Synthesis of pyrrole derivatives from diallylamines by one-pot tandem ring-closing metathesis and metal-catalyzed oxidative dehydrogenation

Article abstract of DOI:10.1021/om400046r

A series of aryl-substituted pyrrole derivatives was synthesized from diallylamines through a ruthenium carbene catalyzed ring-closing metathesis reaction and in situ oxidative dehydrogenation reaction catalyzed by FeCl ₃·6H₂O or CuCl₂·2H₂O in the presence of O₂. The reaction was mild, simple, and convenient. An oxygen atmosphere played a critical role in obtaining high conversion of substituted pyrroles in the proposed catalytic system.

Full text of DOI:10.1021/om400046r

Article
pubs.acs.org/Organometallics
Synthesis of Pyrrole Derivatives from Diallylamines by One-Pot
Tandem Ring-Closing Metathesis and Metal-Catalyzed Oxidative
Dehydrogenation
Weiqiang Chen and Jianhui Wang*
Department of Chemistry, College of Science, Tianjin University, Tianjin 300072, People’s Republic of China
S
* Supporting Information
ABSTRACT: A series of aryl-substituted pyrrole derivatives
was synthesized from diallylamines through a ruthenium
carbene catalyzed ring-closing metathesis reaction and in situ
oxidative dehydrogenation reaction catalyzed by FeCl3·6H2O
or CuCl2·2H2O in the presence of O2. The reaction was mild,
simple, and convenient. An oxygen atmosphere played a
critical role in obtaining high conversion of substituted
pyrroles in the proposed catalytic system.
diallylaniline under the catalysis of ruthenium carbene I or II
(Scheme 1) has also been observed, consistent with previous
INTRODUCTION
■
Pyrrole derivatives are important intermediates in the synthesis
of pharmaceuticals, biologically active natural products, and
organic functional materials.1,2 A variety of substituted pyrroles
also reportedly serve as building blocks in the total synthesis of
heterocyclic compounds.3 Many synthetic strategies have been
developed for the synthesis of pyrrole and its derivatives.4
Traditionally, pyrrole and its derivatives can be prepared by the
Paal−Knorr reaction,5 Clauson−Kass reaction,1b,6 conjugate
addition reaction,7 transition-metal-mediated reaction,8 reduc-
tive coupling,4a aza-Wittig reaction,9 multicomponent reac-
tion,10 and other operations.11 Among these reported methods
for pyrrole synthesis, the Paal−Knorr and Clauson−Kass
reactions are the most typical and commonly used protocols
for the construction of pyrrole frameworks. Some new methods
have also been developed on the basis of the Clauson−Kass
reaction.12 A number of pyrrole syntheses under microwave
irradiation, a nontraditional energy source, have been recently
reported as well.13
Meanwhile, olefin metathesis is a powerful tool for the
construction of C−C double bonds in organic synthesis and
materials chemistry.14 In particular, the ruthenium carbene
catalyzed ring-closing metathesis (RCM) reaction is a powerful
tool for the formation of five-, six-, or seven-membered
carbocyclic or heterocyclic structures from linear diene
substrates.15 Subsequent dehydrogenation of these carbocyclic
or heterocyclic compounds can give aromatic compounds.16
The RCM reaction enables the construction of pyrrole
derivatives through linear diene substrates by tandem
cyclization and dehydrogenation reactions.
Scheme 1. Ruthenium Carbenes I and II Used for Olefin
Metathesis
observations. The yields of pyrrole derivatives in all these
catalytic systems are low, and large amounts of catalyst loadings
are required to achieve higher conversion.17b To achieve higher
yields of pyrrole derivatives using a lower amount of catalyst
loading, special means for dehydrogenated aromatization have
to be applied. Some reports have shown that pyrroline and
pyrrole derivatives can be synthesized by the microwave-
assisted RCM of diene substrates, taking advantage of the
energy source of microwave irradiation.18 Stevens’ group has
developed a new and straightforward protocol for pyrrole
synthesis using a unique one-pot combination of ring-closing
metathesis and in situ oxidative aromatization using a
quinine.19a This strategy has subsequently been applied to the
synthesis of 2-phosphonopyrroles via a one-pot RCM/
oxidation sequence.19b,c These reactions have paved the way
for the use of tandem olefin metathesis and dehydrogenation as
key reactions for the construction of pyrrole derivatives.
In fact, some previous studies have revealed that pyrrole
derivatives are occasionally observed as a side product during
RCM.17 In our previous report,15i the formation of 1-phenyl-
1H-pyrrole as a side product during the ring closing of N,N-
Received: January 18, 2013
© XXXX American Chemical Society
A
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However, the reports cover a limited synthetic scope and the
compounds have been prepared by nontraditional methods
(assisted by microwave irradiation or ultrasound) or by the in
situ dehydrogenation of ring-closing products using a
stoichiometric ratio of oxidant. Hence, the development of
catalytic approaches to the mild, simple, and convenient
synthesis of pyrrole derivatives remains urgent. Notably, several
transition-metal compounds can catalyze dehydrogenation
under mild reaction conditions.20 Thus, the addition of these
metal complexes to the ruthenium carbene catalysis system can
enhance the dehydrogenation process to give aromatized
pyrrole derivatives in high yield. However, some reports have
shown that the addition of metal complexes to a catalysis
system significantly increases the decomposition rate of the
ruthenium carbene catalyst or completely deactivates the
ruthenium carbene catalyst in the extreme case.21 An ideal
two-component catalytic system for the synthesis of pyrrole
derivatives by the corresponding amines should enable the
addition of metal compounds to a system for catalysis
dehydrogenation without interfering with the ruthenium
carbene complexes or without significantly increasing the
decomposition of the ruthenium carbene complexes. The two
reaction steps should be mild, simple, and convenient.
Accordingly, the present study aimed to develop a highly
efficient approach to the synthesis of pyrrole derivatives. A
series of experiments was conducted to examine the
compatibility of these metal compounds with ruthenium
carbenes I and II and to optimize the reaction conditions.
Results showed that the diallylamines were converted to
substituted pyrroles in good to excellent yields in the presence
of ruthenium carbene I/FeCl3·6H2O or II/CuCl2·2H2O under
an O2 atmosphere through tandem reactions of RCM and
dehydrogenation in one pot. This mild, straightforward
procedure for the synthesis of pyrrole derivatives is reported
in this paper.
Table 1. Optimization of Reaction Conditions (1a as Model)
ab
,
entry
Ru cat.
additive
yield of 2a/3a/4a (%)
c
1
I
II
I
I
I
I
I
I
I
I
I
I
I
I
I
I
6/86/0
8/90/0
13/83/0
46/50/0
53/41/0
80/9/0
65/27/0
32/61/0
18/78/0
91/0/0
28/0/0
39/56/0
90/0/0
93/0/0
72/0/0
55/40/0
c
2
3
d
4
c
RuCl3·3H2O
RuCl3·3H2O
RuC13·3H2O
RhC13·3H2O
CoCl2·6H2O
NiCl2·6H2O
PdCl2
5
6
7
8
9
10
11
12
13
14
15
16
Cu(NO3)2·9H2O
CuSO4·5H2O
CuCl2·2H2O
FeCl3 6H2O
Fe(NO3)3·9H2O
Fe2(SO4)3
a
Reaction conditions: [Ru] cat. (0.0125 mmol, 5 mol %), additive
(0.05 mmol, 20 mol %), diallylaniline (0.25 mmol), CH2Cl2 (2.5 mL),
b
40 °C, 24 h under an O2 atmosphere. Yields were obtained by GC-
c
d
MS. Reaction was carried out under an N2 atmosphere. Reaction was
carried out under an N2 atmosphere, additive (0.025 mmol, 10 mol
%).
yield (93%) of 2a was found in the reaction using I as the
catalyst with 20 mol % of FeCl3·6H2O as the additive (Table 1,
entry 14). It is worth noting that compounds 3a and 4a were
not observed in the reaction mixture after 24 h in these catalytic
systems. Therefore, the use of I (5.0 mol %) as the catalyst in
combination with FeCl3·6H2O (20 mol %) in CH2Cl2 at 40 °C
under an O2 atmosphere was selected as the optimized catalytic
system for the transformation of diallylamines to pyrrole
products.
With the optimized catalytic system in hand, the scope and
limitation of this one-pot system was further investigated by the
reaction of various diallylamines with electron-donating or
electron-withdrawing groups under the same conditions, and
the results are shown in Table 2. The reaction of phenyl-
diallylamines 1a−i, which have an electron-donating group
(such as −Me, −Et, −OMe, or −OEt) on the phenyl group,
smoothly proceeded to give the corresponding products 2a−i
in good to excellent yields (82%−91%) when ruthenium
carbene I (5.0 mol %) was used as the catalyst in combination
with FeCl3·6H2O (20 mol %) in CH2Cl2 at 40 °C under a O2
atmosphere (Table 2, entries 1−9). In these reaction systems,
the ring-closing products were completely converted to N-
arylpyrrole derivatives.
However, more sterically hindered substrates such as 1j,k
gave the corresponding N-arylpyrrole derivatives in low yields
(36% for 2j and 28% for 2k) under similar reaction conditions
(Table 2, entries 10 and 11). Diallylamines bearing an electron-
withdrawing group (e.g., −Br, −F, −Cl, −COOEt, −COCH3,
or −NO2) also gave the corresponding products in moderate or
low yields (13%−68%) (Table 2, entries 12−19). Many ring-
closing products remained in these reaction systems, indicating
that the dehydrogenation of these 1-aryl-2,5-dihydro-1H-
pyrroles bearing an electron-withdrawing group on the phenyl
ring was difficult under such reaction conditions. N,N-
RESULTS AND DISCUSSION
■
The RCM reaction of N,N-diallylaniline (1a) was initially
conducted in the presence of ruthenium carbene I (5 mol %) at
40 °C for 24 h under a N2 atmosphere. The desired product N-
phenylpyrrole (2a) was observed in low yield, whereas 1-
phenyl-2,5-dihydro-1H-pyrrole (3a) was obtained as the major
product (Table 1, entry 1). When the catalyst was replaced with
ruthenium carbene II, the yields of 2a and 3a slightly increased
(Table 1, entry 2). The yield of 2a increased to 13% when the
N2 protective atmosphere was changed to an O2 atmosphere
(Table 1, entry 3). This result indicates that oxygen may play
an important role in the formation of 2a by benefiting the
dehydrogenation process. When I was used in combination
with RuCl3·3H2O (10 mol %), the pyrrole product (2a) was
obtained in 46% yield under a N2 atmosphere, and the yield of
2a slightly improved when the amount of RuCl3·3H2O was
increased to 20 mol % (Table 1, entries 4 and 5). Interestingly,
2a was afforded in 80% yield when the N2 atmosphere was
changed to an O2 atmosphere (Table 1, entry 6).
Further experiments show that 2a was obtained in low yields
under similar reaction conditions when RhCl3·3H2O,
CoCl2·6H2O, NiCl2·6H2O, Cu(NO3)2·9H2O, CuSO4·5H2O,
Fe(NO3)3·9H2O, or Fe2(SO4)3 was used as the additive in
combination with I under an O2 atmosphere. PdCl2 and
CuCl2·2H2O were found to be good additives; the diallylamine
was completely converted and 2a was obtained in 91% and 90%
yields, respectively (Table 1, entries 10 and 13). The highest
B
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a
Table 2. Synthesis of N-Arylpyrrole Derivatives by the FeCl3·6H2O-Assisted Ring-Closing Metathesis of Diallylamines
a
Reaction conditions: ruthenium carbene I (0.0125 mmol, 5 mol %), FeCl3·6H2O (0.05 mmol, 20 mol %), diallylaniline 1 (0.25 mmol) in 2.5 mL of
b
CH2Cl2, 40 °C, 24 h, under an O2 atmosphere. Isolated yields.
Diallylnaphthalen-1-amine (1t) was also converted to 1-
(naphthalen-1-yl)-1H-pyrrole (2t) in low yield because of the
steric hindrance of the naphthalene group.
changed to O2 under similar conditions. Unlike the case when
catalyst I was used, the reaction was prevented when
FeCl3·6H2O was added to the reaction system (Table 3,
entry 4), indicating that FeCl3·6H2O was incompatible with II.
The pyrrole derivative 2s was obtained in 38% yield in the
presence of 10 mol % of II and PdCl2 (Table 3, entry 5). Many
ring-closing products remained in the reaction mixtures. The
highest yield (91%) of 2s was obtained when II (10.0 mol %)
was used in combination with CuCl2·2H2O (20.0 mol %).
Decreasing the catalyst loading of II to 5.0 mol % resulted in
incomplete conversion of the ring-closing product. On the basis
of these experiments, the use of II (10.0 mol %) as the catalyst
in combination with CuCl2·2H2O (20.0 mol %) in DCE at 60
°C for 24 h under an O2 atmosphere was selected as the
optimum reaction conditions for the transformation of N,N-
diallylaniline bearing an electron-withdrawing group on the aryl
ring to the corresponding pyrrole products. Thus, sterically
Diallylamines bearing an electron-withdrawing group cannot
be converted to the desired pyrrole derivatives in high yield by
the catalyst of ruthenium carbene I. Thus, the ability of the
ruthenium carbene II catalytic system to achieve favorable
reaction conditions for diallylamines bearing electron-with-
drawing groups was investigated, and the results are shown in
Table 3. When the RCM of N,N-diallyl-3-nitroaniline (1s), a
substrate with a strong electron-withdrawing group, was
conducted in the presence of ruthenium carbene II in
ClCH2CH2Cl (DCE) at 60 °C for 24 h under an N2
atmosphere, the pyrrole derivative 2s was obtained in 7% and
11% yields in the presence of 5.0 and 10.0 mol % of II,
respectively (Table 3, entries 1 and 2). The yield of 2s
increased to 19% (Table 3, entry 3) when the atmosphere was
C
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more hindered substrates (1j,k) and substrates having an
electron-withdrawing group (1l−t) were re-examined using II/
CuCl2·2H2O catalyst. The results are shown in Table 4. The
reaction of the more sterically hindered substrates 1j,k gave the
corresponding pyrrole products 2j,k in 61% and 56% yields,
respectively (Table 4, entries 1 and 2). The desired product
yields of these two sterically hindered substrates significantly
improved in comparison with those of the I/FeCl3·6H2O
catalytic system. Substrates having an electron-withdrawing
group (1l−t) were also found to be converted to the
corresponding pyrrole products (2l−t) in yields higher than
for those using the I/FeCl3·6H2O catalytic system (Table 4,
entries 3−10). Compound 2t was obtained from 1t in 69%
yield using II/CuCl2·2H2O catalyst, which was significantly
improved in comparison with that of the I/FeCl3·6H2O
catalytic system (Table 4, entry 11). The high catalytic activity
of II also allowed the conversion of N-allyl-N-(2-methylallyl)-
aniline (1u) and 1-(4-(allyl(2-methylallyl)amino)phenyl)-
ethanone (1v) to the corresponding 3-methyl-1-phenyl-1H-
pyrrole (2u) and 1-(4-(3-methyl-1H-pyrrol-1-yl)phenyl)-
Table 3. Optimization of Reaction Conditions (1s as Model)
a,b
entry Ru cat. (amt (mol %))
additive
yield of 2s/3s/4s (%)
c
1
2
3
4
5
6
7
II (5.0)
7/90/0
11/86/0
19/78/0
5/0/0
c
II (10.0)
II (10.0)
II (10.0)
II (10.0)
II (5.0)
FeCl3·6H2O
PdCl2
38/60/0
68/27/0
91/0/0
CuCl2·2H2O
CuCl2·2H2O
II (10.0)
a
Reaction conditions: ruthenium carbene II (5%−10%), additive (0.05
mmol, 20 mol %), diallylaniline 1s (0.25 mmol) in 2.5 mL of
ClCH2CH2Cl, 60 °C, 24 h, under an O2 atmosphere. Yields were
obtained by GC-MS. The reaction was carried out under an N2
b
c
atmosphere.
a
Table 4. Synthesis of N-Arylpyrrole Derivatives by CuCl2·2H2O-Assisted Ring-Closing Metathesis of Diallylamines 1j−z
a
Reaction conditions: II (0.025 mmol, 10 mol %), CuCl2·2H2O (0.05 mmol, 20 mol %), diallylaniline 1 (0.25 mmol) in 2.5 mL of ClCH2CH2Cl, 60
b
°C, 24 h, under an O2 atmosphere; Isolated yields.
D
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ethanone (2v) in 88% and 73% yields, respectively (Table 4,
entries 12 and 13). N-Allyl-N-(2-methylallyl)benzamide (1w)
and N,N-diallylbenzamide (1x), in which the N atom is
protected by a benzoyl group, were also converted to benzoyl-
protected pyrroles 2w,x in 83% and 80% yields, respectively,
although a certain amount of ring-closing products remained in
these reaction mixtures (Table 4, entries 14 and 15). However,
when N,N-diallylbenzenesulfonamide (1y), in which the N
atom is protected by a phenylsulfonyl group, was subjected to
the reaction using II/CuCl2·2H2O catalyst, the ring-closing
product completely remained and no pyrrole 2y was formed
(Table 4, entry 16). The II/CuCl2·2H2O catalyst was
completely inert to N-allyl-N-benzylprop-2-en-1-amine (1z);
even the ring-closing product was not observed, indicating that
the II/CuCl2·2H2O catalytic system was not applicable to these
types of substrates (Table 4, entry 17). No pyrrole product was
observed when N-allyl-N-(3-nitrobenzyl)prop-2-en-1-amine
and N,N-diallylcyclohexanamine were subjected to the reaction
under similar reaction conditions, indicating that the current
catalytic system is not suitable for N-alkyl-substituted diallyl-
amines.
The observation of the high activity of II/CuCl2·2H2O to the
catalytic formation of pyrrole from diallylaniline bearing an
electron-withdrawing group prompted us to conduct more
experiments to uncover the catalytic mechanism. Initially, an
independent reaction mechanism was proposed. This mecha-
nism involved the RCM of the diallylaniline catalyzed by
ruthenium carbene I or II to give 1-phenyl-2,5-dihydro-1H-
pyrrole, following by dehydrogenation in the presence of
FeCl3·6H2O or CuCl2·2H2O under O2. Indeed, the 2,5-
dihydropyrrole 3a was completely converted in the presence
of CuCl2·2H2O (20 mol %) or FeCl3·6H2O (20 mol %) under
O2, and pyrrole product 2a was isolated in 89% and 91% yields
(Scheme 2), respectively. These data indicate that the tandem
for substrates bearing a strong electron-withdrawing group. To
prove this hypothesis, 31P NMR was used to track the system
containing II and CuCl2·2H2O. Initially, the ruthenium carbene
II shows a single peak at δ 29.03 ppm. When CuCl2·2H2O was
added to the solution at 60 °C, a new peak appeared at δ 34.31
ppm, indicating the formation of a copper complex of PCy3.
The system was then mixed with 3s at 60 °C and was stirred for
24 h; 3s was converted completely, and 2s was isolated in 90%
yield. These results imply that the copper complex may play a
key role in the catalytic dehydrogenation process.
To further prove this hypothesis, a mixture of PCy3 and
CuCl2·2H2O was used as the catalytic system for the
dehydrogenation of 3s. The yield of 2s was 65%, which is
significantly higher than that with CuCl2·2H2O (39%) under
similar reaction conditions. However, the yield of 2s from the
PCy3/CuCl2·2H2O system was still lower than that for a mixed
ruthenium carbene II/CuCl2·2H2O catalyst. In fact, 2s was
obtained in 29% yield when 10.0 mol % of II was used as the
only catalyst for the dehydrogenation of 3s under similar
reaction conditions. These results indicate that two pathways
may contribute to the dehydrogenation process of 3s: (a)
dehydrogenation by in situ generated copper complexes and
(b) dehydrogenation catalyzed by ruthenium carbene II or its
fragments. In these reactions, the product yield from the
cooperation of ruthenium carbene II and CuCl2·2H2O is
significantly better than that for a single catalyst. Therefore, it is
highly likely that the dehydrogenation reaction happens under
the synergistic catalysis of II and CuCl2·2H2O or through a
complex that forms in situ when CuCl2·2H2O is mixed with II.
In fact, a similar phenomenon has been previously observed by
the Stevens group.19b
CONCLUSIONS
■
Efficient catalyst systems including I/FeCl3·6H2O and II/
CuCl2·2H2O were found to give pyrrole derivatives from
diallylamines through an RCM and oxidation dehydrogenation
tandem reaction. A variety of different substituted pyrrole
derivatives were obtained in moderate to good yields through
this method. An oxygen atmosphere played a critical role in
obtaining high conversion of substituted pyrroles in the current
catalytic system. The catalytic mechanism study showed that
both the in situ generated copper complex and the ruthenium
carbene complex (or its fragments) contribute to the
dehydrogenation process. In addition, the combination of the
two components is more effective than each single catalyst.
Scheme 2. Dehydrogenation of 3a,s in the Presence of
CuCl2·2H2O or FeCl3·6H2O
EXPERIMENTAL SECTION
■
General Considerations. All reactions were carried out under O2
atmosphere except when otherwise noted. Dichloromethane and 1,2-
dichloroethane were dried from calcium hydride under N2 atmosphere
and distilled prior to use. Silica gel (200−300 mesh) was used for flash
chromatography. The diallylamines were prepared according to
literature procedures.22−26 Arylamines, allyl bromide, 3-chloro-2-
methylpropene, and other reagents were commercially obtained and
mechanism may be suitable for the II/CuCl2·2H2O and I/
FeCl3·6H2O catalytic systems. However, when 3s, a substrate
bearing a strong electron-withdrawing group, was subjected to
the reaction in the presence of CuCl2·2H2O or FeCl3·6H2O
under O2, at 40 °C only a small amount of the pyrrole product
2s was isolated. When the temperature was increased to 60 °C,
the yield of 2s increased to 39%. After ruthenium carbene II
(10 mol %) was added to the system, the desired product 2s
was isolated in high yield (90%). It seems that there is a
synergistic effect in the catalytic system of II and CuCl2·2H2O
1
used as received. H and 13C NMR spectra were recorded with a
Bruker AV 400 spectrometer using CDCl3 as a solvent. The chemical
shifts are expressed in parts per million relative to CDCl3 (δ 7.26) for
1H NMR and relative to the central CDCl3 resonance (δ 77.0) for 13
C
NMR. Coupling constants (J) are expressed in hertz. The NMR data
of known compounds agreed with literature values. Products were
1
characterized by comparison of H NMR, 13C NMR, and GC-MS
results.
General Procedure for the Synthesis of Pyrrole Derivatives
2a−i. A Schlenk reaction tube equipped with a magnetic stirring bar
E
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was charged with ruthenium carbene I (0.0125 mmol), FeCl3·6H2O
(0.05 mmol), and diallylamine (0.25 mmol) in 2.5 mL of CH2Cl2. The
tube was placed under an O2 balloon and stirred at 40 °C in an oil bath
for 24 h. After the mixture was cooled to room temperature, the
solvent was removed under reduced pressure and the residue was
purified by flash chromatography to give the desired product.
General Procedure for the Synthesis of Pyrrole Derivatives
2j−x. A Schlenk reaction tube equipped with a magnetic stirring bar
was charged with ruthenium carbene II (0.025 mmol), CuCl2·2H2O
(0.05 mmol), and diallylamine (0.25 mmol) in 2.5 mL of
ClCH2CH2Cl. The tube was placed under an O2 balloon and stirred
at 60 °C in an oil bath for 24 h. After the mixture was cooled to room
temperature, the solvent was removed under reduced pressure and the
residue was purified by flash chromatography to give the desired
product.
(7) Dieter, R. K.; Yu, H. Y. Org. Lett. 2000, 2, 2283.
(8) (a) Ma, H.-C.; Jiang, X.-Z. J. Org. Chem. 2007, 72, 8943.
(b) Reddy, V. P.; Kumar, A. V.; Rao, K. R. Tetrahedron Lett. 2011, 52,
777.
(9) Katritzky, A. R.; Jiang, J. L.; Steel, P. J. J. Org. Chem. 1994, 59,
4551.
(10) (a) Arcadi, A.; Rossi, E. Tetrahedron 1998, 54, 15253.
(b) Periasamy, M.; Srinivas, G.; Bharathi, P. J. Org. Chem. 1999, 64,
4204.
(11) (a) Azizi, N.; Khajeh-Amiri, A.; Ghafuri, H.; Bolourtchian, M.;
Saidi, M. R. Synlett 2009, 2245. (b) Bandyopadhyay, D.; Mukherjee, S.;
Granados, J. C.; Short, J. D.; Banik, B. K. Eur. J. Med. Chem. 2012, 50,
209.
(12) (a) Zhang, X. X.; Shi, J. C. Tetrahedron 2011, 67, 898. (b) Deng,
H.-J.; Fang, Y.-J.; Chen, G.-W.; Liu, M.-C.; Wu, H.-Y.; Chen, J.-X.
Appl. Organomet. Chem. 2012, 26, 164.
(13) (a) Danks, T. N. Tetrahedron Lett. 1999, 40, 3957. (b) Wilson,
M. A.; Filzen, G.; Welmaker, G. S. Tetrahedron Lett. 2009, 50, 4807.
(c) Rivera, S.; Bandyopadhyay, D.; Banik, B. K. Tetrahedron Lett. 2009,
50, 5445. (d) Bandyopadhyay, D.; Mukherjee, S.; Banik, B. K.
Molecules 2010, 15, 2520.
ASSOCIATED CONTENT
* Supporting Information
Text giving experimental details and figures giving H NMR
■
S
1
and 13C NMR spectra of all new compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
(14) (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413.
(b) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012. (c) Hoveyda, A.
̈
AUTHOR INFORMATION
Corresponding Author
*E-mail for J.W.: wjh@tju.edu.cn.
Notes
■
H.; Schrock, R. R. Chem. Eur. J. 2001, 7, 945. (d) Semeril, D.; Bruneau,
́
C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585. (e) van Otterlo,
W. A. L.; de Koning, C. B. Chem. Rev. 2009, 109, 3743. (f) Kurteva, V.
B.; Afonso, C. A. M. Chem. Rev. 2009, 109, 6809.
(15) (a) Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc.
1993, 115, 9856. (b) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal,
J. F.; Hoveyda, A. H. J. Am. Chem. Soc. 1996, 118, 4291. (c) Kirkland,
T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310. (d) Nakamura, I.;
Yamamoto, Y. Chem. Rev. 2004, 104, 2127. (e) Deiters, A.; Martin, S.
F. Chem. Rev. 2004, 104, 2199. (f) Liu, G. Y.; Zhang, J. Z.; Wu, B.;
Wang, J. H. Org. Lett. 2007, 9, 4263. (g) Liu, G. Y.; He, H. Y.; Wang, J.
H. Adv. Synth. Catal. 2009, 351, 1610. (h) Liu, G. Y.; Wang, J. H.
Angew. Chem., Int. Ed. 2010, 49, 4425. (i) Shao, M. B.; Zheng, L.; Qiao,
W. X.; Wang, J. J.; Wang, J. H. Adv. Synth. Catal. 2012, 354, 2743.
(j) Qiao, W. X.; Shao, M. B.; Wang, J. H. J. Organomet. Chem. 2012,
713, 197.
(16) (a) Donohoe, T. J.; Orr, A. J.; Bingham, M. Angew. Chem., Int.
Ed. 2006, 45, 2664. (b) Donohoe, T. J.; Fishlock, L. P.; Procopiou, P.
A. Chem. Eur. J. 2008, 14, 5716. (c) Cadierno, V.; Crochet, P. Curr.
Org. Synth. 2008, 5, 343.
(17) (a) Evans, P.; Grigg, R.; Monteith, M. Tetrahedron Lett. 1999,
40, 5247. (b) Yang, Q.; Xiao, W.-J.; Yu, Z. K. Org. Lett. 2005, 7, 871.
(c) Ahmed-Omer, B.; Barrow, D. A.; Wirth, T. Arkivoc 2011, iv, 26.
(18) (a) Yang, C. M.; Murray, W. V.; Wilson, L. J. Tetrahedron Lett.
2003, 44, 1783. (b) Yang, Q.; Li, X.-Y.; Wu, H.; Xiao, W.-J.
Tetrahedron Lett. 2006, 47, 3893.
(19) (a) Dieltiens, N.; Stevens, C. V.; Vos, D. D.; Allaert, B.;
Drozdzak, R.; Verpoort, F. Tetrahedron Lett. 2004, 45, 8995.
(b) Dieltiens, N.; Stevens, C. V.; Allaert, B.; Verpoort, F. Arkivoc
2005, i, 92. (c) Moonen, K.; Dieltiens, N.; Stevens, C. V. J. Org. Chem.
2006, 71, 4006.
(20) Yamamoto, K.; Chen, Y. G.; Buono, F. G. Org. Lett. 2005, 7,
4673.
(21) Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202.
(22) Li, L.; Jones, W. D. J. Am. Chem. Soc. 2007, 129, 10707.
(23) Ramachary, D. B.; Narayana, V. V. Eur. J. Org. Chem. 2011,
3514.
(24) Shue, Y.-J.; Yang, S.-C. Appl. Organomet. Chem. 2011, 25, 883.
(25) Barbe, G.; Charette, A. B. J. Am. Chem. Soc. 2008, 130, 18.
(26) Larsen, C. R.; Grotjahn, D. B. J. Am. Chem. Soc. 2012, 134,
10357.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by grants from the NSFC (21072149
and 20872108) and the Innovation Foundation of Tianjin
University.
REFERENCES
■
(1) (a) Lipshutz, B. H. Chem. Rev. 1986, 86, 795. (b) Artico, M.;
Silvestri, R.; Massa, S.; Loi, A. G.; Corrias, S.; Piras, G.; Colla, P. L. J.
Med. Chem. 1996, 39, 522. (c) Silvestri, R.; Regina, G. L.; Martino, G.
D.; Artico, M.; Befani, O.; Palumbo, M.; Agostinelli, E.; Turini, P. J.
Med. Chem. 2003, 46, 917. (d) Huffman, J. W.; Padgett, L. W.;
Isherwood, M. L.; Wiley, J. L.; Martin, B. R. Bioorg. Med. Chem. Lett.
2006, 16, 5432. (e) Aydogan, F.; Basarir, M.; Yolacan, C.; Demir, A. S.
Tetrahedron 2007, 63, 9746. (f) Pridmore, S. J.; Slatford, P. A.; Daniel,
A.; Whittlesey, M. K.; Williams, J. M. J. Tetrahedron Lett. 2007, 48,
5115. (g) Liu, K.; Lu, H.; Hou, L.; Qi, Z.; Teixeira, C.; Barbault, F.;
Fan, B.-T.; Liu, S. W.; Jiang, S. B.; Xie, L. J. Med. Chem. 2008, 51, 7843.
(h) Watanabe, T.; Umezawa, Y.; Takahashi, Y.; Akamatsu, Y. Bioorg.
Med. Chem. Lett. 2010, 20, 5807. (i) Ghorab, M. M.; Ragab, F. A.;
Heiba, H. I.; Youssef, H. A.; El-Gazzar, M. G. Bioorg. Med. Chem. Lett.
2010, 20, 6316.
(2) (a) Boger, D. L.; Boyce, C. W.; Labrili, M. A.; Sehon, C. A.; Jin,
Q. J. Am. Chem. Soc. 1999, 121, 54. (b) Jacobi, P. A.; Coutts, L. D.;
Guo, J. S.; Hauck, S. I.; Leung, S. H. J. Org. Chem. 2000, 65, 205.
(c) Domingo, V. M.; Aleman
́
, C.; Brillas, E.; Julia,
́
L. J. Org. Chem.
2001, 66, 4058. (d) Furstner, A. Angew. Chem. 2003, 115, 3706.
̈
(e) Antilla, J. C.; Baskin, J. M.; Barder, T. E.; Buchwald, S. L. J. Org.
Chem. 2004, 69, 5578. (f) Fan, H.; Peng, J. N.; Hamann, M. T.; Hu, J.-
F. Chem. Rev. 2008, 108, 264.
(3) (a) Azizian, J.; Karimi, A. R.; Kazemizadeh, Z.; Mohammadi, A.
A.; Mohammadizadeh, M. R. J. Org. Chem. 2005, 70, 1471. (b) Abid,
M.; Landge, S. M.; Torok, B. Org. Prep. Proced. Int. 2006, 38, 495.
(4) (a) Furstner, A.; Weintritt, H.; Hupperts, A. J. Org. Chem. 1995,
̈
60, 6637. (b) Banik, B. K.; Cardona, M. Tetrahedron Lett. 2006, 47,
7385. (c) Sridhar, R.; Srinivas, B.; Kumar, V. P.; Reddy, V. P.; Kumar,
A. V.; Rao, K. R. Adv. Synth. Catal. 2008, 350, 1489.
(5) Minetto, G.; Raveglia, L. F.; Taddei, M. Org. Lett. 2004, 6, 389.
(6) Rochais, C.; Lisowski, V.; Dallemagne, P.; Rault, S. Tetrahedron
Lett. 2004, 45, 6353.
F
dx.doi.org/10.1021/om400046r | Organometallics XXXX, XXX, XXX−XXX