br s), 34.6, 31.2; IR (cm-1): ν 3051,
2961, 2867, 1686, 1450, 1391, 1307, 1263, 1180, 1065, 818, 800; HRMS (MALDI): Calcd for
C23H26N2ONa [M+Na]+ 369.1937, Found: 369.1942.
(E)-2-(4-methoxystyryl)-N,N-dimethyl-1H-indole-1-carboxamide (3ad). This compound was
obtained as a light yellow solid (87 mg, 91% yield) by following the general procedure except 3.0
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equiv of styrene was used. M.p.: 153-154 C; H NMR (CDCl3, 400 MHz): δ 7.57 (d, J = 7.7 Hz,
1H), 7.45-7.43 (m, 2H), 7.31 (d, J = 8.1 Hz, 1H), 7.21 (td, J = 8.2, 1.1 Hz, 1H), 7.16 (t, J = 7.4 Hz,
1H), 7.09 (d, J = 16.3 Hz, 1H), 7.00 (d, J = 16.3 Hz, 1H), 6.91-6.89 (m, 2H), 6.81 (s, 1H), 3.84 (s,
3H), 3.02 (br s, 6H); 13C NMR (CDCl3, 100 MHz): δ 159.6, 154.1, 137.5, 136.1, 130.4, 129.7,
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128.6, 127.9, 123.1, 121.5, 120.5, 115.3, 114.2, 111.1, 102.2, 55.3, 37.8 (br s), 37.5 (br s); IR (cm-1):
ν 3034, 2964, 1683, 1601, 1508, 1450, 1391, 1175, 816, 650; HRMS (ESI): Calcd for
C20H20N2O2Na [M+Na]+ 343.1417, Found: 343.1412.
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(E)-2-(4-fluorostyryl)-N,N-dimethyl-1H-indole-1-carboxamide (3ae). This compound was
obtained as a light yellow solid (70 mg, 76% yield). M.p.: 136-138 oC; 1H NMR (CDCl3, 400 MHz):
δ 7.58 (d, J = 7.8 Hz, 1H), 7.50-7.43 (m, 2H), 7.30 (d, J = 8.2 Hz, 1H), 7.24 (td, J = 8.2, 1.2 Hz,
1H), 7.19-7.14 (td, J = 7.4, 1.1 Hz, 1H), 7.08-7.02 (m, 4H), 6.85 (s, 1H), 3.02 (br s, 6H); 13C NMR
(CDCl3, 100 MHz): δ 162.5 (d, JC-F = 247.9 Hz), 154.0, 137.0, 136.1, 133.0 (d, JC-F = 3.1 Hz),
129.5, 128.4, 128.1 (d, JC-F = 8.0 Hz), 123.4, 121.6, 120.7, 117.2 (d, JC-F = 2.4 Hz), 115.7 (d, JC-F
=
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21.8 Hz), 111.2, 102.9, 37.5 (br s); F NMR (CDCl3, 376 MHz): δ -113.4 (s); IR (cm-1): ν 3062,
2935, 1684, 1652, 1506, 1489, 1450, 1395, 1180, 822; HRMS (MALDI): Calcd for C19H18FN2O
[M+H]+ 309.1398, Found: 309.1404.
(E)-2-(4-chlorostyryl)-N,N-dimethyl-1H-indole-1-carboxamide (3af). This compound was
obtained as a colorless solid (70 mg, 72% yield). M.p.: 221-223 oC; 1H NMR (CDCl3, 400 MHz): δ
7.58 (d, J = 7.8 Hz, 1H), 7.44-7.41 (m, 2H), 7.34-7.29 (m, 3H), 7.24 (td, J = 8.2, 1.2 Hz, 1H), 7.18
(td, J = 7.8, 1.2 Hz, 1H), 7.13 (d, J = 16.0 Hz, 1H), 7.06 (d, J = 16.1 Hz, 1H), 6.87 (s, 1H), 3.03 (br
s, 6H); 13C NMR (CDCl3, 100 MHz): δ 153.9, 136.9, 136.2, 135.4, 133.5, 129.3, 128.9, 128.4,
127.7, 123.5, 121.7, 120.8, 118.0, 111.2, 103.3, 38.0 (br s); IR (cm-1): ν 3076, 2932, 2360, 1683,
1487, 1448, 1393, 1345, 1175, 1089, 940, 751; HRMS (ESI): Calcd for C19H17ClN2ONa [M+Na]+
347.0922, Found: 347.0919.
(E)-2-(4-bromostyryl)-N,N-dimethyl-1H-indole-1-carboxamide (3ag). This compound was
obtained as a light yellow solid (82 mg, 74% yield) by following the general procedure except 3.0
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equiv of styrene was used. M.p.: 134-136 C; H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 7.8 Hz,
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1H), 7.49-7.46 (m, 2H), 7.37-7.35 (m, 2H), 7.30 (d, J = 8.3 Hz, 1H), 7.24 (td, J = 8.2, 1.2 Hz, 1H),
7.17 (td, J = 7.9, 1.2 Hz, 1H), 7.15 (d, J = 16.4 Hz, 1H), 7.04 (d, J = 16.3 Hz, 1H), 6.87 (s, 1H),
3.04 (s, 6H); 13C NMR (CDCl3, 100 MHz): δ 153.9, 136.8, 136.1, 135.8, 131.8, 129.3, 128.4, 128.0,
123.6, 121.7, 120.8, 118.1, 111.2, 103.4, 37.7 (br s), 37.6 (br s) (one signal missing due to overlap);
IR (cm-1): ν 3024, 2926, 1695, 1684, 1653, 1558, 1473, 1392, 1066, 952; HRMS (ESI): Calcd for
C19H17BrN2ONa [M+Na]+ 391.0417, Found: 391.0416.
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(E)-N,N-dimethyl-2-(2-(naphthalen-2-yl)vinyl)-1H-indole-1-carboxamide
(3ah).
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compound was obtained as light brown solid (69 mg, 68% yield). M.p.: 176-178 C; H NMR
(CDCl3, 400 MHz): δ 7.87-7.83 (m, 4H), 7.73 (d, J = 8.6 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H),
7.52-7.46 (m, 2H), 7.37 (d, J = 8.0 Hz, 1H), 7.31-7.26 (m, 3H), 7.23-7.20 (m, 1H), 6.93 (s, 1H),
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3.05 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 154.0, 137.2, 136.2, 134.3, 133.6, 133.1, 130.8,
128.5, 128.3, 128.0, 127.6, 126.8, 126.4, 126.1, 123.4, 123.3, 121.6, 120.7, 117.6, 111.2, 103.1,
37.7 (br s), 37.5 (br s); IR (cm-1): ν 2961, 1700, 1684, 1675, 1653, 1559, 1541, 1507, 1394, 1304, 821,
745; HRMS (ESI): Calcd for C23H20N2ONa [M+Na]+ 363.1468, Found: 363.1465.
(E)-N,N-dimethyl-2-(perfluorostyryl)-1H-indole-1-carboxamide (3ai). This compound was
obtained as a colorless solid (93 mg, 82% yield). M.p.: 180-182 oC; 1H NMR (CDCl3, 400 MHz): δ
7.61 (d, J = 7.9 Hz, 1H), 7.46 (d, J = 16.8 Hz, 1H), 7.35 (d, J = 8.2 Hz, 1H), 7.28 (td, J = 7.1, 0.7
Hz, 1H), 7.19 (t, J = 7.4 Hz, 1H), 6.98 (d, J = 16.7 Hz, 1H), 6.97 (s, 1H), 3.06 (br s, 6H); 13C NMR
(CDCl3, 100 MHz): δ 153.6, 144.7 (dm, JC-F = 250.8 Hz), 139.8 (dm, JC-F = 254.9 Hz), 137.7 (dm,
JC-F = 251.5 Hz), 136.6, 136.1, 128.2, 125.8 (td, JC-F = 8.9, 2.0 Hz), 124.3, 121.9, 121.1, 113.8,
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112.1 (td, JC-F = 13.7, 4.2 Hz), 111.4, 105.0, 37.62, 37.58; F NMR (CDCl3, 376 MHz): δ -142.6
(dd, J = 21.5, 7.7 Hz, 2F), -155.9 (td, J = 20.8, 3.9 Hz, 1F), -162.7 (td, J = 20.6, 7.6 Hz, 2F); IR
(cm-1): ν 2935, 1685, 1518, 1497, 1387, 1349, 1304, 1180, 1002, 962, 754; HRMS (ESI): Calcd for
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C19H13F5N2ONa [M+Na]+ 403.0840, Found: 403.0844.
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(E)-methyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)acrylate (3aj). This compound was
obtained as a light yellow oil (78 mg, 95% yield) by following the general procedure except using
0.45 mmol of 1a (1.5 equiv) and 0.30 mmol of alkene (2j) (1.0 equiv). 1H NMR (CDCl3, 400 MHz):
δ 7.70 (d, J = 16.0 Hz, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.31-7.30 (m, 2H), 7.06-7.20 (m, 1H), 7.00 (s,
1H), 6.36 (d, J = 16.0 Hz, 1H), 3.80 (s, 3H), 3.01 (br s, 6H); 13C NMR (CDCl3, 100 MHz): δ166.9,
153.1, 136.9, 133.7, 133.07, 127.6, 125.1, 121.9, 121.5, 117.9, 111.3, 108.3, 51.6, 37.4(br s); IR
(cm-1): ν 2949, 1689, 1631, 1447, 1391, 1346, 1305, 1273, 1173, 749; HRMS (ESI): Calcd for
C15H16N2O3 [M+Na]+ 295.1053, Found: 295.1055.
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(E)-ethyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)acrylate (3ak). This compound was
obtained as a light red oil (73 mg, 85% yield) by following the general procedure except using 0.45
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mmol of 1a (1.5 equiv) and 0.30 mmol of alkene (2k) (1.0 equiv). H NMR (CDCl3, 400 MHz): δ
7.68 (d, J = 16.0 Hz, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.32-7.27 (m, 2H), 7.17 (t, J = 7.7 Hz, 1H), 6.98
(s, 1H), 6.35 (d, J = 16.0 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2H), 3.02 (br s, 6H), 1.32 (t, J = 7.1 Hz, 3H);
13C NMR (CDCl3, 100 MHz): δ 166.5, 153.2, 137.0, 133.8, 132.8, 127.8, 125.1, 121.9, 121.5, 118.5,
111.4, 108.3, 60.5, 37.5 (br s), 14.2; IR (cm-1): ν 2980, 2932, 1699, 1633, 1447, 1392, 1345, 1304,
1183, 1036, 973, 747; HRMS (MALDI): Calcd for C16H18N2O3Na [M+Na]+ 309.1210, Found:
309.1209.
(E)-butyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)acrylate (3al). This compound was
obtained as a light yellow oil (79 mg, 84% yield) by following the general procedure except using
0.45 mmol of 1a (1.5 equiv) and 0.30 mmol of alkene (2l) (1.0 equiv). 1H NMR (CDCl3, 400 MHz):
δ 7.68 (d, J = 16.0 Hz, 1H), 7.60 (d, J = 7.9 Hz, 1H), 7.33-7.27 (m, 2H), 7.17 (t, J = 7.2 Hz, 1H),
6.98 (s, 1H), 6.36 (d, J = 16.0 Hz, 1H), 4.20 (t, J = 6.7 Hz, 2H), 3.02 (br s, 6H), 1.72-1.65 (m, 2H),
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1.47-1.38 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H); C NMR (CDCl3, 100 MHz): δ 166.7, 153.2, 137.0,
133.8, 132.8, 127.8, 125.1, 121.9, 121.5, 118.5, 111.4, 108.2, 64.4, 37.6 (br s), 30.6, 19.1, 13.7; IR
(cm-1): ν 2959, 2873, 1695, 1632, 1499, 1448, 1391, 1345, 1306, 1272, 1181, 1146, 744; HRMS
(MALDI): Calcd for C18H22N2O3Na [M+Na]+ 337.1523, Found: 337.1524.
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(E)-benzyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)acrylate (3am). This compound was
obtained as a light yellow oil (97 mg, 93% yield) by following the general procedure except using
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0.45 mmol of 1a (1.5 equiv) and 0.30 mmol of alkene (2m) (1.0 equiv). H NMR (CDCl3, 400
MHz): δ 7.74 (d, J = 16.0 Hz, 1H), 7.61 (d, J = 7.9 Hz, 1H), 7.44-7.35 (m, 5H), 7.32-7.31 (m, 2H),
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(CDCl3, 100 MHz): δ 166.4, 153.2, 137.1, 135.9, 133.8, 133.5, 128.5, 128.3, 128.2, 127.8, 125.2,
122.0, 121.7, 118.0, 111.5, 108.6, 66.4, 37.6 (br s); IR (cm-1): ν 3553, 3413, 1690, 1630, 1447, 1390,
1345, 1303, 1271, 1181, 1163, 1145, 745, 693; HRMS (ESI): Calcd for C21H20N2O3 [M+Na]+
371.1366, Found: 371.1370.
(E)-N,N-dimethyl-2-(2-(phenylsulfonyl)vinyl)-1H-indole-1-carboxamide
(3an).
This
compound was obtained as a light red oil (93 mg, 87% yield). 1H NMR (CDCl3, 400 MHz): δ 7.95
(d, J = 7.4 Hz, 2H), 7.73 (d, J = 15.4 Hz, 1H), 7.60 (dd, J = 7.7, 2.8 Hz, 2H), 7.55 (t, J = 7.5 Hz,
2H), 7.36-7.31 (m, 2H), 7.21-7.17 (m, 1H), 6.99 (s, 1H), 6.77 (d, J = 15.4 Hz, 1H), 2.98 (br s, 6H);
13C NMR (CDCl3, 100 MHz): δ 152.9, 140.4, 137.3, 133.4, 131.4, 131.1, 129.3, 127.5, 127.4, 126.7,
125.8, 122.2, 121.9, 111.6, 110.4, 37.6 (br s), 37.5 (br, s); IR (cm-1): ν 3057, 2963, 1684, 1607, 1446,
1394, 1308, 1261, 1145, 1084, 842; HRMS (MALDI): Calcd for C19H18N2O3SNa [M+Na]+ 377.0930,
Found: 377.0931.
(E)-diethyl 2-(1-(dimethylcarbamoyl)-1H-indol-2-yl)vinylphosphonate (3ao). This compound
was obtained as a light red oil (98 mg, 93% yield). 1H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 7.9
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Hz, 1H), 7.48 (dd, J = 22.9, 17.6 Hz, 1H), 7.31-7.28 (m, 2H), 7.16 (t, J = 7.2 Hz, 1H), 6.93 (s, 1H),
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(CDCl3, 100 MHz): δ 153.2, 137.0, 136.9 (d, JC-P = 5.1 Hz), 134.3 (d, JC-P = 27.7 Hz), 127.6, 125.1,
122.0, 121.6, 115.4, 113.5, 111.4, 107.9, 62.0, 61.9, 37.8 (br s), 37.5 (br s), 16.34, 16.30; 31P NMR
(CDCl3, 162 MHz): δ 18.7 (s); IR (cm-1): ν 2982, 2931, 1684, 1616, 1447, 1392, 1341, 1247, 1179,
1024, 964, 852, 750; HRMS (ESI): Calcd for C17H23N2O4PNa [M+Na]+ 373.1288, Found: 373.1285.
(E)-2-(2-cyanovinyl)-N,N-dimethyl-1H-indole-1-carboxamide (3ap). This compound was
obtained as a light red oil (40 mg, 56% yield) by following the general procedure except using 5.0
mol % of [Ru(p-cymene)Cl2]2, 20.0 mol % of AgSbF6 and 4.0 equiv of alkene (2p) for 30 h. 1H
NMR (CDCl3, 400 MHz): δ 7.62 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 16.6 Hz, 1H), 7.37-7.33 (m, 1H),
7.29 (d, J = 7.7 Hz, 1H), 7.23-7.19 (m, 1H), 7.01 (s, 1H), 5.83 (d, J = 16.6 Hz, 1H), 3.04 (br s, 6H);
13C NMR (CDCl3, 100 MHz): δ 153.0, 138.8, 137.1, 133.0, 127.5, 125.9, 122.4, 122.0, 118.0, 111.6,
108.6, 96.1, 38.0 (br s), 37.7 (br s); IR (cm-1): ν 3060, 2930, 2213, 1684, 1489, 1445, 1393, 1345,
1307, 1181, 1065, 800; HRMS (ESI): Calcd for C14H13N3ONa [M+Na]+ 262.0951, Found: 262.0955.
(E)-methyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)but-2-enoate (3aq). This compound was
obtained as a light red oil (77 mg, 90% yield) by following the general procedure except using 5.0
mol % of [Ru(p-cymene)Cl2]2, 20.0 mol % of AgSbF6 and 4.0 equiv of alkene (2q) for 30 h. 1H
NMR (CDCl3, 400 MHz): δ 7.60 (d, J = 7.9 Hz, 1H), 7.36 (d, J = 8.1 Hz, 1H), 7.30 (td, J = 7.6, 1.1
Hz, 1H), 7.18 (td, J = 7.4, 1.0 Hz, 1H), 6.83 (s, 1H), 6.04 (d, J = 1.2 Hz, 1H), 3.74 (s, 3H), 3.16 (s,
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3H), 2.85 (s, 3H), 2.58 (d, J = 1.2 Hz, 3H); C NMR (CDCl3, 100 MHz): δ 166.7, 154.0, 145.8,
140.3, 137.4, 127.8, 124.8, 121.9, 121.4, 116.6, 111.3, 108.2, 51.2, 37.8 (br s), 37.0 (br s), 17.7; IR
(cm-1): ν 2949, 1693, 1623, 1450, 1392, 1206, 1163, 1050, 810, 744; HRMS (MALDI): Calcd for
C16H18N2O3Na [M+Na]+ 309.1210, Found: 309.1214.
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(E)-methyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)-3-phenylacrylate (3ar). This compound
was obtained as a light yellow solid (57 mg, 55% yield) by following the general procedure except
using 5.0 mol % of [Ru(p-cymene)Cl2]2, 20.0 mol % of AgSbF6 and 4.0 equiv of alkene (2r) for 30
h. M.p.: 111-113 oC; 1H NMR (CDCl3, 400 MHz): δ 7.60 (d, J = 7.9 Hz, 1H), 7.38-7.35 (m, 3H),
7.31-7.26 (m, 3H), 7.22-7.16 (m, 2H), 6.76 (s, 1H), 6.38 (s, 1H), 3.63 (s, 3H), 2.79 (br s, 3H), 2.62
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(br s, 3H); C NMR (CDCl3, 100 MHz): δ 166.0, 153.1, 148.1, 140.2, 137.4, 136.9, 129.5, 128.8,
127.8, 127.5, 124.8, 121.9, 121.6, 117.3, 111.3, 110.1, 51.4, 38.4, 36.4; IR (cm-1): ν 2949, 1719,
1683, 1558, 1474, 1449, 1388, 1206, 1166, 1130, 763, 699; HRMS (MALDI): Calcd for
C21H20N2O3Na [M+Na]+ 371.1366, Found: 371.1375.
(E)-methyl 3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)-2-methylacrylate (3as). This compound
was obtained as light brown oil (38 mg, 44% yield) by following the general procedure except using
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5.0 mol % of [Ru(p-cymene)Cl2]2, 20.0 mol % of AgSbF6 and 4.0 equiv of alkene (2s) for 30 h. H
NMR (CDCl3, 400 MHz): δ 7.64-7.62 (m, 2H), 7.34 (d, J = 8.1 Hz, 1H), 7.30 (t, J = 7.5 Hz, 1H),
7.19 (t, J = 7.3 Hz, 1H), 6.90 (s, 1H), 3.82 (s, 3H), 3.01 (br s, 6H), 2.27 (s, 3H); 13C NMR (CDCl3,
100 MHz): δ 168.5, 153.4, 135.7, 133.9, 128.9, 128.3, 126.9, 124.7, 121.8, 121.4, 111.5, 109.3, 52.2,
37.8 (br), 14.9; IR (cm-1): ν 3054, 2951, 1699, 1627, 1490, 1449, 1391, 1309, 1262, 1218, 1113,
802, 751; HRMS (ESI): Calcd for C16H18N2O3Na [M+Na]+ 309.1210, Found: 309.1210.
N,N-dimethyl-2-(3-oxocyclopentyl)-1H-indole-1-carboxamide (3at). This compound was
obtained as a light yellow solid (49 mg, 60% yield) by following the general procedure except using
5.0 mol % of [Ru(p-cymene)Cl2]2 and 20.0 mol % of AgSbF6 for 30 h. M.p.: 174-176 oC; 1H NMR
(CDCl3, 400 MHz): δ 7.54 (d, J = 7.8 Hz, 1H), 7.25-7.21 (m, 1H), 7.18-7.13 (m, 2H), 6.40 (s, 1H),
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3.88-3.84 (m, 1H), 3.09 (br s, 6H), 2.73-2.70 (m, 1H), 2.47-2.09 (m, 5H); C NMR (CDCl3, 100
MHz): δ 217.5, 154.2, 142.3, 135.5, 128.0, 122.9, 121.3, 120.6, 110.8, 101.9, 44.5, 38.0, 34.2, 29.0
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(br s) (one carbon signal missing due to overlap); IR (cm-1): ν 2918, 1742, 1685, 1637, 1617, 1456,
1392, 1300, 1187, 1060, 749, 621; HRMS (ESI): Calcd for C16H18N2O2 [M+Na]+ 293.1261, Found:
293.1263.
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(E)-3-(1-(dimethylcarbamoyl)-1H-indol-2-yl)acrylic acid (3au). This compound was obtained
as a gray white solid (66 mg, 85% yield). M.p.: 172-174 oC; 1H NMR (CDCl3, 400 MHz): δ 7.80 (d,
J = 15.9 Hz, 1H), 7.63 (d, J = 7.9 Hz, 1H), 7.33 (d, J = 3.7 Hz, 2H), 7.23-7.18 (m, 1H), 7.07 (s, 1H),
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6.37 (d, J = 16.0 Hz, 1H), 3.07 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 171.7, 153.3, 137.2,
135.0, 133.5, 127.7, 125.5, 122.1, 121.8, 117.4, 111.5, 109.2, 37.6 (br s); IR (cm-1): ν 2928, 1684,
1629, 1489, 1448, 1394, 1183, 748; HRMS (ESI): Calcd for C14H14N2O3 [M-H]- 257.0932, Found:
257.0935.
2-allyl-N,N-dimethyl-1H-indole-1-carboxamide (3av). This compound was obtained as light
yellow oil (21 mg, 31% yield) by following the general procedure except using 5.0 mol % of
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[Ru(p-cymene)Cl2]2, 20.0 mol % of AgSbF6 and 4.0 equiv of alkene (2v). H NMR (CDCl3, 400
MHz): δ 7.53 (d, J = 7.7 Hz, 1H),7.19 (d, J = 3.7 Hz, 2H), 7.16-7.11 (m,1H), 6.38 (s, 1H), 6.00-5.90
(m, 1H), 5.18-5.10 (m, 2H), 3.63 (d, J = 6.4 Hz, 2H), 3.01 (br s, 6H); 13C NMR (CDCl3, 100 MHz):
δ 154.2, 138.5, 135.6, 134.7, 128.4, 122.4, 121.0, 120.3, 116.8, 110.8, 104.0, 37.6 (br s), 37.4 (br s),
31.7; IR (cm-1): ν 3054, 2961, 2926, 1684, 1489, 1455, 1391, 1302, 1063, 797; HRMS (ESI): Calcd
for C14H16N2ONa [M+Na]+ 251.1155, Found: 251.1156.
(E)-2-(4-bromostyryl)-N,N,3-trimethyl-1H-indole-1-carboxamide (3bg). This compound was
obtained as a slight yellow oil (69 mg, 60% yield) by following the general procedure except using
5.0 mol % of [Ru(p-cymene)Cl2]2 and 0.90 mmol of 4-Bromostyrene (3.0 equiv) for 30 h. 1H NMR
(CDCl3, 400 MHz): δ 7.56 (d, J = 7.8 Hz, 1H), 7.48 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H),
7.32 (d, J = 7.7 Hz, 1H), 7.30-7.26 (m, 1H), 7.23-7.17 (m, 2H), 6.76 (d, J = 16.5 Hz, 1H), 3.00 (br s,
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6H), 2.45 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ 154.5, 136.2, 135.8, 132.1, 131.7, 129.4, 129.0,
127.7, 124.1, 121.4, 121.1, 119.1, 117.7, 114.8, 110.9, 37.5 (br s), 9.8; IR (cm-1): ν 3049, 2926,
1684, 1630, 1487, 1454, 1392, 1108, 1008, 807; HRMS (ESI): Calcd for C20H19BrN2ONa [M+Na]+
405.0573, Found: 405.0570.
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(E)-2-(4-bromostyryl)-4-chloro-N,N-dimethyl-1H-indole-1-carboxamide
(3cg).
This
compound was obtained as a slight yellow oil (112 mg, 93% yield). 1H NMR (CDCl3, 400 MHz): δ
7.48 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.20 (dd, J = 7.1, 1.8 Hz, 1H), 7.18-7.14 (m, 2H),
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7.13-7.11 (m, 2H), 6.97 (s, 1H), 3.14 (br s, 3H), 2.91 (br s, 3H); C NMR (CDCl3, 100 MHz): δ
153.2, 137.3, 136.4, 135.4, 131.7, 130.4, 128.0, 127.2, 125.8, 123.9, 121.9, 121.3, 117.3, 109.7,
101.1, 37.5 (br s); IR (cm-1): ν 3056, 2962, 2927, 1690, 1487, 1426, 1397, 1261, 1168, 1071, 1008,
808; HRMS (MALDI): Calcd for C19H16BrClN2ONa [M+Na]+ 425.0027, Found: 425.0026.
(E)-2-(4-bromostyryl)-5-fluoro-N,N-dimethyl-1H-indole-1-carboxamide
(3dg).
This
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compound was obtained as a slight yellow solid (83 mg, 72% yield). M.p.: 182-184 C; H NMR
(CDCl3, 400 MHz): δ 7.48 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.21-7.25 (m, 2H), 7.11 (d,
J = 16.4 Hz, 1H), 7.05 (d, J = 16.4 Hz, 1H), 6.98 (td, J = 9.1, 2.5 Hz, 1H), 6.82 (s, 1H), 3.02 (s,
6H); 13C NMR (CDCl3, 100 MHz): δ 158.8 (d, JC-F = 237.5 Hz), 153.7, 138.4, 135.6, 132.6, 131.9,
130.1, 129.0 (d, JC-F = 10.6 Hz), 128.1, 122.0, 117.8, 112.0 (d, JC-F = 9.7 Hz), 111.7 (d, JC-F = 26.2
Hz), 105.7 (d, JC-F = 23.8 Hz), 103.0 (d, JC-F = 4.5 Hz), 37.7 (br s); 19F NMR (CDCl3, 376 MHz): δ
-112.1 (s); IR (cm-1): ν 3064, 2931, 1683, 1615, 1581, 1486, 1444, 1068, 941, 807; HRMS (ESI):
Calcd for C19H16BrFN2ONa [M+Na]+ 409.0322, Found: 409.0325.
(E)-2-(4-bromostyryl)-5-chloro-N,N-dimethyl-1H-indole-1-carboxamide (3eg).
This
compound was obtained as a slight yellow solid (100 mg, 83% yield). M.p.: 174-176 oC; 1H NMR
(CDCl3, 400 MHz): δ 7.54 (d, J = 1.6 Hz, 1H), 7.48 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.5 Hz, 2H),
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7.22 (d, J = 8.7 Hz, 1H), 7.18 (dd, J = 8.7, 1.8 Hz, 1H), 7.11 (d, J = 16.4 Hz, 1H), 7.05 (d, J = 16.4
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Hz, 1H), 6.79 (s, 1H), 3.00 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 153.4, 138.1, 135.4, 134.4,
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131.8, 130.2, 129.4, 128.0, 127.2, 123.6, 122.0, 120.1, 117.5, 112.2, 102.4, 37.7 (br s), 37.6 (br s);
IR (cm-1): ν 3028, 2933, 1684, 1653, 1488, 1437, 1392, 1175, 1059, 963, 813; HRMS (MALDI): Calcd
for C19H17BrClN2O [M+H]+ 403.0207, Found: 403.0209.
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(E)-2-(4-bromostyryl)-5-bromo-N,N-dimethyl-1H-indole-1-carboxamide
(3fg).
This
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compound was obtained as a slight yellow solid (121 mg, 90% yield). M.p.: 145-147 C; H NMR
(CDCl3, 400 MHz): δ 7.71 (d, J = 1.7 Hz, 1H), 7.49 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H),
7.32 (dd, J = 8.7, 1.8 Hz, 1H), 7.17 (d, J = 8.7 Hz, 1H), 7.11 (d, J = 16.4 Hz, 1H), 7.06 (d, J = 16.4
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Hz, 1H), 6.80 (s, 1H), 3.01 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 153.4, 138.0, 135.5, 134.7,
131.9, 130.4, 130.1, 128.1, 126.3, 123.2, 122.0, 117.5, 114.9, 112.6, 102.3, 37.74 (br s), 37.68 (br s);
IR (cm-1): ν 3025, 2932, 1686, 1487, 1436, 1390, 1307, 1175, 1050, 812; HRMS (ESI): Calcd for
C19H16Br2N2ONa [M+Na]+ 468.9522, Found: 468.9514.
(E)-2-(4-bromostyryl)-5-methoxy-N,N-dimethyl-1H-indole-1-carboxamide
(3gg).
This
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compound was obtained as a slight red solid (72 mg, 60% yield). M.p.: 128-130 C; H NMR
(CDCl3, 400 MHz): δ 7.47 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.5 Hz, 2H), 7.20 (d, J = 8.9 Hz, 1H),
7.13 (d, J = 16.3 Hz, 1H), 7.02(dd, J = 9.4, 6.9 Hz, 2H), 6.89 (dd, J = 8.9, 2.4 Hz, 1H), 6.80 (s, 1H),
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3.86 (s, 3H), 3.02 (br s, 6H); C NMR (CDCl3, 100 MHz): δ 155.4, 154.0, 137.5, 135.4, 131.8,
131.3, 129.14, 129.06, 128.0, 121.7, 118.2, 113.5, 112.1, 103.2, 102.3, 55.7, 37,9 (br s), 37.7 (br s);
IR (cm-1): ν 2962, 1674, 1653, 1487, 1471, 1262, 1100, 1068, 1031, 802; HRMS (MALDI): Calcd
for C20H20BrN2O2 [M+H]+ 399.0703, Found: 399.0706.
(E)-2-(4-bromostyryl)-N,N-dimethyl-5-nitro-1H-indole-1-carboxamide
(3hg).
This
compound was obtained as a light yellow solid (56 mg, 45% yield) by following the general
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procedure except using 5.0 mol % of [Ru(p-cymene)Cl2]2 and 0.90 mmol of 4-Bromostyrene (3.0
equiv) for 30 h. 1H NMR (CDCl3, 400 MHz): δ 8.51 (d, J = 1.9 Hz, 1H), 8.13 (dd, J = 9.0, 2.0 Hz,
1H), 7.50 (d, J = 8.4 Hz, 2H), 7.38-7.34 (m, 3H), 7.14 (d, J = 16.3 Hz, 1H), 7.06 (d, J = 16.4 Hz,
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1H), 6.98 (s, 1H), 3.26 (s, 3H), 2.84 (s, 3H); C NMR (CDCl3, 100 MHz): δ 152.6, 143.2, 139.9,
138.7, 135.1, 132.0, 131.8, 128.2, 127.8, 122.6, 118.8, 117.4, 116.7, 111.1, 103.8, 37.6 (br s), 37.2
(br s); IR (cm-1): ν 2936, 1698, 1507, 1488, 1395, 1338, 1303, 1178, 1073, 810, 745, 669; HRMS
(ESI): Calcd for C19H16BrN3O3Na [M+Na]+ 436.0267, Found: 436.0268.
(E)-2-(4-bromostyryl)-6-chloro-N,N-dimethyl-1H-indole-1-carboxamide
(3ig).
This
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compound was obtained as a light yellow solid (111 mg, 92% yield). M.p.: 144-146 C; H NMR
(CDCl3, 400 MHz): δ 7.48 (d, J = 8.3 Hz, 3H), 7.35 (d, J = 8.3 Hz, 2H), 7.31 (br s, 1H), 7.14 (d, J =
8.4 Hz, 1H), 7.09 (d, J = 16.4 Hz, 1H), 7.03 (d, J = 16.3 Hz, 1H), 6.82 (s, 1H), 3.03 (br s, 6H); 13C
NMR (CDCl3, 100 MHz): δ 153.3, 137.5, 136.4, 135.5, 131.8, 129.8, 129.3, 128.0, 126.9, 122.4,
121.9, 121.5, 117.6, 111.2, 103.1, 37.9 (br s), 37.6 (br s); IR (cm-1): ν 2962, 1683, 1486, 1389, 1302,
1261, 1100, 1070, 1053, 1008, 805; HRMS (ESI): Calcd for C19H16BrClN2ONa [M+Na]+ 425.0027,
Found: 425.0032.
(E)-2-(4-bromostyryl)-N,N,7-trimethyl-1H-indole-1-carboxamide (3jg). This compound was
obtained as a light yellow oil (10 mg, 9% yield) by following the general procedure except using
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5.0 mmol % of [Ru(p-cymene)Cl2]2 and 0.90 mmol of 4-Bromostyrene (3.0 equiv) for 30 h. H
NMR (CDCl3, 400 MHz): δ 7.48 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 7.8 Hz, 1H), 7.35 (d, J = 8.5 Hz,
2H), 7.12-7.05 (m, 2H), 7.01-6.96 (m, 2H), 6.85 (s, 1H), 3.25 (s, 3H), 2.56 (s, 3H), 2.44 (s, 3H); 13C
NMR (CDCl3, 100 MHz): δ 154.9, 135.73, 135.72, 135.0, 131.8, 129.5, 128.6, 128.0, 125.5, 121.7,
121.5, 121.0, 118.7, 117.2, 102.3, 37.7, 36.6, 17.4; IR (cm-1): ν 3047, 2958, 2925, 1689, 1486, 1394,
1311, 1263, 1072, 1008, 809, 741; HRMS (ESI): Calcd for C20H19BrN2ONa [M+Na]+ 405.0573,
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Found: 405.0574.
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(2E,2'E)-diethyl 3,3'-(1-(dimethylcarbamoyl)-1H-pyrrole-2,5-diyl)diacrylate (5a). This
compound was obtained as a light green oil (80 mg, 80% yield) by following the general procedure
except using 5.0 mol % of [Ru(p-cymene)Cl2]2, 5.0 equiv of acrylic acid ester and 2.0 equiv of
Cu(OAc)2·H2O. 1H NMR (CDCl3, 400 MHz): δ 7.39 (d, J = 15.9 Hz, 1H), 6.68 (s, 2H), 6.20 (d, J =
15.9 Hz, 2H), 4.22 (qd, J = 7.1, 1.7 Hz, 4H), 3.23 (s, 3H), 2.61 (s, 3H), 1.30 (t, J = 7.1 Hz, 6H); 13C
NMR (CDCl3, 100 MHz): δ 166.7, 152.0, 131.4, 130.8, 116.7, 114.0, 60.5, 37.7, 37.0, 14.3; IR
(cm-1): ν 2981, 2935, 1704, 1620, 1410, 1393, 1332, 1166, 1039, 970, 794; HRMS (MALDI): Calcd
for C17H22N2O5Na [M+Na]+ 357.1421, Found: 357.1428.
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(2E,2'E)-benzyl 3,3'-(1-(dimethylcarbamoyl)-1H-pyrrole-2,5-diyl)diacrylate (5b). This
compound was obtained as a light red oil (98 mg, 72% yield) by following the general procedure
except using 5.0 mol % of [Ru(p-cymene)Cl2]2, 5.0 equiv of acrylic acid ester and 2.0 equiv of
Cu(OAc)2·H2O. 1H NMR (CDCl3, 400 MHz): δ 7.44 (d, J = 15.9 Hz, 2H), 7.39-7.38 (m, 6H), 6.69
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(s, 2H), 6.25 (d, J = 15.9 Hz, 2H), 5.22 (s, 4H), 3.21 (s, 3H), 2.60 (s, 3H); C NMR (CDCl3, 100
MHz): δ 166.4, 151.7, 135.9, 131.4, 131.3, 128.5, 128.1, 116.3, 114.1, 66.3, 37.6, 36.9 (one signal
missing due to overlap); IR (cm-1): ν 3065, 3033, 2949, 1704, 1620, 1497, 1409, 1391, 1263, 1159,
969, 785; HRMS (MALDI): Calcd for C27H26N2O5Na [M+Na]+ 481.1734, Found: 481.1731.
(E)-ethyl 3-(1-(dimethylcarbamoyl)-1H-pyrrol-2-yl)acrylate (6a). This compound was
obtained as a light brown solid (49 mg, 69% yield) by following the general procedure except using
1.5 equiv of pyrrole substrate and 1.0 equiv of acrylic acid ester. M.p.: 68-70 oC; 1H NMR (CDCl3,
400 MHz): δ 7.55 (d, J = 15.9 Hz, 1H), 6.94-6.93 (m, 1H), 6.67-6.66 (m, 1H), 6.26 (t, J = 2.9 Hz,
1H), 6.11 (d, J = 15.9 Hz, 1H), 4.20 (q, J = 7.1 Hz, 2H), 2.96 (s, 6H), 1.29 (t, J = 7.1 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 167.2, 153.5, 132.5, 129.1, 123.8, 114.7, 113.6, 111.1, 60.2, 37.8 (br s),
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14.3; IR (cm-1): ν 3146, 3128, 3070, 2964, 1700, 1684, 1653, 1625, 1437, 1387, 1262, 1100, 1058,
1028, 880, 800, 727; HRMS (MALDI): Calcd for C12H16N2O3Na [M+Na]+ 259.1053, Found:
259.1060.
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(E)-benzyl 3-(1-(dimethylcarbamoyl)-1H-pyrrol-2-yl)acrylate (6b). This compound was
obtained as a colorless solid (76 mg, 85% yield) by following the general procedure except using
o
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1.5 equiv of pyrrole and 1.0 equiv of acrylic acid ester. M.p.: 70 - 72 C; H NMR (CDCl3, 400
MHz): δ 7.63 (d, J = 15.9 Hz, 1H), 7.41-7.32 (m, 5H), 6.96 (dd, J = 2.9, 1.5 Hz, 1H), 6.69 (dd, J =
3.6, 1.3 Hz, 1H), 6.28 (t, J = 3.3 Hz, 1H), 6.18 (d, J = 15.9 Hz, 1H), 5.22 (s, 2H), 2.96 (br s, 6H);
13C NMR (CDCl3, 100 MHz): δ 166.9, 153.4, 136.1, 133.0, 129.0, 128.4, 128.09, 128.06, 124.0,
114.2, 113.8, 111.2, 66.0, 37.8 (br s); IR (cm-1): ν 3123, 3066, 3039, 2932, 1670, 1684, 1653, 1623,
1558, 1489, 1456, 1275, 1157, 741; HRMS (MALDI): Calcd for C17H18N2O3Na [M+Na]+ 321.1210,
Found: 321.1216.
(E)-butyl 3-(1-(dimethylcarbamoyl)-5-((E)-3-ethoxy-3-oxoprop-1-enyl)-1H-pyrrol-2-yl)acrylate
(7a). This compound was obtained as a slight red oil (65 mg, 60% yield) by following the general
1
procedure except using 3.0 equiv of acrylic acid ester. H NMR (CDCl3, 400 MHz): δ 7.38 (d, J =
15.9 Hz, 1H), 7.37 (d, J = 15.9 Hz, 1H), 6.68 (s, 2H), 6.189 (d, J = 15.9 Hz, 1H), 6.185 (d, J = 15.9
Hz, 1H), 4.24-4.14 (m, 4H), 3.22 (s, 3H), 2.60 (s, 3H), 1.68-1.61 (m, 2H), 1.44-1.35 (m, 2H), 1.29 (t,
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J = 7.1 Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H); C NMR (CDCl3, 100 MHz): δ 166.85, 166.80, 152.0,
131.4, 130.8, 116.7, 114.0, 113.9, 64.4, 60.5, 37.7, 37.0, 30.7, 19.1, 14.3, 13.7; IR (cm-1): ν 3524,
3446, 3306, 2960, 1704, 1626, 1558, 1457, 1393, 1304, 1265, 1168, 1038; HRMS (ESI): Calcd for
C19H26N2O5 [M+Na]+ 385.17341, Found: 385.1739.
(E)-benzyl 3-(5-((E)-3-butoxy-3-oxoprop-1-enyl)-1-(dimethylcarbamoyl)-1H-pyrrol-2-yl)acrylate
(7b). This compound was obtained as a slight red oil (102 mg, 80% yield) by following the general
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procedure except using 3.0 equiv of acrylic acid ester. H NMR (CDCl3, 400 MHz): δ 7.44 (d, J =
15.9 Hz, 1H), 7.40-7.33 (m, 6H), 6.69 (s, 2H), 6.25 (d, J = 16.5 Hz, 1H), 6.21 (d, J = 16.1 Hz, 1H),
5.22 (s, 2H), 4.17 (td, J = 6.7, 1.0 Hz, 2H), 3.22 (s, 3H), 2.61 (s, 3H), 1.69-1.62 (m, 2H), 1.45-1.36
(m, 2H), 0.95 (t, J = 7.4 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 166.7, 166.4, 151.6, 135.8, 131.5,
131.3, 131.2, 130.6, 128.4, 128.1, 116.8, 116.1, 114.0, 113.8, 66.2, 64.3, 37.6, 36.9, 30.5, 19.0, 13.6;
IR (cm-1): ν 2923, 1704, 1558, 1539, 1456, 1393, 1265, 1161, 970, 749, 699; HRMS (ESI): Calcd
for C24H28N2O5 [M+Na]+ 447.1890, Found: 447.1893.
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Competition experiments with indoles 1g and 1h (eq 2). A mixture of indole substrates 1g
(0.45 mmol, 1.5 equiv), 1h (0.45 mmol, 1.5 equiv), [Ru(p-cymene)Cl2]2 (4.59 mg, 0.0075 mmol,
2.5 mol %), Cu(OAc)2·H2O (60.0 mg, 0.30 mmol, 1.0 equiv.), and 4-bromostyrene (2g) (0.30 mmol,
1.0 equiv) was combined in a Schlenk tube followed by addition of Dioxane (2.0 mL) under Ar
atmosphere. Then the reaction mixture was heated to 100 oC with stirring for 24 hours. Afterwards,
the vial was cooled to room temperature. Silica was added to the flask and volatiles were
evaporated under reduced pressure. The purification was performed by flash column
chromatography on silica gel. Only the product 3gg (62 mg, 52% yield) was isolated.
Competition Experiments with Alkenes 2d and 2e (eq 3). A mixture of indole substrate (1a)
(0.30 mmol, 1.0 equiv), [Ru(p-cymene)Cl2]2 (4.59 mg, 0.0075 mmol, 2.5 mol %), Cu(OAc)2·H2O
(60.0 mg, 0.30 mmol, 1.0 equiv.), 4-vinylanisole (2d) (0.90 mmol, 3.0 equiv) and 4-fluorostyrene
(2e) (0.90 mmol, 3.0 equiv) was combined in a Schlenk tube followed by addition of dioxane (2.0
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mL) under Ar atmosphere. Then the reaction mixture was heated to 100 C with stirring for 24
hours. Afterwards, the vial was cooled to room temperature. Silica was added to the flask and
volatiles were evaporated under reduced pressure. The purification was performed by flash column
chromatography on silica gel to afford products 3ad (62 mg, 65% yield) and 3ae (18 mg, 20%
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yield).
Procedure
for
removal
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dimethylcarbamoyl
moiety
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N,N-dimethyl-2-styryl-1H-indole-1-carboxamide (0.15 mmol) was charged in a 50 mml round
bottom flask, then 6.0 equiv KOtBu (0.90 mmol, 101 mg) and THF (2.5 mL) was added. The
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reaction mixture was stirred at 25 C for about 16h. The solution was then diluted with NH4Cl
solution, the aqueous phase was extacted with EtOAc. The combined organic layer was washed
with brine, dried over Na2SO4, and evaporated under reduced pressure. Then the crude product can
be purified by column chromatography on silica gel.
(E)-2-(4-tert-butylstyryl)-1H-indole (8a). This compound was obtained as a grey solid (37
mg, 90% yield). M.p.: 127-129 oC; 1H NMR (CDCl3, 400 MHz): δ 8.24 (s, 1H), 7.58 (d, J = 7.8 Hz,
1H), 7.45 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.0 Hz, 1H), 7.19 (t, J = 7.5 Hz,
1H), 7.11-7.07 (m, 2H), 6.90 (d, J = 16.5 Hz, 1H), 6.60 (s, 1H), 1.35 (s, 9H); 13C NMR (CDCl3, 100
MHz): δ 151.0, 136.9, 136.5, 134.0, 129.0, 127.0, 126.0, 125.7, 122.7, 120.5, 120.1, 118.2, 110.5,
103.5, 34.6, 31.3. IR (cm-1): ν 3450, 2962, 2865, 1457, 1410, 1362, 1262, 1103, 1024, 819, 800,
737. HRMS (ESI): Calcd for C20H20N [M-H]- 274.1601, Found: 274.1603.
(E)-2-(4-bromostyryl)-1H-indole (8b). This compound was obtained as a light yellow solid
(35 mg, 78% yield). M.p.: 229-231 oC; 1H NMR (DMSO-d6, 400 MHz): δ 11.40 (s, 1H), 7.57 (d, J
= 8.4 Hz, 2H), 7.52-7.49 (m, 3H), 7.35 (d, J = 8.1 Hz, 1H), 7.30 (d, J = 16.5 Hz, 1H), 7.17-7.09 (m,
2H), 6.97 (t, J = 7.4 Hz, 1H), 6.60 (s, 1H); 13C NMR (DMSO-d6, 100 MHz): δ 137.4, 136.5, 136.3,
131.7, 128.3, 128.1, 125.7, 122.3, 120.5, 120.3, 120.2, 119.3, 111.0, 103.5. IR (cm-1): ν 3393, 1684,
1653, 1635, 1558, 1486, 1031, 998, 966, 810, 752, 655. HRMS (ESI): Calcd for C16H11BrN [M-H]-
296.0080, Found: 296.0082.
Procedure for removal of dimethylcarbamoyl moiety (eq 5). (E)-ethyl
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pressure, the residue was diluted with Et2O (25 mL). The pH of the solution was adjusted to 2-3 at 0
oC using a solution of 3M HCl. The aqueous solution was extacted with Et2O (3 × 20 mL) and the
combined the organic layers was washed with brine, dried over Na2SO4, and evaporated under
reduced pressure. The residue was purified by flash chromatography over silica gel (eluent:
CH3OH/CH2Cl2 = 1 : 40, v/v) to give the (E)-3-(1H-indol-2-yl)acrylic acid (9)[27] as a sligtly yellow
solid (135 mg, 72% yield). 1H NMR (DMSO-d6, 400 MHz): δ 12.34 (s, 1H), 11.55 (s, 1H), 7.56 (d,
J = 16.1 Hz, 1H), 7.55 (d, J = 7.1 Hz, 1H), 7.36 (d, J = 8.2 Hz, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.01 (t,
J = 7.4 Hz, 1H), 6.86 (s, 1H), 6.45 (d, J = 16.0 Hz, 1H); 13C NMR (DMSO-d6, 100 MHz): δ 167.8,
138.1, 134.5, 134.0, 128.0, 123.8, 121.1, 119.8, 116.9, 111.5, 108.0.
X-ray crystallography studies: Data collection was performed by using
graphite-monochromated MoKα radiation (ω-2θ scans). Semiempirical absorption corrections were
applied for all complexes.[28] The structures were solved by direct methods and refined by
full-matrix least-squares. All calculations were done using the SHELXL-97 program system.[29] All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms were assigned idealized
positions and were included in structure factor calculations. The crystal data and summary of the
X-ray data collection are presented in Table S1 in the Supporting Information.
ASSOCIATED CONTENT
Supporting information
Full spectroscopic data for all new compounds, and CIF files giving X-ray structural
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information for 3af and 3at. This material is available free of charge via the Internet at
http://pubs.acs.org.
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AUTHOR INFORMATION
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Corresponding Author
*Email: nklibin@nankai.edu.cn, bqwang@nankai.edu.cn
Author Contributions
§J. Ma and W. Xie contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful to NSFC (Nos. 21072097, 21072101, 21121002, and 21372121) and SRFDP (No.
20110031110009) for financial support.
REFERENCE
(1) For selected recent reviews about C-H bond functionalizations, see: (a) Ackermann, L. Acc.
Chem. Res. 2013, DOI: 10.1021/ar3002798. (b) Kozhushkov, S. I.; Ackermann, L. Chem. Sci. 2013,
4, 886. (c) Neufeldt, S. R.; Sanford, M. S. Acc. Chem. Res. 2012, 45, 936. (d) Song, G.; Wang, F.;
Li, X. Chem. Soc. Rev. 2012, 41, 3651. (e) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Chem.
Rev. 2012, 112, 5879. (f) Kuhl, N.; Hopkinson, M. N.; Wencel-Delord, J.; Glorius, F. Angew.
Chem., Int. Ed. 2012, 51, 10236. (g) Yamaguchi, J.; Yamaguchi, A. D.; Itami, K. Angew. Chem., Int.
Ed. 2012, 51, 8960. (h) Patureau, F. W.; Wencel-Delord, J.; Glorius, F. Aldrichimica Acta 2012, 45,
31. (i) Engle, K. M.; Mei, T. S.; Wasa, M.; Yu, J.-Q. Acc. Chem. Res. 2012, 45, 788. (j) Colby, D.
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