Rhodium(iii)-catalyzed cascade oxidative annulation reactions of aryl imidazolium salts with alkynes involving multiple C-H bond activation

Article abstract of DOI:10.1039/c5ob00823a

The cascade oxidative annulation reactions of aryl imidazolium salts with alkynes proceed efficiently in the presence of [CpRhCl₂]₂ and Cu(OAc)₂·H₂O to give substituted imidazo[1,2-a]-quinolinium salts and benzo[ij]imidazo[2,1,5-de]quinolizinium salts. The reactions were through the normal and abnormal N-heterocyclic carbene (NHC)-directed cyclometalation, alkyne insertion into the Rh-C bond, and reductive elimination of alkenyl and NHC ligands. The reactions are highly regioselective with unsymmetrical alkynes and can be achieved stepwise by controlling the reaction conditions. This provides a new application of NHCs as directing groups and substrates in the synthesis of fused N-heterocyclic compounds. The N-substituting group of the benzo[ij]imidazo[2,1,5-de]quinolizinium salts could be removed successfully with pyridine to afford benzo[ij]imidazo[2,1,5-de]quinolizines in excellent yields. Moreover, some of the benzo[ij]imidazo[2,1,5-de]quinolizinium salts exhibit intense fluorescence which might be useful in organic electronic materials.

Full text of DOI:10.1039/c5ob00823a

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ARTICLE
Rhodium(III)-Catalyzed Cascade Oxidative Annulation Reactions of
Aryl Imidazolium Salts with Alkynes involving Multiple C−H Bond
Activation
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Qingmei Ge,a Bin Li,a Haibin Song,a and Baiquan Wang*a,b,c
www.rsc.org/
The cascade oxidative annulation reactions of aryl imidazolium salts with alkynes proceed efficiently in the presence of
[Cp*RhCl2]2 and Cu(OAc)2⋅H2O to give substituted imidazo[1,2-a]-quinolinium salts and benzo[ij]imidazo[2,1,5-
de]quinolizinium salts. The reactions were through the normal and abnormal N-heterocyclic carbenes (NHCs)- directed
cyclometalation, alkynes insertion into the Rh−C bond, and reductive elimination of alkenyl and NHC ligands. The reactions
are highly regioselective with unsymmetrical alkynes and can be achieved stepwise by controlling the reaction conditions.
This provides a new application of NHCs as directing groups and substrates in synthesis of fused N-heterocyclic
compounds. The N-substituting group of the benzo[ij]imidazo[2,1,5-de]quinolizinium salts could be removed successfully
with pyridine to afford benzo[ij]imidazo[2,1,5-de]quinolizines in excellent yields. Moreover, some of the
benzo[ij]imidazo[2,1,5-de]quinolizinium salts exhibit intense fluorescence which might be useful in organic electronic
materials.
for NHC transition metal complexes, the reductive eliminations
of alkyl, aryl, or acyl transition metal−NHC complexes have
been much studied.2,6-8 However, most works about NHCs and
aNHCs have focused on their mechanism and prevention of
Introduction
N-heterocyclic carbenes (NHCs) have been extensively used as
ligands in transition metal catalysis and organometallic
chemistry due to their σ-electron-donating capability and
steric effects.1 Typical transition-metal NHC complexes show
“normal” binding at C2 position of the imidazole ring.2
Crabtree and co-workers firstly reported an “abnormal” NHC
(aNHC) complex in which the metalation is at the C5 position
of the NHC ring.3 Blocking C2 position with a substituent, such
as Me or Ph group, will also encourage bonding in the C5
position.4 The Achilles’ heel in (NHC)M-catalyzed reactions is
the tendency for NHC reductive elimination to the imidazolium
salt [NHC-R]+.5 Reductive elimination is a key step of transition
metal catalyzed C−C or C−heteroatom coupling reactions.
Generally, it involves two anionic ligands and hence reductive
elimination of a neutral molecule. If the reductive elimination
is from an anionic and a neutral ligand such as NHC, the
product is a salt. As a major catalyst decomposition pathway
reductive elimination. There are only a few reports on
annulation reactions of NHC or aNHC-based cyclometalated
complexes, and there are rare reports about transition-mental
catalyzed C−H bond activation reaction from NHCs or
imidazolium salts.9 More recently, the direct C−H acꢀvaꢀon of
non-NHC based (hetero)arene substrates without the
coordination assistance from directing group has attracted
growing attention.10 For example, Miura10a,10e,10g and
Chen10b,10d have developed Rh(III)
-catalyzed C−H acꢀvaꢀon to
synthesize polycyclic aromatics. Hua10f and co-workers
reported synthesis of multisubstituted 2-aminoquinolines via
Rh(III)-catalyzed annulation reaction between tetrazoles and
internal alkynes. Significantly, the structures of imidazo[1,2-a]-
quinolinium
moieties are similar to aza-fused heterocyclic frameworks such
as imidazophenanthridinium (IPs) and
and
benzo[ij]imidazo[2,1,5-de]quinolizinium
dihydroimidazophenanthridinium derivatives (DIPs) (Chart 1)
which exist in many compounds that express diverse physical,
chemical, and biological properties.11,12,13 Additionally, these
molecules with extended conjugated π-systems display
fluorescence property which might be useful in organic
electronic materials.14
a.State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry,
Nankai University, Tianjin 300071, China. E-mail: bqwang@nankai.edu.cn
b.Collaborative Innovation Center of Chemical Science and Engineering, Nankai
University, Tianjin 300071, China
c.State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China
On the basis of our previous work on NHC complexes15 and
transition-metal-catalyzed C−H bond activation processes,16
we devote to explore the synthesis of polyheteroaromatic
† Electronic Supplementary Informaꢀon (ESI) available: For ESI and crystallographic
data in CIF or other electronic format See DOI: 10.1039/x0xx00000x
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compounds through double or multiple C−H bond activation great yields (Table 2). When the substituents were located at
and annulation. Herein, we report an efficient Rh(III)-catalyzed the para position of the phenyl imidazolium moiety, 4-fluoro,
C–H bond activation and annulation reaction from aryl 4-chloro, and 4-bromophenyl imidazolium salts 1b−d afforded
imidazolium salts and alkynes with the normal and abnormal benzo[ij]imidazo[2,1,5-de]quinolizinium salts 4ba
NHCs as directing groups leading to imidazo[1,2-a]quinolinium yields (76−85%). 4-Methyl, 4-tert-butyl substituted and
salts and benzo[ij]imidazo[2,1,5-de]quinolizinium salts. During electron-rich substrates 1e reacted nicely with 2a to give
the preparation of our manuscript, Choudhury reported a the corresponding products 4ea ha in excellent yields
−da in good
−
h
−
similar work.17 Different from our conditions, AgOTf was used (80−97%). In contrast, electron-withdrawing 4-nitrophenyl
in their system and all products contained TfO− as the anion. imidazolium salt 1i provided 4ia only in 53% yield. N-Phenyl
But in our cases the chloride anion of aryl imidazolium salts and N-methyl substituted imidazolium substrates 1j and 1l also
was remained in the final products. A different catalytic could provide the corresponding products (4ja and 4la) in good
intermediate was isolated and characterized by us. yields. Aside from 2a, other symmetrical alkynes were also
Furthermore, we also demonstrated that two different alkynes tested for the present reaction. Gratifyingly, substituted
could be introduced in the annulation reaction and the N- diphenylacetylenes both with electron-rich or electron-
substituent at the benzo[ij]imidazo[2,1,5-de]quinolizinium deficient groups could give high yields (87–99%). 3-Hexyne
salts could be removed successfully with pyridine to afford could react with 1a to give the expected product, however, the
benzo[ij]imidazo[2,1,5-de]quinolizines in excellent yields.
pure compound could not be isolate mainly from the one
molecule of alkyne annulation by-product by column
chromatography or recrystallization. Surprisingly, 1-phenyl-1-
Chart 1.
propyne
(2i) and 1-phenyl-1-butyne (2j) provided single
regioisomeric products of 4ai and 4aj in high yields,
respectively. The structure of 4aj was confirmed by single-
crystal X-ray diffraction analysis (Figure 1). It was regrettable
that phenylacetylene could not react with phenylimidazolium
salt 1a to produce the expected product.
N
N
X
X
N
N
R = aryl, alkyl
X = halogen
R
R
DIPs
IPs
Table 1. Optimization of reaction conditions a
Ph
Ph
Ph
[Cp*RhCl2]2
Base
Mes
Results and discussion
N
N
Mes
Ph
N
+
N
2
Cu(OAc)2.H2O
Solvent, 80 o
Our study began by investigating the potential reaction of
phenylimidazolium salt 1a and diphenylacetylene 2a to form
benzo[ij]imidazo[2,1,5-de]quinolizinium salt 4aa in which two
Cl
Cl
C
Ph
1a
2a
Ph
Ph
4aa
alkyne units were incorporated. As shown in Table 1
treatment of 1a (0.2 mmol) with diphenylacetylene (2a, 0.4
mmol) in the presence of [Cp*RhCl2]2 (5 mol %), Cu(OAc)2 H2O Entry
，
Equiv of 1a
⋅
Base
Solvent
MeOH
Yieldsb (%)
o
(0.8 mmol), and Cs2CO3 (0.8 mmol) in t-AmOH (2 mL) at 80 C
for 12 h led to the desired product 4aa in 88% yield (Table 1,
1
1
Cs2CO3
trace
88%
trace
87%
87%
N.D.
N.D
1
entry 2). Compound 4aa was characterized by H and 13C NMR
2
1
Cs2CO3
t-AmOH
CH2Cl2
spectroscopy and high-resolution mass spectrometry (HRMS).
The reaction also could proceed in CH3CN (Table 1, entry 4).
But only trace of the annulation product was observed when t-
AmOH was replaced by MeOH or CH2Cl2 (Table 1, entries 1 and
3). Moreover, the reaction could proceed smoothly without
any bases (Table 1, entry 5). Pleasingly, when the amount of 1a
was increased slightly, the reaction completed in 4 h with 96%
yield (Table 1, entries 8 and 10). The yields had tiny reduction
owing to the reduced amount of catalyst (Table 1, entry 9).
When the reaction was carried out in the absence of the
rhodium catalyst or oxidant, no product was observed (Table
1, entries 6 and 7). Finally, we chose 5 mol % of [Cp*RhCl2]2
3
1
Cs2CO3
4
1
Cs2CO3
CH3CN
5
1
-
-
-
-
-
-
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
6c
7d
8
1
1
1.1
1.1
1.1
96%
93%
96%
9e
10f
aReaction conditions: 1a
,
2a (0.4 mmol, 2.0 equiv), [Cp*RhCl2]2 (5 mol%),
and 0.8 mmol of Cu(OAc)2⋅
H2O in t-AmOH (2 mL) at 80 oC
under argon as the standard reaction conditions.
Cu(OAc)2
mL), 80
⋅H2O (0.8 mmol, 4.0 equiv), Base (0.8 mmol, 4.0 equiv), solvent (2
C, under Ar atmosphere, for 12 h. bIsolated yield. cWithout
[Cp*RhCl2]2. dWithout Cu(OAc)
°
With the optimal reaction conditions established, various
substituted phenylimidazolium salts 1a–j were treated with
f
⋅
H2O. e[Cp*RhCl2]2 (2.5 mol%). Reaction time
4 h. N.D.= no detected.
diphenylacetylene (2a) to give the corresponding products
4 in
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Table 2. Substrate scope of rhodium-catalyzed cascade oxidative annulation with alkynes a,b
R3
R4
R3
R2
[Cp*RhCl2]2 (5 mol%)
Cu(OAc)2`H2O (4 equiv)
R2
+
N
X
N
X
2
N
N
t-AmOH, 80oC
R1
R1
R4
R3
R4
1a-j
4
2a-k
R1 = H,
, 4 h, 96%
F, 4ba, 7 h, 85%
4aa
Ph
Ph
Ph
Ph
Ph
Cl, 4ca, 9 h, 84%
Br, 4da, 9 h,76%
Me, 4ea, 7 h, 97%
OMe, 4fa, 9 h, 80%
NMe2, 4ga, 9 h, 88%
t-Bu, 4ha, 7 h, 89%
NO2, 4ia, 10 h, 53%
H Ph
N
Mes
N
N
R1
N
Cl
Cl
Ph
Ph
Ph
4ja, 10 h, 80%
R3, R4 = 4-FC6H4, 4ab, 6 h, 99%
R3
R4
4ac
, 6 h, 98%
R3, R4 = 4-ClC6H4,
R3, R4 = 4-BrC6H4,
Ph
Ph
Ph
4ad
, 7 h, 92%
4ae
R3, R4 = 4-MeC6H4,
R3, R4 = 4-OMeC6H4,
R3, R4 = 4-CO2EtC6H4,
, 4 h, 91%
4af
, 4 h, 96%
H
N
H
N
Mes
N
N
4ag
, 5 h, 88%
R
3 = Me, R4 = Ph, 4ah, 4 h, 98%
I
Cl
R3 = Et, R4 = Ph, 4ai, 4 h, 98%
R3 = H, R4 = Ph,
or R3 = Ph, R4 = H, 4aj, 0%
R3
Ph
R4
4la, 12 h, 75%
aReaction conditions:
1
(0.22 mmol, 1.1 equiv), 2 (0.4 mmol, 2.0 equiv), [Cp*RhCl2]2 (5 mol %), Cu(OAc)2⋅H2O (0.8 mmol, 4.0 equiv), t-AmOH (2.0 mL), 80 °C,
Ar atmosphere, TLC monitored. bIsolated yields are given.
to form imidazo[1,2-a]-quinolinium salts was next briefly
explored (Table 3). It was found that substituted
phenylimidazolium salts bearing electron-rich and electron-
deficient groups were fully tolerated in this transformation,
and the corresponding products were isolated in good to high
yields (3aa−ia). N-Phenyl substituted imidazolium substrate 1j
also could provide the corresponding product (3ja) in good
yield. Benzimidazolium substrate 1k provided 3ka in 91% yield.
And the alkyne substrates 2b−j also smoothly completed the
reaction in excellent yields (88–98%). Similarly, 1-phenyl-1-
propyne
regioisomeric products. As expected, the imidazo[1,2-a]-
quinolinium salts could further react with one molecule of
alkyne to form benzo[ij]imidazo[2,1,5-de]quinolizinium salts
(2i) and 1-phenyl-1-butyne (2j) provided single
3
4
Figure 1. Molecular structure of 4ai
.
(Scheme 1a). If the second alkynes are different from 2a, e.g.
1,2-di-p-tolylacetylene and 1,2-bis(4-methoxyphenyl)acetylene,
the annulation products 4aae and 4aaf with two different
alkynes were obtained in nearly quantitative yields. Following
this line, 2-methyl imidazolium salt 1m could react with
diphenylacetylene to form the desired product 4ma (Scheme
1b).
To further demonstrate the efficiency and practicality of
this cascade reaction, a scale-up reaction was performed.
Thus, gram-scale synthesis of 4aa was achieved in 76% yield.
In addition, when reducing by half the amount of
[Cp*RhCl2]2 and Cu(OAc)2
annulation reaction with one molecule of diphenylacetylene
2a in MeOH leading to imidazo[1,2-a]-quinolinium salt 3aa
⋅H2O, 1a underwent the oxidative
.
The scope of the imidazolium salts and alkynes for the reaction
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Table 3. Substrate scope of rhodium-catalyzed 1:1 oxidative annulation with alkynes a,b
R3
R4
R3
R2
[Cp*RhCl2]2 (2.5 mol%)
Cu(OAc)2`H2O (2 equiv)
R2
N
N
N
+
N
MeOH, 80 oC, 4 h
R1
X= Cl, Br
R1
X
R4
X
3
1a-k
Ph
2a-j
R1= H, 3aa, 84%
Ph
Ph
Ph
3ba
, 83%
F,
3ca
, 84%
3da
, 82%
Cl,
Br,
Me,
Ph
N
N
Mes
R1
N
N
3ea
, 84%
3fa
OMe,
, 88%
Cl
Cl
NMe2, 3ga, 85%
t-Bu, 3ha, 94%
NO2, 3ia, 88%
3ja, 77%
R3, R4 = 4-FC6H4, 3ab, 98%
R3, R4 = 4-ClC6H4, 3ac, 97%
R3, R4 = 4-BrC6H4, 3ad, 90%
R3, R4 = 4-MeC6H4, 3ae, 97%
R3, R4 = 4-OMeC6H4, 3af, 98%
R3, R4 = 4-CO2EtC6H4, 3ag, 92%
R3, R4 = Et, 3ah, 88%
R3
R4
Ph
Ph
N
Mes
N
Mes
N
N
Cl
Br
3ka, 91%
R3 = Me, R4 = Ph, 3ai, 98%
R3 = Et, R4 = Ph, 3aj, 94%
aReaction conditions:
1
(0.2 mmol, 1.0 equiv),
2
(0.2 mmol, 1.0 equiv), [Cp*RhCl2]2 (2.5 mol %), Cu(OAc)2⋅H2O (0.4 mmol, 2.0 equiv), MeOH (2.0 mL), 80 °C,
Ar atmosphere. bIsolated yields are given.
Ph
Ph
Ph
Ph
R
a)
[Cp*RhCl2]2 (5 mol%)
Cu(OAc)2 H2O (2 equiv)
Mes
.
N
Mes
N
N
+
N
t-AmOH, 4 h, 80 o
C
R
Cl
Cl
R
R
3aa
2
4
4aa
, 98%
R = Ph,
4aae
R = 4-MeC6H4,
R = 4-OMeC6H4,
, 99%
4aaf
, 99%
Ph
b)
[Cp*RhCl2]2 (5 mol%)
Cu(OAc)2 H2O (2 equiv)
.
N
Mes
N
Mes
Ph
N
N
+
t-AmOH, 80 o
12 h, Yield = 61%
C
Cl
Cl
Ph
Ph
Ph
1m
4ma
2a
Scheme 1. aNHCs-directed C-H bond activation and annulation reactions
To gain more insight into the mechanism of this reaction, reactions of
A
and B with 2a at 80 °C were performed and the
the rhodacycle intermediates
A
and
B
were isolated by the final products 3aa and 4aa were obtained in 74% and 53%
and were
reactions of 1a and 3aa with [Cp*RhCl2]2 and NaOAc, yields, respectively (Schemes 2b and 3b). Then
A
B
respectively (Schemes 2a and 3a). They have been fully used as the catalyst instead of [Cp*RhCl2]2 in the reactions of
characterized by 1H and 13C NMR spectra and HRMS. The 1a and 3aa with 2a under the standard reaction conditions to
structure of intermediate
B was further confirmed by single- form 3aa and 4aa in 92% and 97% yields, respectively
crystal X-ray diffraction analysis (Figure 2). The stoichiometric (Schemes 2c and 3c).
4 | J. Name., 2015, 00, 1-18
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a)
Cl
[Cp*RhCl2]2 (0.5 equiv)
N
Mes
Rh
N
Mes
N
NaOAc (4 equiv)
THF, 80 oC
Cl
N
Yield = 90%
1a
A
Ph
Ph
Ph
b)
c)
Cl
MeOH, 80 o
C
Rh
Mes
Mes
+
N
N
Yield = 74%
N
Cl
N
Ph
A
2a
3aa
Ph
Ph
Ph
A (2.5 mol%)
Cu(OAc)2.H2O (2 equiv)
N
Mes
Mes
N
+
MeOH, 80 o
Yield = 92%
C
N
Cl
N
Cl
Ph
1a
3aa
2a
Scheme 2. Synthesis of the intermediate
A and its use as either the reactant or catalyst in the annulation reaction
Ph
Ph
Ph
Ph
a)
Mes
Mes
N
[Cp*RhCl2]2 (0.5 equiv)
N
N
N
Cl
NaOAc (4 equiv)
THF, 80oC
3aa
Rh
Yield = 90%
Cl
B
Ph
Ph
Ph
Ph
Ph
b)
Ph
Mes
N
t-AmOH, 80 o
Yield = 53%
C
N
Mes
N
+
N
Cl
Ph
Rh
Ph
Cl
2a
4aa
B
Ph
Ph
c)
Ph
B
(10 mol%)
Mes
N
Mes
N
Cu(OAc)2.H2O (2 equiv)
+ 2
N
N
Cl
t-AmOH, 80 oC
Cl
Ph
Yield = 97%
Ph
Ph
2a
1a
4aa
Scheme 3. Synthesis of the intermediate
B
and its use as either the reactant or catalyst in the annulation reaction
To afford the structurally diverse neutral compounds, we
tried to remove the trimethylbenzyl group from the
benzo[ij]imidazo[2,1,5-de]quinolizinium salts. Upon treatment
of 4aa in pyridine at 140 oC,20e,20f,25 the corresponding
benzo[ij]imidazo[2,1,5-de]quinolizine 5aa was obtained in 99%
yields (Table 4). According to this method, we obtained various
benzo[ij]imidazo[2,1,5-de]quinolizine
5
with
diverse
substituent patterns incorporated and demonstrated the high-
throughput of the methodology.
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Table
Journal Name
4.
Deionization
of
benzo[ij]imidazo[2,1,5-
de]quinolizinium salts
R3
R4
R3
R4
N
Mes
N
N
N
N
140 oC, 12 h
R1
R1
Cl
R3
R4
R3
R4
5
4
EtO2C
CO2Et
Figure 2. Molecular structure of intermediate B.
N
N
N
N
EtO2C
CO2Et
5aa, 99%
5ag
, 93%
N
N
N
MeO
N
Figure 3. Fluorescence spectra of selected compounds
and Alq3 at a concentration of 1
10−5 M in CH2Cl2.
4, 5,
×
Moreover, we tested a series of kinetic isotope effect (KIE)
experiments shown in the Scheme 5. For the annulation
5ai, 81%
5fa
, 99%
aReaction conditions:
yields are given.
4 (0.1 mmol), pyridine (1.0 mL), 140 °
C. bIsolated
reaction with one molecule of alkyne to form 3, the kH/kD value
of ~1.2 indicated that cleavage of the C−H bond of the phenyl
ring, in which normal NHC acted as directing group, was not
involved in the rate-determining step (Scheme 4a).
Interestingly, the KIE experiments for the cascade reaction and
the second step reaction gave different results. The kH/kD
values of ~6.7 and ~2.8 indicated that cleavage of the C−H
bond of the phenyl ring, in which abnormal NHC participated
as directing group, was involved in the rate-determining step
(Scheme 4b and 4c).18
Most of the benzo[ij]imidazo[2,1,5-de]quinolizinium salts
4
obtained above exhibited intense fluorescence in a range of
470−479 nm (Figure 3). Notably, 4ag was found to exhibit the
most intense luminescence (λemis = 479 nm), and the intensity
of 4ag was almost seven times stronger than that of
benzo[ij]imidazo[2,1,5-de]quinolizine 5ag
stronger than the intensity of tris(8-quinolinolato)aluminum
Alq3) in the preliminary estimation. The molecular structure
, and was much
(
of 4ai (Figure 1) shows that the cyclic framework is coplanar
with the mean deviation of 0.0171 Å from the plane. The
presence of N-substituent in the benzo[ij]imidazo[2,1,5-
de]quinolizinium salts
4 has important effect on the
luminescence property by increasing the donor-accepter effect.
The electron-donor group at the N-phenyl ring and the
electron-withdrawing group at the phenyl ring of the
diarylacetylene unit may also increase the donor-accepter
effect and the luminescence intensity.
6 | J. Name., 2015, 00, 1-18
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Journal Name
ARTICLE
Ph
Ph
Ph
Ph
Ph
[Cp*RhCl2]2 (2.5 mol%)
Cu(OAc)2`H2O (2 equiv)
H5
N
N
Mes
Mes
a)
N
+
H4
N
Mes
Mes
MeOH, 80 oC, 25 min
Cl
Cl
N
Cl
Cl
Ph
2a
3aa
1a
Ph
[Cp*RhCl2]2 (2.5 mol%)
Cu(OAc)2`H2O (2 equiv)
D5
N
+
N
D4
MeOH, 80 oC, 25 min
N
Ph
kH/kD = ~1.2
D5-1a
2a
D4-3aa
Ph
Ph
Ph
[Cp*RhCl2]2 (5 mol%)
H3
H5
N
Mes
Cu(OAc)2`H2O (4 equiv)
N
Mes
b)
N
+
N
2
t-AmOH, 80oC, 50 min
Cl
Cl
Cl
Cl
Ph
2a
Ph
Ph
Ph
Ph
Ph
1a
4aa
[Cp*RhCl2]2 (5 mol%)
D5
D3
N
Mes
Cu(OAc)2`H2O (4 equiv)
N
Mes
N
2
N
+
t-AmOH, 80 oC, 50 min
Cl
Ph
kH/kD = ~6.7
Ph
Ph
D5-1a
2a
D3-4aa
Ph
Ph
Ph Ph
Ph
[Cp*RhCl2]2 (5 mol%)
H4
N
Mes
H3
Mes
Cu(OAc)2`H2O (2 equiv)
N
c)
N
+
N
Cl
t-AmOH, 80 oC, 15 min
Ph
Ph
Ph
Ph
Ph
3aa
2a
4aa
Ph
Ph
Ph
[Cp*RhCl2]2 (5 mol%)
D4
N
Mes
D3
N
Mes
Cu(OAc)2`H2O (2 equiv)
N
+
N
Cl
t-AmOH, 80 oC, 15 min
Cl
Ph
kH/kD = ~2.8
Ph
Ph
D4-3aa
2a
D3-4aa
Scheme 4. Kinetic isotope effect experiments
Based on the above experimental results and the relating membered cyclometalated intermediate
references,19,20 a possible mechanism is proposed for the coordinates following by inserting the coordinated alkyne into
present catalytic reaction (Figure 4). The first step is likely to the Rh C bond to give the seven-membered rhodacycle or I’
be a C H bond activation process thus affording the five- Then, or I’ reacts with Cu(OAc)2 H2O and HCl to give and
A. Then an alkyne
−
I
.
−
I
⋅
3
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regenerates the rhodium(III) species. Compound
3
reductive elimination from II or II’ affords the annulation
continuously proceeded C−H bond activation affording the product
cyclometalated intermediate
4
and the rhodium(III) species which continues the
B
. Similar to A, the alkyne catalytic cycle.
coordinates and inserts to generate II or II’. Subsequent
[Cp*RhCl2]2
[Cp*RhCl2]
Cu(OAc)2. H2O
4
[Cp*Rh(OAc)Cl]
HOAc + HCl
.
2
2
N
Mes
Ph
N
R3
R4
R3
R4
Cl
1a
Mes
or
Mes
N
N
Cl
N
N
Rh
Mes
Cl
N
Rh
R4
Rh
R3
N
R4
Cl R3
A
II
II'
R3
R4
R3
R4
R4
R3
R4
Cl
R3
R3
Cl
or
Mes
Rh
N
N
R4
Mes
N
N
N
N
Rh
Mes
I
I'
R3
R4
Cl
.
2
2
B
[
C
Mes
p
*
R
N
h
(
O
Cl
N
A
c
)
C
l
]
[Cp*Rh(OAc)Cl]
3
Figure 4. Proposed mechanistic pathway of the annulation reaction.
benzo[ij]imidazo[2,1,5-de]quinolizinium salts exhibit intense
fluorescence which might be useful in organic electronic
materials. Further investigations and applications on the
catalytic reactions of the aryl-substituted imidazolium salts
with alkynes are currently underway in our laboratory.
Conclusions
In conclusion, we have successfully developed a new method
for efficient synthesis of imidazo[1,2-a]quinolinium salts and
benzo[ij]imidazo[2,1,5-de]quinolizinium salts via rhodium(III)-
catalyzed cascade oxidative annulation reaction of aryl
imidazolium salts with alkynes, in which normal and abnormal
Experimental
NHCs participated as directing group in C−H bond activation.
General Information
The reactions are highly regioselective with unsymmetrical
alkynes and can be achieved stepwise by controlling the
reaction conditions. Notably, two catalytically competent five-
membered rhodacycles have been characterized, thus
revealing two key active species in the catalytic cycle. This
provides a new application of NHCs as directing groups and
substrates in synthesis of fused N-heterocyclic compounds.
The N-substituting group of the benzo[ij]imidazo[2,1,5-
de]quinolizinium salts could be removed successfully with
pyridine to afford benzo[ij]imidazo[2,1,5-de]quinolizines in
All the reactions were carried out under argon atmosphere
using standard Schlenk technique. 1H NMR (400 MHz), 19F (376
M Hz), and 13C NMR (101 MHz) were recorded on a NMR
spectrometer with DMSO-d6 and CDCl3 as solvent. Column
chromatography was performed on silica gel 200−300 mesh or
alumina 200−300 mesh. Analyꢀcal thin-layer chromatography
(TLC) was performed on pre-coated, glass-backed silica gel
plates. IR spectra were recorded as KBr disks on a FT-IR
spectrometer. High-resolution mass spectrometry (HRMS) was
done on a FTICR-mass spectrometer. [Cp*RhCl2]2 was prepared
excellent
yields.
Moreover,
some
of
the
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Journal Name ARTICLE
.
1
from RhCl3 xH2O following a literature procedure.21 The N- White solid, 88.0 mg (84%). M.p.: 209 − 210 °C. H NMR (400 MHz,
arylimidazoles,22 1,3-diphenylimidazolium chloride,23 and DMSO-d6) δ 9.34 (d, J = 2.5 Hz, 1H), 8.99 (d, J = 9.2 Hz, 1H), 8.20 (dd,
arylimidazolium salts15d,24 were prepared following the J = 9.1, 2.3 Hz, 1H), 7.56 (dd, J = 7.9, 1.4 Hz, 2H), 7.41 (dd, J = 12.5,
literature procedures. Unless otherwise noted below, all other 5.0 Hz, 5H), 7.37 − 7.34 (m, 3H), 7.28 − 7.24 (m, 2H), 6.97 (s, 2H),
compounds have been reported in the literature or are 4.45 (s, 2H), 2.25 (s, 3H), 2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6)
commercially available without any further purification.
δ 143.9, 139.0, 138.1, 136.6, 133.7, 132.5, 132.3, 131.8, 130.8,
129.6, 129.3, 128.5, 128.2, 126.8, 125.4, 125.2, 124.8, 123.7, 119.3,
114.7, 47.7, 20.5, 18.9. HRMS (ESI) m/z Calcd for C33H28ClN2 [M-Cl]+
General procedure for Rh(III)-catalyzed oxidative annulation
1
487.1941, found 487.1931. IR (cm− ) ν 3006, 2859, 1607, 1541, 1487,
Reaction of aryl imidazolium salts with one molecule of alkynes.
1442, 1351, 1220, 1140, 825, 760, 704.
A mixture of substituted arylimidazolium salts 1 (0.2 mmol, 1.0
equiv.), alkyne 2 (0.2 mmol, 1.0 equiv.), [Cp*RhCl2]2 (3.1 mg, 0.005
mmol, 2.5 mol %), and Cu(OAc)2⋅H2O (80.0 mg, 0.4 mmol, 2.0 equiv,)
were weighted in a Schlenk tube equipped with a stir bar. Dry
7-Bromo-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
a]quinolinium chloride (3da)
MeOH (2.0 mL) was added and the mixture was stirred at 80 °C for White solid, 93.4 mg (82%). M.p.: 215 − 216 °C. 1H NMR (DMSO-d6,,
4 h under Ar atmosphere. After the mixture was cooled to room 400 MHz) δ 9.34 (d, J = 2.4 Hz, 1H), 8.92 (d, J = 9.1 Hz, 1H), 8.30 (dd,
temperature, the solvent was evaporated under reduced pressure J = 9.0, 2.1 Hz, 1H), 7.55 (d, J = 6.5 Hz, 2H), 7.49 (d, J = 2.1 Hz, 1H),
and the residue was absorbed onto a small amount of alumina. 7.44 − 7.33 (m, 7H), 7.28 − 7.23 (m, 2H), 6.96 (s, 2H), 4.44 (s, 2H),
Products 3 were isolated by column chromatography on an alumina 2.24 (s, 3H), 2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 143.8,
using CH2Cl2/MeOH (50/1) as eluant.
139.0, 138.2, 136.7, 134.5, 133.8, 132.4, 130.8, 129.9 129.7, 129.6,
129.4, 128.5, 128.3, 125.5, 124.8, 123.7, 120.8, 119.5, 114.7, 47.8,
20.6, 19.0. HRMS (ESI) m/z Calcd for C33H28BrN2 [M-Cl]+ 531.1436,
4,5-Diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-a]quinolinium
1
found 531.1425. IR (cm− ) ν 3003, 2859, 1605, 1538, 1487, 1442,
chloride (3aa)
1352, 1216, 1139, 1029, 823, 759, 703.
1
White solid, 82.3 mg (84%). M.p.: 184 − 185 °C. H NMR (400 MHz,
7-Methyl-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
CDCl3) δ 10.73 (s, 1H), 9.38 (d, J = 8.5 Hz, 1H), 7.99 (t, J = 7.7 Hz, 1H),
7.59 (t, J = 7.6 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 7.40 – 7.28 (m, 8H),
a]quinolinium chloride (3ea)
7.17 – 7.12 (m, 2H), 7.02 (s, 1H), 6.88 (s, 2H), 4.50 (s, 2H), 2.26 (s,
1
3H), 2.04 (s, 6H). H NMR (400 MHz, DMSO-d6) δ 9.32 (s, 1H), 8.91 White solid, 84.4 mg (84%). M.p.: 200 − 201 °C.1H NMR (DMSO-d6,,
(d, J = 8.5 Hz, 1H), 8.09 (t, J = 7.0 Hz, 1H), 7.79 (t, J = 6.5 Hz, 1H), 400 MHz) δ 9.34 (d, J = 2.1 Hz, 1H), 8.86 (d, J = 8.7 Hz, 1H), 7.93 (d, J
7.57 (d, J = 6.1 Hz, 2H), 7.48 (d, J = 7.7 Hz, 1H), 7.36 (d, J = 20.2 Hz, = 8.5 Hz, 1H), 7.57 (d, J = 6.9 Hz, 2H), 7.42 − 7.32 (m, 6H), 7.30 −
7H), 7.25 (d, J = 6.0 Hz, 2H), 6.96 (s, 2H), 4.45 (s, 2H), 2.24 (s, 3H), 7.21 (m, 4H), 6.96 (s, 2H), 4.44 (s, 2H), 2.42 (s, 3H), 2.24 (s, 3H), 2.06
2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 145.0, 138.9, 138.2, (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 145.0, 139.1, 138.3, 138.0,
136.7, 134.4, 132.7, 131.9, 131.0, 130.5, 129.7, 129.4, 129.2, 128.4, 136.5, 134.5, 133.5, 132.9, 131.1, 129.8, 129.5, 129.3, 128.8, 128.3,
128.2, 128.1, 125.7, 123.8, 123.5, 123.4, 117.0, 114.5, 47.7, 20.6, 128.2, 127.5, 125.8, 123.9, 123.5, 123.4, 116.9, 114.2, 47.70, 21.0,
19.0. HRMS (ESI) m/z Calcd for C33H29N2 [M-Cl]+ 453.2331, found 20.9, 19.1. HRMS (ESI) m/z Calcd for C34H31N2 [M-Cl]+ 467.2487,
1
1
453.2322. IR (cm− ) ν 3014, 2859, 1603, 1548, 1491, 1442, 1349, found 467.2484. IR (cm− ) ν 3017, 2857, 1606, 1549, 1488, 1442,
1231, 1137, 1030, 851, 754, 702.
1354, 1234, 1139, 1031, 822, 758, 700.
7-Fluoro-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
7-Methoxy-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
a]quinolinium chloride (3ba)
a]quinolinium chloride (3fa)
1
White solid, 84.0 mg (83%). M.p.: 207 − 208 °C. 1H NMR (400 MHz, White solid, 91.1 mg (88%). M.p.: 192 − 193 °C. H NMR (400 MHz,
DMSO-d6) δ 9.35 (s, 1H), 9.04 (dd, J = 9.1, 4.2 Hz, 1H), 8.07 (td, J = DMSO-d6) δ 9.32 (s, 1H), 8.91 (d, J = 9.3 Hz, 1H), 7.75 (dd, J = 9.2, 2.5
9.3, 2.8 Hz, 1H), 7.57 (d, J = 6.6 Hz, 2H), 7.44 − 7.33 (m, 7H), 7.28 − Hz, 1H), 7.58 (d, J = 7.4 Hz, 2H), 7.37 (dt, J = 7.1, 6.0 Hz, 6H), 7.29 −
7.23 (m, 2H), 7.08 (dd, J = 9.5, 2.7 Hz, 1H), 6.96 (s, 2H), 4.44 (s, 2H), 7.24 (m, 3H), 6.96 (s, 2H), 6.76 (d, J = 2.5 Hz, 1H), 4.43 (s, 2H), 3.73
2.24 (s, 3H), 2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ161.5, (s, 3H), 2.24 (s, 3H), 2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ
159.0, 144.2, 139.0, 138.2, 136.5, 133.9, 132.5, 130.8, 129.6, 129.4, 145.0, 139.1, 138.3, 138.0, 136.5, 134.5, 133.5, 132.97, 131.1, 129.8,
129.3, 128.4, 128.2, 127.4, 125.5, 124.7, 123.6, 120.6, 120.4, 120.2, 129.5, 129.3, 128.8, 128.3, 128.2, 127.5, 125.8 123.9, 123.5, 123.4,
120.1, 114.8, 112.7 (JC-F = 24.4 Hz), 47.7, 20.6, 19.0. 19F NMR 116.9, 114.2, 47.7, 21.0, 20.7, 19.1. HRMS (ESI) m/z Calcd for
1
(DMSO-d6) δ −111.2 (s). HRMS (ESI) m/z Calcd for C33H28FN2 [M-Cl]+ C34H31N2O [M-Cl]+ 483.2436, found 483.2434. IR (cm− ) ν 3017, 2859,
1
471.2237, found 471.2234. IR (cm− ) ν 3016, 2859, 1613, 1549, 1488, 1734, 1614, 1550, 1488, 1442, 1379, 1278, 1178, 1030, 823, 728,
1442, 1379, 1277, 1214, 1178, 850,759, 728, 701.
702.
7-Chloro-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
7-(Dimethylamino)-4,5-diphenyl-3-(2,4,6-
a]quinolinium chloride (3ca)
trimethylbenzyl)imidazo[1,2-a]quinolinium chloride (3ga)
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1
White solid, 90.8 mg (85%). M.p.: 156 − 157 °C. H NMR (400 MHz, (m, 6H), 7.29 (d, J = 7.7 Hz, 2H), 7.12 (d, J = 8.5 Hz, 1H), 6.84 (s, 2H),
DMSO-d6) δ 9.20 (d, J = 2.2 Hz, 1H), 8.71 (d, J = 9.4 Hz, 1H), 7.60 − 5.08 (s, 2H), 2.19 (s, 3H), 1.92 (s, 6H). 13C NMR (101 MHz, DMSO-d6)
7.52 (m, 3H), 7.41 − 7.31 (m, 6H), 7.25 (d, J = 6.9 Hz, 2H), 7.20 (d, J = δ 151.3, 141.9, 137.9, 136.5, 134.5, 133.4, 132.9, 132.7, 131.0,
2.2 Hz, 1H), 6.95 (s, 2H), 6.36 (d, J = 2.5 Hz, 1H), 4.40 (s, 2H), 2.86 (s, 129.8, 129.4, 129.3, 129.1, 128.5, 128.3, 128.0, 127.9, 126.7, 126.5,
6H), 2.24 (s, 3H), 2.05 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 149.0, 124.3, 123.0, 118.0, 117.3, 113.7, 47.8, 20.4, 19.6. HRMS (ESI) m/z
144.4, 138.8, 138.1, 135.1, 134.8, 133.0, 131.0, 129.5, 129.3, 129.04 Calcd for C37H31N2 [M-Br]+ 503.2487, found 503.2482. IR (cm− ) ν
1
128.1, 128.0, 125.8, 125.3, 123.2, 123.0, 122.1, 118.4, 117.6, 113.5, 3020, 2920, 1592, 1526, 1490, 1445, 1335, 1282, 1234, 1019, 855,
106.4, 47.4, 20.6, 19.0. HRMS (ESI) m/z Calcd for C35H34N3 [M-Cl]+ 760, 701.
1
496.2753, found 496.2751. IR (cm− ) ν 3021, 2919, 1612, 1543, 1489,
4,5-Bis(4-fluorophenyl)-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
1443, 1381, 1340, 1222, 815, 756, 701.
a]quinolinium chloride (3ab)
7-(tert-Butyl)-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
White solid, 101.7 mg (98%). M.p.: 212 − 213 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.32 (d, J = 2.4 Hz, 1H), 8.92 (d, J = 8.5 Hz, 1H), 8.16 −
a]quinolinium chloride (3ha)
White solid, 103.0 mg (94%). M.p.: 174 − 175 °C. 1H NMR (400 MHz, 8.04 (m, 1H), 7.80 (dd, J = 11.5, 4.1 Hz, 1H), 7.62 (dd, J = 8.6, 5.5 Hz,
DMSO-d6) δ 9.34 (d, J = 2.4 Hz, 1H), 8.86 (d, J = 9.0 Hz, 1H), 8.19 (dd, 2H), 7.50 (dd, J = 8.3, 0.9 Hz, 1H), 7.35 (d, J = 2.4 Hz, 1H), 7.27 (d, J =
J = 9.0, 2.0 Hz, 1H), 7.61 − 7.54 (m, 2H), 7.44 − 7.34 (m, 7H), 7.32 (d, 8.8 Hz, 6H), 6.98 (s, 2H), 4.51 (s, 2H), 2.26 (s, 3H), 2.08 (s, 6H). 13C
J = 2.3 Hz, 1H), 7.29 − 7.23 (m, 2H), 6.96 (s, 2H), 4.45 (s, 2H), 2.24 (s, NMR (101 MHz, DMSO-d6) δ 163.1(JC-F = 57.0 Hz), 160.7(JC-F = 56.3
3H), 2.06 (s, 6H), 1.23 (s, 9H). 13C NMR (101 MHz, DMSO-d6) δ 150.6, Hz), 144.6, 138.9, 138.2, 136.6, 133.2, 133.1, 132.1, 132.0, 131.9,
145.2, 138.9, 138.1, 136.5, 134.5, 132.8, 131.0, 130.2, 129.7, 129.4, 130.7, 130.5, 129.4, 129.0, 128.3, 125.7, 123.7, 123.5, 123.0, 116.9,
129.2, 128.7, 128.2, 128.0, 125.8, 123.5, 123.4, 123.2, 116.8, 114.3, 115.6, 115.4, 115.1, 114.4, 47.9, 20.6, 19.0. 19F NMR (DMSO-d6) δ
47.6, 34.7, 30.5, 20.6, 19.0. HRMS (ESI) m/z Calcd for C37H37N2 [M- −111.5 (s), −113.2 (s). HRMS (ESI) m/z Calcd for C33H27F2N2 [M-Cl]+
1
1
Cl]+ 509.2957, found 509.2955. IR (cm− ) ν 3023, 2961, 1603, 1546, 489.2142, found 489.2136. IR (cm− ) ν 3016, 1610, 1596, 1510, 1457,
1465, 1442, 1365, 1258, 1207, 1140, 848, 762, 701.
1354, 1225, 1158, 826, 754.
7-Nitro-4,5-diphenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
4,5-Bis(4-chlorophenyl)-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
a]quinolinium chloride (3ia)
a]quinolinium chloride (3ac)
1
White solid, 93.7 mg (88%). M.p.: 205 − 206 °C. H NMR (400 MHz, White solid, 109.3 mg (98%). M.p.: 199 − 201 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.48 (s, 1H), 9.20 (d, J = 9.0 Hz, 1H), 8.84 (d, J = 9.2 Hz, DMSO-d6) δ 9.36 (d, J = 2.0 Hz, 1H), 8.94 (d, J = 8.6 Hz, 1H), 8.10 (t, J
1H), 8.21 (s, 1H), 7.59 (d, J = 6.7 Hz, 2H), 7.42 (s, 7H), 7.30 (d, J = 6.2 = 7.8 Hz, 1H), 7.80 (t, J = 7.7 Hz, 1H), 7.62 (d, J = 8.3 Hz, 2H), 7.50 (dd,
Hz, 2H), 6.97 (s, 2H), 4.48 (s, 2H), 2.25 (s, 3H), 2.07 (s, 6H). 13C NMR J = 14.9, 7.1 Hz, 5H), 7.36 (s, 1H), 7.27 (d, J = 8.3 Hz, 2H), 6.98 (s, 2H),
(101 MHz, DMSO-d6) δ 145.9, 144.7, 139.1, 138.2, 137.6, 133.5, 4.53 (s, 2H), 2.26 (s, 3H), 2.08 (s, 6H). 13C NMR (101 MHz, DMSO-d6)
133.4, 132.2, 130.8, 129.9, 129.5, 129.4, 129.3, 128.8, 128.4, 128.3, δ 144.0, 138.9, 138.2, 136.4, 134.1, 133.2, 132.8, 132.1, 131.6,
125.7, 125.4, 124.2, 124.0, 123.8, 119.2, 115.4, 48.0, 20.6, 19.0. 130.5, 129.3, 128.4, 125.7, 123.4, 122.6, 117.2, 114.7, 47.9, 20.6,
HRMS (ESI) m/z Calcd for C33H28N3O2 [M-Cl]+ 498.2182, found 19.1. HRMS (ESI) m/z Calcd for C33H27Cl2N2 [M−Cl]+ 521.1546, found
1
1
498.2182. IR (cm− ) ν 3019, 2966, 1604, 1524, 1443, 1348, 1269, 521.1554. IR (cm− ) ν 3009, 2856, 1607, 1546, 1491, 1348, 1258,
1117, 850, 748, 704.
1088, 1018, 813, 755.
3,4,5-Triphenylimidazo[1,2-a]quinolinium chloride (3ja)
4,5-Bis(4-bromophenyl)-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
White solid, 66.9 mg (77%). M.p.: 262 − 263 °C. 1H NMR (DMSO-d6,,
400 MHz) δ 9.67 (s, 1H), 9.03 (d, J = 8.2 Hz, 1H), 8.59 (s, 1H), 8.17 (t,
J = 7.5 Hz, 1H), 7.83 (t, J = 7.3 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.31 (s,
3H), 7.23 (d, J = 6.7 Hz, 3H), 7.14 (s, 4H), 6.93 (d, J = 6.8 Hz, 2H), 6.85
(d, J = 7.4 Hz, 1H), 6.80 (d, J = 6.7 Hz, 2H). 13C NMR (101 MHz,
DMSO-d6) δ 145.7, 136.9, 135.3, 134.4, 132.1, 131.0, 130.9, 130.4,
129.8, 129.2, 128.6, 128.5, 128.4, 128.1, 128.0, 127.6, 127.1, 127.0,
124.0, 123.6, 117.0, 114.2. HRMS (ESI) m/z Calcd for C29H21N2 [M-
a]quinolinium chloride (3ad)
White solid, 116.3 mg (90%). M.p.: 193 − 195 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.44 (s, 1H), 8.97 (d, J = 8.6 Hz, 1H), 8.09 (t, J = 7.8 Hz,
1H), 7.79 (t, J = 7.7 Hz, 1H), 7.64 (t, J = 7.7 Hz, 4H), 7.58 (d, J = 8.3 Hz,
2H), 7.46 (d, J = 8.2 Hz, 1H), 7.33 (d, J = 2.2 Hz, 1H), 7.22 (d, J = 8.3
Hz, 2H), 6.97 (s, 2H), 4.54 (s, 2H), 2.25 (s, 3H), 2.08 (s, 6H). 13C NMR
(101 MHz, DMSO-d6) δ 144.0, 139.0, 138.2, 136.3, 133.6, 133.1,
132.2, 131.9, 131.3, 130.5, 129.4, 128.3, 125.7, 123.4, 122.9, 122.5,
121.8, 117.1, 114.6, 47.9, 20.6, 19.1. HRMS (ESI) m/z Calcd for
1
Cl]+ 397.1705, found 397.1703. IR (cm− ) ν 2989, 1593, 1538, 1497,
1443, 1343, 1260, 1097, 1021, 801, 761, 697.
C33H27Br2N2 [M−Cl]+ 609.0536, found 609.0541. IR (cm− ) ν 3009,
2857, 1604, 1544, 1488, 1388, 1348, 1208, 1135, 1069, 1013, 815,
1
5,6-Diphenyl-7-(2,4,6-trimethylbenzyl)benzo[4,5]imidazo[1,2-
756.
a]quinolinium bromide (3ka)
4,5-Di-p-tolyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-a]quinolinium
White solid, 106.1 mg (91%). M.p.: 240 − 241 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.41 (d, J = 8.8 Hz, 1H), 9.30 (d, J = 8.7 Hz, 1H), 8.25 (dd,
J = 11.7, 4.1 Hz, 1H), 7.86 (dt, J = 19.4, 7.8 Hz, 2H), 7.69 (t, J = 7.9 Hz,
1H), 7.61 (d, J = 8.1 Hz, 1H), 7.50 (dd, J = 6.3, 2.7 Hz, 2H), 7.42 – 7.31
chloride (3ae)
10 | J. Name., 2015, 00, 1-18
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1
White solid, 100.1 mg (97%). M.p.: 174 − 176 °C. 1H NMR (400 MHz, White solid, 84.0 mg (98%). M.p.:197 − 199 °C. H NMR (400 MHz,
DMSO-d6) δ 9.35 (d, J = 2.4 Hz, 1H), 8.91 (d, J = 8.5 Hz, 1H), 8.06 (dd, DMSO-d6) δ 9.26 (d, J = 1.5 Hz, 1H), 8.85 (d, J = 8.5 Hz, 1H), 8.42 (d, J
J = 11.5, 4.2 Hz, 1H), 7.77 (t, J = 7.8 Hz, 1H), 7.46 (d, J = 7.8 Hz, 3H), = 8.2 Hz, 1H), 8.08 (t, J = 7.7 Hz, 1H), 7.92 (t, J = 7.7 Hz, 1H), 7.70 (d,
7.31 (d, J = 2.3 Hz, 1H), 7.26 – 7.17 (m, 4H), 7.13 (d, J = 8.0 Hz, 2H), J = 3.9 Hz, 5H), 7.19 (d, J = 1.3 Hz, 1H), 6.95 (s, 2H), 4.42 (s, 2H), 2.50
6.96 (s, 2H), 4.45 (s, 2H), 2.30 (s, 3H), 2.25 (s, 6H), 2.06 (s, 6H). 13C (s, 3H), 2.23 (s, 3H), 2.05 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ
NMR (101 MHz, DMSO-d6) δ 145.2, 138.9, 138.5, 138.2, 137.4, 141.0, 138.9, 138.1, 136.7, 133.4, 131.8, 130.5, 130.3, 129.8, 129.3,
136.8, 131.8, 131.6, 130.8, 130.4, 129.8, 129.6, 129.4, 128.8, 128.7, 129.2, 128.1, 127.0, 125.8, 123.4, 122.9, 122.7, 117.0, 114.0, 47.4,
128.4, 128.1, 125.8, 124.0, 123.5, 123.4, 116.8, 114.3, 47.6, 20.8, 20.6, 19.0, 16.2. HRMS (ESI) m/z Calcd for C28H27N2 [M-Cl]+
1
20.7, 20.6, 19.0. HRMS (ESI) m/z Calcd for C35H33N2 [M-Cl]+ 391.2174, found 391.217. IR (cm− ) ν 3015, 2916, 1613, 1547, 1467,
1
481.2644, found 481.2643. IR (cm− ) ν 3016, 2918, 1602, 1549, 1509, 1366, 1238, 1206, 1005, 853, 752, 706.
1456, 1351, 1234, 1137, 849, 753.
5-Ethyl-4-phenyl-3-(2,4,6-trimethylbenzyl)-3-dihydroimidazo[1,2-a]
4,5-Bis(4-methoxyphenyl)-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
quinolinium chloride (3aj)
a]quinolinium chloride (3af)
1
White solid, 83.2 mg (94%). M.p.: 194 − 197 °C. H NMR (400 MHz,
White solid, 108.0 mg (98%). M.p.: 178 − 180 °C. 1H NMR (400 MHz, DMSO-d6) δ 9.31 (d, J = 1.6 Hz, 1H), 8.90 (d, J = 8.5 Hz, 1H), 8.45 (d, J
DMSO-d6) δ 9.34 (s, 1H), 8.90 (d, J = 8.5 Hz, 1H), 8.06 (t, J = 7.7 Hz, = 8.3 Hz, 1H), 8.07 (t, J = 7.7 Hz, 1H), 7.93 (t, J = 7.6 Hz, 1H), 7.75 (d,
1H), 7.78 (t, J = 7.7 Hz, 1H), 7.55 – 7.44 (m, 3H), 7.28 (d, J = 1.9 Hz, J = 7.0 Hz, 2H), 7.72 − 7.61 (m, 3H), 7.15 (d, J = 1.6 Hz, 1H), 6.95 (s,
1H), 7.17 (d, J = 8.5 Hz, 2H), 6.96 (s, 6H), 4.50 (s, 2H), 3.74 (d, J = 2H), 4.39 (s, 2H), 2.92 (dd, J = 14.2, 6.8 Hz, 2H), 2.24 (s, 3H), 2.05 (s,
16.6 Hz, 6H), 2.25 (s, 3H), 2.08 (s, 6H). 13C NMR (101 MHz, DMSO-d6) 6H), 1.17 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, DMSO-d6) δ 145.7,
δ 159.4, 158.7, 145.4, 138.9, 138.2, 137.1, 132.4, 131.8, 131.1, 138.7, 138.1, 136.6, 133.0, 131.6, 130.6, 130.3, 129.8, 129.2, 129.0,
130.4, 129.4, 128.5, 128.1, 126.6, 125.9, 124.7, 124.2, 123.6, 123.3, 128.1, 126.6, 125.6, 122.6, 122.1, 117.4, 114.2, 47.3, 22.1, 20.5,
116.9, 114.3, 113.7, 113.6, 55.0, 47.7, 20.6, 19.1. HRMS (ESI) m/z 19.0, 14.8. HRMS (ESI) m/z Calcd for C29H29N2 [M−Cl]+ 405.2325,
1
1
Calcd for C35H33N2O2 [M-Cl]+ 513.2542, found 513.25. IR (cm− ) ν found 405.2331. IR (cm− ) ν 2967, 2924, 1604, 1544, 1454, 1372,
2933, 2836, 1609, 1543, 1506, 1458, 1290, 1248, 1178, 1026, 816, 1233, 1178, 1028, 849, 755, 707.
761.
General procedure for Rh(III)-catalyzed cascade oxidative
4,5-Bis(4-(ethoxycarbonyl)phenyl)-3-(2,4,6-
annulation reaction of aryl imidazolium salts with two molecules
trimethylbenzyl)imidazo[1,2-a]quinolinium chloride (3ag)
of alkynes
White solid, 116.2 mg (92%). M.p.: 206 − 208 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.37 (s, 1H), 8.95 (d, J = 8.6 Hz, 1H), 8.11 (t, J = 7.8 Hz,
A mixture of aryl substituted imidazolium salts 1 (0.22 mmol, 1.1
equiv.), alkyne 2 (0.4 mmol, 2.0 equiv.), [Cp*RhCl2]2 (6.2 mg, 0.01
1H), 7.96 (d, J = 8.0 Hz, 4H), 7.78 (dd, J = 16.5, 8.0 Hz, 3H), 7.43 (t, J
mmol, 5 mol %), and Cu(OAc)2⋅H2O (160.0 mg, 0.8 mmol, 4.0 equiv.)
were weighted in a Schlenk tube equipped with a stir bar. Dry t-
= 7.0 Hz, 3H), 7.37 (s, 1H), 6.96 (s, 2H), 4.48 (s, 2H), 4.34 – 4.20 (m,
4H), 2.24 (s, 3H), 2.07 (s, 6H), 1.29 (dt, J = 14.3, 7.0 Hz, 6H). 13C NMR
AmOH (2.0 mL) was added and the mixture was stirred at 80 °C
(101 MHz, DMSO-d6) δ 165.0, 143.9, 139.1, 138.9, 138.2, 137.3,
under Ar atmosphere. The reaction process was monitored by TLC.
136.2, 132.2，131.5, 130.6, 130.4, 130.3, 129.6, 129.3, 128.9, 128.2,
After the reaction finished, the mixture was cooled to room
125.6, 123.5, 123.2, 122.5, 117.1, 114.8, 60.9, 47.9, 20.5, 19.0, 13.9.
HRMS (ESI) m/z Calcd for C39H37N2O4 [M−Cl]+ 597.2748, found
temperature, the solvent was evaporated under reduced pressure,
1
597.2760. IR (cm− ) ν 2982, 1718, 1606, 1547, 1461, 1401, 1368,
and the residue was absorbed onto a small amount of alumina.
Products 4 were isolated by column chromatography on an alumina
1274, 1105, 1022, 853, 755.
using CH2Cl2/MeOH (80/1−50/1) as eluant.
4,5-Diethyl-3-(2,4,6-trimethylbenzyl)-3-imidazo[1,2-a]quinolinium
3,4,8,9-Tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
chloride (3ah)
dihydrobenzo[ij]imidazo[2,1,5-de] quinolizinium chloride (4aa)
1
White solid, 69.0 mg (88%). M.p.: 173 − 175 °C. H NMR (400 MHz,
1
DMSO-d6) δ 9.11 (s, 1H), 8.73 (d, J = 8.4 Hz, 1H), 8.39 (d, J = 8.1 Hz,
Yellow-green solid, 128.5 mg (96%). M.p.: >300 °C. H NMR (400
MHz, CDCl3) δ 7.70 (d, J = 7.2 Hz, 2H), 7.66 – 7.60 (m, 1H), 7.58 (d, J
1H), 7.96 (t, J = 7.5 Hz, 1H), 7.85 (t, J = 7.4 Hz, 1H), 7.10 (d, J = 15.6
= 7.7 Hz, 1H), 7.51 (d, J = 7.8 Hz, 1H), 7.37 – 7.23 (m, 12H), 7.18 (d, J
Hz, 3H), 5.78 (d, J = 13.4 Hz, 2H), 3.42 (d, J = 7.0 Hz, 2H), 3.30 (d, J =
7.2 Hz, 2H), 2.33 (s, 3H), 2.27 (s, 6H), 1.46 (s, 3H), 1.33 (s, 3H). 13C
= 8.8 Hz, 6H), 6.88 (s, 1H), 6.78 (s, 2H), 4.98 (s, 2H), 2.16 (s, 3H), 2.10
(s, 6H). 1H NMR (400 MHz, DMSO-d6) δ 7.92 (t, J = 8.0 Hz, 1H), 7.63
NMR (101 MHz, DMSO-d6) δ 145.1, 138.9, 138.5, 137.9, 130.8,
(d, J = 7.2 Hz, 2H), 7.57 (d, J = 7.8 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H),
130.1, 129.4, 127.9, 126.1, 123.6, 122.5, 117.2, 114.0, 48.1, 20.6,
20.2, 19.1, 15.6, 14.9. HRMS (ESI) m/z Calcd for C25H29N2 [M−Cl]+
7.49 − 7.37 (m, 9H), 7.36 − 7.21 (m, 9H), 6.90 (s, 2H), 6.68 (s, 1H),
4.69 (s, 2H), 2.17 (s, 3H), 2.07 (s, 6H). 13C NMR (101 MHz, DMSO-d6)
1
357.2325, found 357.2333. IR (cm− ) ν 2925, 2867, 1601, 1544, 1517,
δ 144.7, 139.2, 138.2, 136.0, 134.2, 133.5, 132.9, 132.1, 130.9,
1456, 1341, 1198, 1049, 854, 761.
129.8, 129.3, 129.1, 128.8, 128.7, 128.6, 128.4, 128.1, 127.9, 127.5,
5-Methyl-4-phenyl-3-(2,4,6-trimethylbenzyl)imidazo[1,2-
125.7, 125.3, 125.0, 124.7, 124.6, 124.5, 124.1, 114.5, 47.9, 20.5,
18.9. HRMS (ESI) m/z Calcd for C47H37N2 [M−Cl]+ 629.2951, found
a]quinolinium chloride (3ai)
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1
1
629.2967. IR (cm− ) ν 3053, 2921, 1608, 1553, 1486, 1444, 1339, [M−Cl]+ 643.3108, found 643.3121. IR (cm− ) ν 3052, 2921, 2857,
1174, 1028, 851, 764, 705.
1612, 1578, 1485, 1443, 1334, 1196, 1161, 1027, 856, 797, 710.
6-Fluoro-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
6-Methoxy-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ba)
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4fa)
1
1
Yellow-green solid, 116.4 mg (85%). M.p.: >300 °C. H NMR (400 Yellow-green solid, 111.4 mg (80%). M.p.: >300 °C. H NMR (400
MHz, DMSO-d6) δ 7.61 (s, 2H), 7.53 − 7.39 (m, 9H), 7.37 − 7.15 (m, MHz, DMSO-d6) δ 7.65 (d, J = 6.4 Hz, 2H), 7.43 (dd, J = 20.9, 5.8 Hz,
11H), 6.91 (s, 2H), 6.78 (s, 1H), 4.71 (s, 2H), 2.18 (s, 3H), 2.06 (s, 6H). 9H), 7.35 (d, J = 6.7 Hz, 2H), 7.27 (d, J = 14.9 Hz, 7H), 7.02 (s, 1H),
13C NMR (101 MHz, DMSO-d6) δ 161.4, 158.9, 144.0, 139.3, 138.2, 6.89 (s, 3H), 6.68 (s, 1H), 4.69 (s, 2H), 3.65 (s, 3H), 2.17 (s, 3H), 2.07
135.4, 133.7, 133.1, 132.5, 131.8, 130.8, 129.8, 129.5, 129.3, 129.1, (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 158.1, 143.9, 139.1, 138.2,
129.0, 128.8, 128.7, 128.5, 128.3, 128.2, 126.6, 126.5, 125.9, 125.2, 135.4, 134.1, 133.4, 132.1, 130.9, 129.7, 129.3, 129.1, 128.8, 128.7,
125.0, 124.7, 115.5, 111.7 (JC-F = 26.7 Hz), 109.6 (JC-F = 25.3 Hz), 48.1, 128.6, 128.5, 128.4, 128.3, 128.1, 127.4, 126.1, 125.3, 125.1, 124.4,
20.5, 18.9. 19F NMR (376 MHz, DMSO-d6) δ −108.8 (s). HRMS (ESI) 123.2, 114.9, 111.8, 107.1, 55.5, 47.8, 20.4, 18.9. HRMS (ESI) m/z
1
1
m/z Calcd for C47H36FN2 [M−Cl]+ 647.2857, found 647.2868. IR (cm− ) Calcd for C48H39N2O [M−Cl]+ 659.3057, found 659.3071. IR (cm− ) ν
ν 3053, 2923, 2856, 1608, 1577, 1515, 1442, 1404, 1338, 1188, 3054, 2918, 1610, 1578, 1469, 1408, 1369, 1298, 1208, 1133, 1032,
1122, 1026, 857, 800, 712.
845, 796, 707.
6-Chloro-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
6-(Dimethylamino)-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ca)
1-benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ga)
1
1
Yellow-green solid, 117.7 mg (84%). M.p.: >300 °C. H NMR (400 Yellow-green solid, 124.3 mg (88%). M.p.: >300 °C. H NMR (400
MHz, DMSO-d6) δ 7.92 (t, J = 8.0 Hz, 1H), 7.65 (d, J = 7.1 Hz, 2H), MHz, DMSO-d6) δ 7.66 − 7.58 (m, 2H), 7.42 (d, J = 20.2 Hz, 9H), 7.35
7.58 (d, J = 7.9 Hz, 1H), 7.52 (d, J = 8.3 Hz, 1H), 7.49 – 7.38 (m, 9H), − 7.18 (m, 9H), 6.89 (s, 2H), 6.81 (s, 1H), 6.55 (d, J = 7.9 Hz, 2H), 4.62
7.34 (m, 2H), 7.30 – 7.23 (m, 6H), 6.90 (s, 2H), 6.69 (s, 1H), 4.72 (s, (s, 2H), 2.74 (s, 6H), 2.17 (s, 3H), 2.06 (s, 6H). 13C NMR (101 MHz,
2H), 2.17 (s, 3H), 2.07 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 144.7, DMSO-d6) δ 149.0, 143.7, 139.1, 138.1, 135.7, 134.5, 134.4, 133.7,
139.3, 138.2, 136.0, 134.2, 133.5, 132.9, 132.1, 130.9, 129.8, 129.3, 132.4, 131.3, 130.9, 129.7, 129.2, 129.1, 128.8, 128.6, 128.5, 128.3,
129.2, 128.8, 128.7, 128.6, 128.4, 128.2, 127.9, 127.5, 125.7, 125.3, 127.5, 126.7, 125.9, 125.4, 124.6, 124.1, 120.7, 114.4, 109.0, 104.9,
125.0, 124.7, 124.6, 124.5, 124.1, 114.5, 47.9, 20.5, 18.9. HRMS (ESI) 47.6, 20.4, 18.9. HRMS (ESI) m/z Calcd for C49H42N3 [M−Cl]+
1
m/z Calcd for C47H36ClN2 [M−Cl]+ 663.2562, found 663.2556. IR 672.3373, found 672.3387. IR (cm− ) ν 3052, 2918, 1609, 1577, 1484,
1
(cm− ) ν 3052, 2921, 2857, 1621, 1554, 1485, 1444, 1336, 1173, 1443, 1375, 1185, 1130, 1027, 847, 791, 708.
1026, 764, 706.
6-(tert-Butyl)-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
6-Bromo-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ha)
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4da)
1
Yellow-green solid, 128.8 mg (89%). M.p.: >300 °C. H NMR (400
1
Yellow-green solid, 113.7 mg (76%). M.p.: >300 °C. H NMR (400 MHz, DMSO-d6) δ 7.71 (d, J = 7.1 Hz, 2H), 7.60 (s, 1H), 7.48 (d, J =
MHz, DMSO-d6) δ 7.92 (m, 1H), 7.61 (s, 3H), 7.45 (d, J = 2.7 Hz, 9H), 6.9 Hz, 7H), 7.44 − 7.36 (m, 5H), 7.35 − 7.22 (m, 7H), 6.88 (s, 2H),
7.29 (t, J = 19.1 Hz, 9H), 6.91 (s, 2H), 6.68 (s, 1H), 4.69 (s, 2H), 2.18 (s, 6.70 (s, 1H), 4.74 (s, 2H), 2.15 (s, 3H), 2.08 (s, 6H), 1.14 (s, 9H). 13C
3H), 2.06 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 144.6, 139.1, NMR (101 MHz, DMSO-d6) δ 150.4, 144.7, 139.1, 138.1, 136.0,
138.1, 135.9, 134.2, 133.5, 132.8, 132.1, 130.9, 129.8, 129.3, 129.2, 134.2, 133.5, 132.7, 132.1, 130.9, 129.8, 129.3, 129.1, 128.8, 128.7,
129.1, 128.7, 128.6, 128.5, 128.3, 127.9, 127.4, 125.7, 125.3, 125.0, 128.5, 128.4, 128.3, 127.5, 126.3, 125.6, 125.4, 124.8, 124.6, 124.3,
124.6, 124.5, 124.0, 114.5, 47.9, 20.4, 18.9. HRMS (ESI) m/z Calcd 121.8, 120.2, 114.5, 47.8, 34.9, 30.7, 20.4, 18.9. HRMS (ESI) m/z
1
1
for C47H36BrN2 [M−Cl]+ 707.2056, found 707.2051. IR (cm− ) ν 3051, Calcd for C51H45N2 [M−Cl]+ 685.3577, found 685.3610. IR (cm− ) ν
2921, 2857, 1609, 1551, 1485, 1443, 1335, 1172, 1026, 854, 764, 3054, 2960, 1617, 1514, 1483, 1442, 1267, 1169, 1026, 851, 770,
705.
708.
6-Methyl-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
6-Nitro-3,4,8,9-tetraphenyl-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ea)
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ia)
1
1
Yellow-green solid, 131.8 mg (97%). M.p.: >300 °C. H NMR (400 Pale brown solid, 75.7 mg (53%). M.p.: 154 − 156 °C. H NMR (400
MHz, DMSO-d6) δ 7.63 (s, 2H), 7.53 – 7.20 (m, 20H), 6.90 (s, 2H), MHz, DMSO-d6) δ 8.21 (d, J = 4.7 Hz, 2H), 7.67 (t, J = 8.0 Hz, 2H),
6.65 (s, 1H), 4.68 (s, 2H), 2.42 (s, 3H), 2.17 (s, 3H), 2.07 (s, 6H). 13C 7.58 − 7.44 (m, 9H), 7.42 − 7.25 (m, 9H), 6.92 (s, 2H), 6.87 (s, 1H),
NMR (101 MHz, DMSO-d6) δ 144.3, 139.2, 138.2, 137.9, 135.8, 4.78 (s, 2H), 2.18 (s, 3H), 2.08 (s, 6H). 13C NMR (101 MHz, DMSO-d6)
134.2, 133.5, 132.6, 132.1, 130.9, 129.8, 129.3, 129.2, 128.8, 128.7, δ 145.8, 144.7, 139.4, 138.3, 135.5, 133.6, 133.4, 133.3, 132.9,
128.6, 128.3, 127.6, 126.3, 125.7, 125.3, 124.8, 124.7, 124.6, 123.9, 131.6, 130.8, 130.1, 129.9, 129.7, 129.6, 129.5, 129.3, 129.1, 128.9,
114.5, 47.8, 21.7, 20.4, 18.9. HRMS (ESI) m/z Calcd for C48H39N2 128.8, 128.7, 128.5, 127.0, 126.7, 125.2, 125.1, 118.4, 117.9, 116.2,
48.4, 20.4, 19.0. HRMS (ESI) m/z Calcd for C47H36N3O2 [M−Cl]+
12 | J. Name., 2015, 00, 1-18
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1
674.2802, found 674.2801. IR (cm− ) ν 3053, 2918, 2852, 1636, 1513,
3,4,8,9-Tetrakis(4-chlorophenyl)-1-(2,4,6-trimethylbenzyl)-1-
1457, 1341, 1261, 1174, 1027, 802, 756, 704.
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ac)
1,3,4,8,9-Pentaphenyl-1H-benzo[ij]imidazo[2,1,5-de]quinolizinium
1
Yellow-green solid, 157.4 mg (98%). M.p.: >300 °C. H NMR (400
MHz, DMSO-d6) δ 7.93 (s, 1H), 7.61 (d, J = 39.2 Hz, 10H), 7.47 − 7.20
chloride (4ja)
Yellow-green solid, 97.2 mg (80%). M.p.: 190 − 193 °C. 1H NMR (400 (m, 8H), 6.89 (d, J = 20.5 Hz, 3H), 4.79 (s, 2H), 2.19 (s, 3H), 2.07 (s,
MHz, DMSO-d6) δ 8.52 (t, 1H), 7.94 (t, 1H), 7.68 − 7.07 (m, 22H), 6H). 13C NMR (101 MHz, DMSO-d6) δ 144.0, 139.2, 138.2, 135.3,
6.93 (dd, J = 33.1, 11.8 Hz, 5H). 13C NMR (101 MHz, DMSO-d6) δ 134.4, 133.6, 133.4, 133.3, 132.8, 132.6, 132.1, 131.8, 131.3, 131.1,
144.9, 136.0, 134.8, 134.4, 134.2, 133.5, 132.9, 130.6, 130.0, 129.6, 130.7, 129.3, 129.1, 128.9, 128.7, 128.4, 127.9, 126.7, 125.3, 125.0,
129.4, 128.9, 128.6, 128.5, 128.4, 128.2, 128.1, 128.0, 127.7, 127.2, 124.7, 124.2, 123.7, 115.0, 48.3, 20.5, 19.0. HRMS (ESI) m/z Calcd
127.0, 125.9, 124.8, 124.7, 124.1, 120.9. HRMS (ESI) m/z Calcd for for C47H33Cl4N2 [M−Cl]+ 765.1392, found 765.1390. IR (cm− ) ν 3019,
1
C43H29N2 [M−Cl]+ 573.2325, found 573.2330. IR (cm− ) ν 3054, 2922, 2962, 2921, 1622,1487, 1396, 1341, 1174, 1090, 1015, 814, 765.
1
1624, 1548, 1494, 1442, 1342, 1180, 1039, 765, 703.
3,4,8,9-Tetrakis(4-bromophenyl)-1-(2,4,6-trimethylbenzyl)-1-
1-methyl-3,4,8,9-tetraphenyl-benzo[ij]imidazo[2,1,5-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ad)
de]quinolizinium iodide (4la)
1
Yellow-green solid, 179.8 mg (92%). M.p.: >300 °C. H NMR (400
Yellow-green solid, 95.9 mg (75%). M.p.: >300 °C. 1H NMR (400 MHz, MHz, DMSO-d6) δ 7.96 – 7.88 (m, 1H), 7.69 (m, 6H), 7.56 (m, 6H),
CDCl3) δ 7.92 (s, 1H), 7.71 – 7.62 (m, 2H), 7.56 – 7.47 (m, 3H), 7.42 7.34 – 7.15 (m, 6H), 6.90 (d, J = 18.7 Hz, 3H), 4.77 (s, 2H), 2.20 (s,
(d, J = 7.3 Hz, 2H), 7.33 (dt, J = 15.6, 7.8 Hz, 12H), 7.26 – 7.18 (m, 3H), 2.07 (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 143.9, 139.2,
4H), 3.72 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 145.4, 136.3, 134.3, 138.2, 135.3, 133.2, 132.9, 132.6, 132.4, 132.1, 132.0, 131.8, 131.9,
133.8, 133.3, 132.0, 131.0, 130.9, 129.9, 129.6, 129.3, 129.1, 128.6, 131.5, 131.4, 131.1, 129.4, 128.5, 127.9, 126.7, 125.3, 125.2, 125.1,
128.5, 128.4, 128.3, 128.2, 128.0, 127.5, 126.3, 125.2, 125.0, 124.7, 124.7, 124.5, 124.2, 123.6, 123.1, 122.3, 122.1, 122.0, 115.0, 48.3,
124.5, 124.1, 120.7, 39.0. HRMS (ESI) m/z Calcd for C38H27N2 [M−Cl]+ 20.5, 19.0. HRMS (ESI) m/z Calcd for C47H33Br4N2 [M−Cl]+ 940.9372,
1
1
511.2169, found 511.2184. IR (cm− ) ν3054, 2908, 1708, 1629, 1558, found 940.9366. IR (cm− ) ν 3017, 1628, 1586, 1484, 1389, 1339,
1441, 1238, 1073, 752, 701.
1173, 1070, 1010, 813, 765.
1-Methyl-4,5-diphenyl-2-(2,4,6-trimethylbenzyl)-2-imidazo[1,5-
3,4,8,9-Tetra-p-tolyl-1-(2,4,6-trimethylbenzyl)-1-
n]quinolinium chloride (4ma)
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ae)
1
1
White solid, 61.5 mg (61%). M.p.: 112 − 115 °C. H NMR (400 MHz, Yellow-green solid, 131.7 mg (91%). M.p.: >300 °C. H NMR (400
DMSO-d6) δ 8.71 (d, J = 8.5 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.68 (t, J MHz, DMSO-d6) δ 7.88 (t, J = 7.3 Hz, 1H), 7.51 (dd, J = 19.5, 10.8 Hz,
= 7.3 Hz, 1H), 7.37 (dd, J = 14.5, 7.9 Hz, 4H), 7.24 (s, 3H), 7.17 (d, J = 4H), 7.34 − 7.05 (m, 14H), 6.90 (s, 2H), 6.69 (s, 1H), 4.69 (s, 2H), 2.30
7.9 Hz, 4H), 6.96 (s, 2H), 6.54 (s, 1H), 5.63 (s, 2H), 3.46 (s, 3H), 2.22 (d, J = 15.8 Hz, 9H), 2.19 (d, J = 17.4 Hz, 6H), 2.07 (s, 6H).. 13C NMR
(s, 9H). 13C NMR (101 MHz, DMSO-d6) δ 140.9, 138.9, 138.3, 134.8, (101 MHz, DMSO-d6) δ 144.8, 139.2, 138.7, 138.2, 138.1, 137.6,
134.6, 133.9, 130.3, 130.2, 129.6, 129.4, 129.3, 128.3, 128.1, 128.0, 137.5, 135.9, 133.0, 131.5, 131.4, 130.8, 130.7, 129.7, 129.5, 129.3,
127.9, 126.5, 126.4, 125.5, 118.8, 112.1, 47.3, 20.5, 19.1, 15.2. 129.2, 129.1, 128.0, 127.8, 127.3, 125.9, 125.5, 125.1, 124.7, 124.0,
HRMS (ESI) m/z Calcd for C34H31N2 [M−Cl]+ 467.2482, found 114.4, 47.9, 20.8, 20.6, 20.5, 19.0. HRMS (ESI) m/z Calcd for
1
1
467.2484. IR (cm− ) ν 3055, 2919, 1620, 1560, 1479, 1444, 1378, C51H45N2 [M−Cl]+ 685.3577, found 685.3584. IR (cm− ) ν 3021, 2918,
1305, 1183, 1085, 1028, 853, 766, 702.
2860, 1618, 1557, 1502, 1457, 1338, 1175, 1022, 853, 769, 728.
3,4,8,9-Tetrakis(4-fluorophenyl)-1-(2,4,6-trimethylbenzyl)-1-
3,4,8,9-Tetrakis(4-methoxyphenyl)-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ab)
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4af)
1
1
Yellow-green solid, 146.8 mg (99%). M.p.: >300 °C. H NMR (400 Yellow-green solid, 151.3 mg (96%). M.p.: >300 °C. H NMR (400
MHz, DMSO-d6) δ 7.94 (t, J = 7.1 Hz, 1H), 7.68 (s, 2H), 7.60 (d, J = 7.7 MHz, DMSO-d6) δ 7.89 (t, J = 7.6 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H),
Hz, 1H), 7.56 (d, J = 7.8 Hz, 1H), 7.33 (t, J = 12.7 Hz, 12H), 7.19 (t, J = 7.53 (d, J = 7.4 Hz, 3H), 7.24 (d, J = 7.8 Hz, 2H), 7.17 (t, J = 9.0 Hz,
7.9 Hz, 2H), 6.92 (s, 2H), 6.79 (s, 1H), 4.78 (s, 2H), 2.19 (s, 3H), 2.08 4H), 7.03 (s, 6H), 6.92 (s, 2H), 6.86 (d, J = 6.9 Hz, 2H), 6.71 (s, 1H),
(s, 6H). 13C NMR (101 MHz, DMSO-d6) δ163.3 (JC-F = 56.9 Hz), 160.8 4.74 (s, 2H), 3.78 (s, 6H), 3.75 (s, 3H), 3.70 (s, 3H), 2.19 (s, 3H), 2.09
(JC-F = 55.3 Hz), 144.4, 139.2, 138.2, 133.1, 133.0, 132.8, 132.2, (s, 6H). 13C NMR (101 MHz, DMSO-d6) δ 159.5, 159.0, 158.8, 145.0,
132.1, 131.7, 131.6, 131.5, 130.3, 129.7, 129.3, 128.4, 128.2, 127.0, 139.3, 138.2, 135.5, 133.2, 132.2, 131.2, 130.7, 130.5, 129.3, 127.9,
125.6, 125.4, 124.9, 124.5, 124.3, 124.1, 116.1, 115.9, 115.7, 114.7, 127.7, 127.2, 126.4, 126.1, 125.7, 125.6, 125.2, 124.9, 124.6, 124.5,
48.2, 20.5, 18.9. 19F NMR (376 MHz, DMSO-d6) δ −111.1 (s), −111.9 124.1, 124.0, 114.3, 114.0, 113.8, 55.0, 48.0, 20.5, 19.0. HRMS (ESI)
(s), −112.7 (s), −112.8 (s). HRMS (ESI) m/z Calcd for C47H33F4N2 m/z Calcd for C51H45N2O4 [M−Cl]+ 749.3374, found 749.3388. IR
1
1
[M−Cl]+ 701.2574, found 701.2576. IR (cm− ) ν 3041, 2920, 1604, (cm− ) ν 2927, 2836, 1611, 1510, 1461, 1291, 1248, 1176, 1028, 816,
1503, 1406, 1226, 1158, 1014, 820, 770.
771.
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ARTICLE
Journal Name
were isolated by column chromatography on an alumina using
CH2Cl2/MeOH (500/1) as eluant.
3,4,8,9-Tetrakis(4-(ethoxycarbonyl)phenyl)-1-(2,4,6-
trimethylbenzyl)-1-benzo[ij]imidazo[2,1,5-de]quinolizinium
chloride (4ag)
3,4,8,9-Tetraphenylbenzo[ij]imidazo[2,1,5-de]quinolizine
(5aa)20e,20f,25
1
Yellow-green solid, 49.2 mg (99%). M.p.: >300 °C. 1H NMR (400 MHz,
CDCl3) δ 7.68 (s, 1H), 7.37 (d, J = 6.9 Hz, 2H), 7.34 (s, 1H), 7.33 – 7.26
(m, 8H), 7.21 (m, 12H). 13C NMR (101 MHz, CDCl3) δ 138.7, 136.6,
136.5, 135.9, 134.6, 132.2, 130.7, 130.6, 130.5, 130.4, 129.8, 128.8,
128.6, 128.5, 128.2, 128.0, 127.8, 127.7, 127.6, 127.5, 126.5, 126.4,
125.6, 125.2, 124.9, 121.9, 121.3. HRMS (ESI) m/z Calcd for C37H25N2
Yellow-green solid, 168.6 mg (88%). M.p.: 125 − 127 °C. H NMR
(400 MHz, CDCl3) δ 8.00 (d, J = 5.8 Hz, 8H), 7.83 (d, J = 7.6 Hz, 2H),
7.65 (t, J = 7.9 Hz, 1H), 7.52 (d, J = 7.8 Hz, 1H), 7.46 (d, J = 8.1 Hz,
1H), 7.40 (d, J = 7.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 7.27 (d, J = 9.7
Hz, 2H), 6.88 (s, 1H), 6.78 (s, 2H), 5.01 (s, 2H), 4.41 – 4.24 (m, 8H),
2.16 (s, 3H), 2.13 (s, 6H), 1.34 (dd, J = 15.3, 7.7 Hz, 12H). 13C NMR
(101 MHz, CDCl3) δ 165.7, 144.6, 139.7, 138.9, 138.6, 138.5, 137.8,
136.6, 136.0, 132.7, 131.6, 131.4, 130.63, 130.5, 130.1, 129.8, 129.6,
128.8, 127.7, 127.4, 125.9, 125.3, 125.0, 124.7, 124.4, 116.2, 61.2,
61.1, 49.5, 20.9, 19.8, 14.1. HRMS (ESI) m/z Calcd for C59H53N2O8
1
[M+H]+ 497.2018, found 497.2021. IR (cm− ) ν 3052, 2922, 1599,
1551, 1486, 1441, 1413, 1333, 1179, 1071, 811, 756, 700.
Tetraethyl 4,4',4'',4'''-benzo[ij]imidazo[2,1,5-de]quinolizine-
[M−Cl]+ 917.3796, found 917.3811. IR (cm− ) ν 2977, 1717, 1611,
1
3,4,8,9-tetrayl) tetrabenzoate (5ag)20e,20f,25
1518, 1465, 1402, 1274, 1177, 1104, 1020, 866, 767, 719.
Yellow-green solid, 72.9 mg (93%). M.p.: 256 − 258 °C. 1H NMR (400
MHz, CDCl3) δ 8.06 (dd, J = 8.2, 3.5 Hz, 4H), 7.98 (dd, J = 8.3, 2.1 Hz,
4H), 7.71 (s, 1H), 7.51 – 7.44 (m, 3H), 7.42 (dt, J = 6.7, 2.6 Hz, 3H),
7.38 – 7.31 (m, 5H), 4.38 (m, 8H), 1.44 – 1.35 (m, 12H). 13C NMR
(101 MHz, CDCl3) δ 166.2, 166.1, 166.0, 141.1, 140.9, 140.2, 139.2,
135.2, 131.4, 130.8, 130.7, 130.6, 130.5, 130.2, 130.1, 130.0, 129.9,
129.8, 129.7, 129.4, 128.7, 127.0, 126.1, 125.8, 125.1, 124.6, 122.0,
121.2, 61.1, 60.9, 14.3. HRMS (ESI) m/z Calcd for C49H41N2O8 [M+H]+
4,8-Dimethyl-3,9-diphenyl-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4ai)
1
Yellow-green solid, 108.3 mg (98%). M.p.: 119 − 121 °C. H NMR
(400 MHz, DMSO-d6) δ 8.46 (d, J = 8.1 Hz, 1H), 8.37 (d, J = 7.7 Hz,
1H), 8.23 (t, J = 7.9 Hz, 1H), 7.78 − 7.66 (m, 5H), 7.60 − 7.49 (m, 3H),
7.45 (d, J = 7.0 Hz, 2H), 6.89 (s, 2H), 6.50 (s, 1H), 4.65 (s, 2H), 2.57 (s,
3H), 2.46 (s, 3H), 2.17 (s, 3H), 2.03 (s, 6H). 13C NMR (101 MHz,
DMSO-d6) δ 140.6, 139.1, 138.1, 133.9, 132.9, 132.2, 130.8, 130.3,
129.9, 129.3, 129.2, 129.1, 128.1, 126.8, 126.4, 125.4, 125.3, 124.5,
123.7, 123.6, 123.5, 123.0, 112.8, 47.6, 20.5, 18.9, 16.3, 15.4. HRMS
(ESI) m/z Calcd for C37H33N2 [M−Cl]+ 505.2638, found 505.2642. IR
1
785.2863, found 785.2877. IR (cm− ) ν 2979, 1718, 1608, 1456, 1401,
1367, 1274, 1177, 1104, 1021, 867, 766, 719.
4,8-Dimethyl-3,9-diphenylbenzo[ij]imidazo[2,1,5-de]quinolizine
(5ai)20e,20f,25
1
(cm− ) ν 3021, 2921, 1700, 1617, 1516, 1446, 1278, 1170, 1023, 854,
Yellow-green solid, 30.3 mg (81%). M.p.: 212 − 214 °C. 1H NMR (400
MHz, CDCl3) δ 7.88 − 7.84 (m, 1H), 7.76 (d, J = 4.4 Hz, 2H), 7.56 (dd,
J = 4.9, 3.8 Hz, 6H), 7.53 (d, J = 2.2 Hz, 3H), 7.52 − 7.49 (m, 1H), 7.49
− 7.46 (m, 1H), 2.54 (s, 3H), 2.41 (s, 3H). 13C NMR (101 MHz, CDCl3)
δ 138.5, 136.6, 135.5, 130.3, 129.6, 129.4, 129.1, 128.8, 128.6,
128.5, 128.1, 128.0, 126.1, 126.0, 125.2, 124.9, 124.8, 119.4, 118.7,
16.1, 15.5. HRMS (ESI) m/z Calcd for C27H21N2 [M+H]+ 373.1705,
768, 706.
4,8-Diethyl-3,9-diphenyl-1-(2,4,6-trimethylbenzyl)-1-
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4aj)
1
Yellow-green solid, 111.6 mg (98%). M.p.: 160 − 162 °C. H NMR
(400 MHz, DMSO-d6) δ 8.48 (d, J = 8.2 Hz, 1H), 8.40 (d, J = 7.4 Hz,
1H), 8.21 (t, J = 7.9 Hz, 1H), 7.79 − 7.67 (m, 5H), 7.61 − 7.50 (m, 3H),
7.40 (d, J = 6.6 Hz, 2H), 6.88 (s, 2H), 6.35 (s, 1H), 4.57 (s, 2H), 2.99 (d,
J = 7.1 Hz, 2H), 2.92 − 2.81 (m, 2H), 2.17 (s, 3H), 2.01 (s, 6H), 1.27 −
1.16 (m, 6H). 13C NMR (101 MHz, DMSO-d6) δ 145.7, 139.1, 138.2,
136.4, 133.7, 132.5, 132.3, 130.2, 130.0, 129.2, 128.6, 128.2, 127.9,
126.3, 125.2, 124.8, 124.3, 123.5, 123.4, 123.0, 122.7, 112.8, 47.4,
22.5, 21.4, 20.4, 18.8, 13.6, 13.3. HRMS (ESI) m/z Calcd for C39H37N2
1
found 373.1697. IR (cm− ) ν 3048, 2911, 1598, 1568, 1487, 1441,
1416, 1364, 1173, 1074, 763, 703.
6-Methoxy-3,4,8,9-tetraphenylbenzo[ij]imidazo[2,1,5-
de]quinolizine (5fa)20e,20f,25
Yellow-green solid, 52.1 mg (99%). M.p.: >300 °C. 1H NMR (400 MHz,
CDCl3) δ 7.64 (s, 1H), 7.31 (d, J = 7.7 Hz, 2H), 7.29 − 7.24 (m, 5H),
7.23 − 7.14 (m, 13H), 6.86 (dd, J = 6.6, 2.2 Hz, 2H), 3.57 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 157.0, 136.8, 136.5, 136.1, 135.4, 134.9,
131.5, 130.7, 130.6, 130.5, 129.8, 128.6, 128.1, 127.9, 127.8, 127.7,
127.6, 127.5, 126.6, 126.4, 126.1, 107.9, 106.1, 55.5. HRMS (ESI)
[M−Cl]+ 533.2951, found 533.2959. IR (cm− ) ν 3051, 2925, 1617,
1
1557, 1450, 1315, 1278, 1169, 1024, 853, 770, 707.
General procedure for preparation of benzo[ij]imidazo[2,1,5-
de]quinolizine from benzo[ij]imidazo[2,1,5-de]quinolizinium salts
1
m/z Calcd for C38H27N2O [M+H]+ 527.2123, found 527.2117. IR (cm− )
A Schlenk tube with a magnetic stir bar was charged with
benzo[ij]imidazo[2,1,5-de]quinolizinium salts (0.1 mmol) and
pyridine (1.0 mL). The reaction mixture was heated at 140 oC for 12
h. The reaction mixture was then allowed to cool to room
ν 3055, 2960, 1602, 1560, 1446, 1416, 1261, 1205, 1070, 1018, 780,
709.
Preparation of 4 from 3aa
temperature, diluted with 10−15 mL of dichloromethane. The A mixture of 3aa (97.8 mg, 0.2 mmol), alkyne 2 (0.2 mmol),
pyridine was evaporated under reduced pressure, and the resulting [Cp*RhCl2]2 (6.2 mg, 0.01 mmol), and Cu(OAc)2·H2O (80.0 mg, 0.4
residue was absorbed onto a small amount of alumina. Products 5 mmol) were weighted in a Schlenk tube equipped with a stir bar.
14 | J. Name., 2015, 00, 1-18
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Dry t-AmOH (2.0 mL) was added and the mixture was stirred at washed with CH2Cl2. The combined filtrates were washed with
80 °C for 4 h under Ar atmosphere. After the mixture was cooled to dilute NH4OH solution, dilute Na2SO3, and water, dried over
room temperature, the solvent was evaporated under reduced anhydrous Na2SO4, filtered, and evaporated under reduced
pressure and the residue was absorbed onto a small amount of pressure. The resulting residue was utilized directly for further
alumina. Products 4 were isolated by column chromatography on reaction purpose.
Preparation of N-(d5-phenyl)imidazole23
an alumina using CH2Cl2/MeOH (80/1−50/1) as eluant.
8,9-diphenyl-3,4-di-p-tolyl-1-(2,4,6-trimethylbenzyl)-
A mixture of CuI (53.8 mg, 0.28 mmol), Cs2CO3 (1.84 g, 5.6 mmol),
imidazole (269.4 mg, 3.9 mmol), and d5-iodobenzene (591 mg, 2.8
mmol) in DMF (60 mL) was stirred for 30 min at room temperature
under Ar, and then heated at 120 oC for 40 h. After cooling to room
temperature, the mixture was diluted with ethyl acetate, filtered
through a pad of silica gel, and washed with water. Then the
organic phase was dried over anhydrous Na2SO4 and the filtrate was
evaporated under reduced pressure. The resulting residue was
purified by column chromatography on silica gel with
EtOAc/petroleum (1/1) to provide the desired product (209 mg,
50%).
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4aae)
1
Yellow-green solid, 137.0 mg (99%). M.p.: >300 °C. H NMR (400
MHz, CDCl3) δ 7.74 (d, J = 7.5 Hz, 2H), 7.64 (q, J = 7.8 Hz, 2H), 7.53 (d,
J = 7.2 Hz, 1H), 7.40 – 7.27 (m, 8H), 7.18 – 7.05 (m, 6H), 6.99 (d, J =
7.3 Hz, 2H), 6.93 (s, 1H), 6.82 (s, 2H), 5.03 (s, 2H), 2.35 (s, 3H), 2.25
(s, 3H), 2.21 (s, 3H), 2.14 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 146.0,
139.6, 138.3, 137.9, 136.8, 134.0, 132.3, 131.9, 131.4, 131.1, 130.6,
129.7, 129.6, 129.4, 129.2, 129.1, 128.5, 128.4, 128.3, 127.6, 126.7,
125.9, 125.5, 124.9, 124.5, 124.4, 115.4, 49.0, 21.1, 21.0, 20.8, 19.7.
HRMS (ESI) m/z Calcd for C49H41N2 [M−Cl]+ 657.3264, found
1
Preparation of 1-(d5-phenyl)-3-(2,4,6-trimethylbenzyl)imidazolium
chloride (1a-d5)
657.3284. IR (cm− ) ν 3021, 2917, 1618, 1555, 1493, 1444, 1337,
1272, 1173, 933, 854, 763, 705.
3,4-bis(4-methoxyphenyl)-8,9-diphenyl-1-(2,4,6-trimethylbenzyl)-
A mixture of the N-(d5-phenyl)imidazole (435.4 mg, 2.9 mmol) and
2-(chloromethyl)-1,3,5-trimethylbenzene (492.3 mg, 2.9 mmol) in
THF (10 mL) were refluxed overnight in a round-bottom flask
equipped with a condenser. After cooling to room temperature, 1a-
d5 (645.0 mg, 70%) was obtained as a white solid by filtered,
benzo[ij]imidazo[2,1,5-de]quinolizinium chloride (4aaf)
1
Yellow-green solid, 143.5 mg (99%). M.p.: >300 °C. H NMR (400
MHz, CDCl3) δ 7.76 (d, J = 7.3 Hz, 2H), 7.66 (d, J = 4.7 Hz, 2H), 7.56 –
7.49 (m, 1H), 7.42 – 7.27 (m, 8H), 7.17 (d, J = 7.9 Hz, 2H), 7.11 (d, J =
7.6 Hz, 2H), 6.94 (s, 1H), 6.89 (d, J = 7.5 Hz, 2H), 6.83 (s, 2H), 6.74 (d,
J = 7.7 Hz, 2H), 5.05 (s, 2H), 3.81 (s, 3H), 3.75 (s, 3H), 2.22 (s, 3H),
2.16 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 159.2, 159.1, 146.0, 139.6,
138.2, 136.3, 134.0, 132.2, 131.9, 131.1, 130.6, 129.6, 129.4, 129.3,
1
washed with hexane, and dried. H NMR (400 MHz, CDCl3) δ 11.31
(s, 1H), 8.15 (s, 1H), 6.85 (s, 1H), 6.81 (s, 2H), 5.66 (s, 2H), 2.18 (s,
9H).
Preparation of 3aa-d4
128.5, 128.4, 128.3, 127.6, 127.4, 126.7, 126.5, 125.9, 125.8, 125.4, A mixture of 1a-d5 (47.0 mg, 0.15 mmol), diphenylacetylene (26.7
125.3, 124.9, 124.4, 124.3, 115.3, 114.1, 113.8, 55.0, 49.0, 20.8, mg, 0.15 mmol), [Cp*RhCl2]2 (2.4 mg, 0.0037 mmol), and
19.7. HRMS (ESI) m/z Calcd for C49H41N2O2 [M−Cl]+ 689.3123, found Cu(OAc)2⋅H2O (60.0 mg, 0.3 mmol) were weighted in a Schlenk tube
1
689.3186. IR (cm− ) ν 2923, 1714, 1613, 1495, 1460, 1290, 1175, equipped with a stir bar. Dry MeOH (1.5 mL) was added and the
830, 766, 705.
mixture was stirred at 80 °C for 4 h under Ar atmosphere. After
cooling to room temperature, the solvent was evaporated under
reduced pressure and the residue was absorbed onto a small
amount of alumina. Purification by column chromatography on an
alumina with CH2Cl2/MeOH (50/1) afforded 3aa-d4 (69.4 mg) in 94%
yield. 1H NMR (400 MHz, DMSO-d6) δ 9.36 (d, J = 2.1 Hz, 1H), 7.58 (d,
J = 6.8 Hz, 2H), 7.37 (ddd, J = 20.6, 10.2, 4.3 Hz, 7H), 7.25 (d, J = 6.8
Hz, 2H), 6.96 (s, 2H), 2.25 (s, 3H), 2.07 (s, 6H).
Gram-scale synthesis of 4aa
A
mixture of imidazolium salt 1a (1.0 g, 3.2 mmol),
diphenylacetylene (2a) (1.036 g, 5.8 mmol), [Cp*RhCl2]2 (90.1 mg,
0.145 mmol, 5 mol%), and Cu(OAc)2·H2O (2.326 g, 11.6 mmol) were
weighted in a Schlenk tube equipped with a stir bar. Dry t-AmOH
(29 mL) was added and the mixture was stirred at 80 °C for 4 h
under Ar atmosphere. Then the mixture was cooled to room
temperature, diluted with CH2Cl2 and transferred to a round bottom
KIE experiments
flask. Alumina was added to the flask and the solvents were (a) A mixture of 1a (31.3 mg, 0.1 mmol) or 1a-d5 (31.8 mg, 0.1
evaporated under reduced pressure. After purification by flash mmol), diphenylacetylene (17.8 mg, 0.1 mmol), [Cp*RhCl2]2 (1.6 mg,
column chromatography on alumina, 1.6 g (76%) of 4aa was 0.0025 mmol), and Cu(OAc)2⋅H2O (40.0 mg, 0.2 mmol) were
obtained.
weighed in a Schlenk tube equipped with a stir bar. Dry MeOH (1.0
mL) was added and the mixture was stirred at 80 °C for 25 min
under Ar atmosphere. Afterward, the two independent reaction
mixtures were poured into a same round flask. The solvent was
evaporated under reduced pressure, and the residue was absorbed
to a small amount of alumina. The purification was performed by
column chromatography on an alumina using CH2Cl2/MeOH (50/1)
as eluant.
Preparation of d5-iodobenzene
The d5-iodobenzene was prepared by following a similar procedure
for the synthesis of iodobenzene according to the published
procedure.26 A mixture of d6-benzene (0.46 mL, 5 mmol), AgOTf
(1.284 g, 5 mmol), and iodine (1.27 g, 5 mmol) in dry CH2Cl2 (20 mL)
was stirred for 15 min at room temperature in dark condition. Then
the reaction mixture was passed through a short Celite pad and
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ARTICLE
Journal Name
(b) A mixture of 1a (17.2 mg, 0.055 mmol) or 1a-d5 (17.5 mg, 0.055 cooling to room temperature, the solvent was evaporated under
mmol), diphenylacetylene (17.8 mg, 0.1 mmol), [Cp*RhCl2]2 (1.6 mg, reduced pressure and the residue was absorbed onto a small
0.0025 mmol), and Cu(OAc)2⋅H2O (40 mg, 0.2 mmol) were weighed amount of alumina. After purification by column chromatography
in a Schlenk tube equipped with a stir bar. Dry t-AmOH (0.5 mL) was on an alumina with CH2Cl2/ MeOH (50/1) as eluant, 91.6 mg (92%)
added and the mixture was stirred at 80 °C for 50 min under Ar of 3aa was obtained.
atmosphere. Afterward, the two independent reaction mixtures
Preparation of intermediate B
were poured into a same round flask. The solvent was evaporated
A mixture of imidazolium salt 3aa (24.5 mg, 0.05 mmol), [Cp*RhCl2]2
under reduced pressure, and the residue was absorbed to a small
(15.4 mg, 0.025 mmol, 0.5 equiv), NaOAc (16.4 mg, 0.2 mmol), and
amount of alumina. The purification was performed by column
THF (2 mL) in a Schlenk tube equipped with a stir bar was stirred at
chromatography on an alumina using CH2Cl2/MeOH (80/1−50/1) as
eluant.
80 °C for 12 h. After cooling to room temperature, the solvent was
evaporated under reduced pressure and the residue was absorbed
(c) A mixture of 3aa (24.5 mg, 0.05 mmol) or 3aa-d4 (24.7 mg, 0.05
onto a small amount of alumina. After purification by column
mmol), diphenylacetylene (8.9 mg, 0.05 mmol), [Cp*RhCl2]2 (1.6 mg,
chromatography on an alumina with EtOAc/petroleum (1/4) as
0.0025 mmol), and Cu(OAc)2⋅H2O (20 mg, 0.1 mmol) were weighed
eluant, intermediate B (32.6 mg, 90%) was obtained as an orange-
in a Schlenk tube equipped with a stir bar. Dry t-AmOH (0.5 mL) was
red solid. M.p.: >300 oC. 1H NMR (400 MHz, DMSO-d6) δ 8.00 (s, 1H),
added and the mixture was stirred at 80 °C for 15 min under Ar
7.59 − 7.44 (m, 3H), 7.34 (s, 7H), 7.22 (m, 1H), 7.04 (s, 1H), 6.96 (s,
atmosphere. Afterward, the two independent reaction mixtures
2H), 6.68 (s, 1H), 4.59 (d, J = 14.1 Hz, 1H), 4.50 (d, J = 13.2 Hz, 1H),
2.25 (s, 3H), 2.08 (s, 6H), 1.72 (s, 15H). 13C NMR (101 MHz, DMSO-d6)
were poured into a same round flask. The solvent was evaporated
under reduced pressure, and the residue was absorbed to a small
δ 153.9, 153.6, 144.1, 144.0, 143.5, 138.4, 138.2, 137.5, 135.6,
amount of alumina. The purification was performed by column
135.0, 133.1, 131.0, 129.9, 129.1, 128.6, 128.1, 128.0, 127.8, 127.7,
chromatography on an alumina using CH2Cl2/MeOH (80/1−50/1) as
127.6, 127.3, 127.2, 124.3, 121.9, 121.6, 121.1, 100.7, 46.1, 20.5,
eluant.
18.9, 9.0. HRMS (ESI) m/z Calcd for C43H42N2Rh [M−Cl]+ 689.2403,
Preparation of intermediate A
1
found 689.2412. IR (cm− ) ν 2918, 2852, 1605, 1513, 1457, 1375,
A mixture of imidazolium salt 1a (15.6 mg, 0.05 mmol), [Cp*RhCl2]2 1341, 1261, 1175, 1101, 1027, 802, 757, 704.
(15.4 mg, 0.025 mmol, 0.5 equiv), NaOAc (16.4 mg, 0.2 mmol), and
Stoichiometric reaction of intermediate B with diphenylacetylene
THF (2 mL) in a Schlenk tube equipped with a stir bar was stirred at
A
mixture of intermediate
B
(36.3 mg, 0.05 mmol),
80 °C for 8 h. After cooling to room temperature, the solvent was
evaporated under reduced pressure and the residue was absorbed
onto a small amount of alumina. After purification by column
chromatography on an alumina with EtOAc/petroleum (1/6) column
as eluant, intermediate A (25.6 mg, 93%) was obtained as an
diphenylacetylene (8.9 mg, 0.05 mmol), and t-AmOH (2 mL) in a
Schlenk tube equipped with a stir bar was stirred at 80 °C for 4 h.
After cooling to room temperature, the solvent was evaporated
under reduced pressure and the residue was absorbed onto a small
amount of alumina. After purification by column chromatography
on an alumina with CH2Cl2/MeOH (80/1−50/1) as eluant, 17.5 mg
(53%) of 4aa was obtained.
o
1
orange-red solid. M.p.: 228 − 230 C. H NMR (400 MHz, DMSO-d6)
δ 7.92 (s, 1H), 7.70 (s, 1H), 7.36 (s, 1H), 6.97 (s, 4H), 6.50 (s, 1H),
5.46 (dd, J = 32.3, 13.2 Hz, 2H), 2.27 (s, 9H), 1.70 (s, 15H). 13C NMR
(101 MHz, DMSO-d6) δ 158.6, 146.0, 138.2, 137.8, 137.2, 129.0,
128.0, 124.2, 122.1, 119.5, 115.3, 111.1, 97.0, 47.2, 20.5, 19.6, 9.7,
9.4. HRMS (ESI) m/z Calcd for C28H33N2Rh [M−Cl]+ 513.1777, found
Catalytic reaction with intermediate B
A mixture of imidazolium salt 1a (0.22 mmol, 1.1 equiv.), alkyne 2a
(0.4 mmol, 2.0 equiv), intermediate B (7.3 mg, 0.01 mmol, 10
mol %), and Cu(OAc)2⋅H2O (80.0 mg, 2.0 equiv) were weighted in a
Schlenk tube equipped with a stir bar. Dry t-AmOH (2.0 mL) was
added and the mixture was stirred at 80 °C for 4 h under Ar
atmosphere. After cooling to room temperature, the solvent was
evaporated under reduced pressure and the residue was absorbed
onto a small amount of alumina. After purification by column
chromatography on an alumina with CH2Cl2/MeOH (80/1−50/1) as
eluant, 129.0 mg (97%) of 4aa was obtained.
1
513.1782. IR (cm− ) ν 3015, 2919, 1603, 1548, 1442, 1349, 1231,
1137, 1030, 851, 754, 702.
Stoichiometric reaction of intermediate A with diphenylacetylene
A
mixture of intermediate
A
(27.5 mg, 0.05 mmol),
diphenylacetylene (8.9 mg, 0.05 mmol), and MeOH (2 mL) in a
Schlenk tube equipped with a stir bar was stirred at 80 °C for 4 h.
After cooling to room temperature, the solvent was evaporated
under reduced pressure and the residue was absorbed onto a small
amount of alumina. After purification by column chromatography
on an alumina with CH2Cl2/ MeOH (50/1) as eluant, 18.2 mg (74%)
of 3aa was obtained.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (Nos 21372122 and 21421062) for financial support.
Catalytic reaction with intermediate A
A mixture of imidazolium salt 1a (0.2 mmol, 1.0 equiv.), alkyne 2a
(0.2 mmol, 1.0 equiv), intermediate A (5.5 mg, 0.01 mmol, 5 mol %),
and Cu(OAc)2⋅H2O (80.0 mg, 2.0 equiv) were weighted in a Schlenk
tube equipped with a stir bar. Dry MeOH (2.0 mL) was added and
the mixture was stirred at 80 °C for 4 h under Ar atmosphere. After
References
16 | J. Name., 2015, 00, 1-18
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DOI: 10.1039/C5OB00823A
Journal Name ARTICLE
1
(a) D. Bourissou, O. Guerret, F. P. Gabbaï and G.Bertrand, 79, 11541; (g) T. Iitsuka, K. Hirano, T. Satoh and M. Miura, J.
Chem. Rev., 2000, 100, 39; (b) W. A. Herrmann, Angew. Org. Chem., 2015, 80, 2804.
Chem., Int. Ed., 2002, 41, 1290; (c) C. M. Crudden and D. P. 11 (a) P. E. Vivas-Mejía, O. Cox and F. A. González, Mol. Cell.
Allen, Coord. Chem. Rev., 2004, 247, 2247; (d) V. Dragutan, I.
Dragutan, L. Delaude and A. Demonceau, Coord. Chem. Rev.,
2007, 251, 765; (e) S. Würtz and F.Glorius, Acc. Chem. Res.,
2008, 41, 1523; (f) F. E. Hahn and M. C. Jahnke, Angew.
Biochem., 1998, 178, 203; (b) A. T. Balaban, Chem. Rev.,
2004, 104, 2777; (c) M. Hranjec, I. Piantanida, M. Kralj, L.
Šuman, K. Pavelić and G. Karminski-Zamola, J. Med. Chem.,
2008, 51, 4899.
Chem., Int. Ed., 2008, 47, 3122; (g) K. Cavell, Dalton Trans., 12 (a) A. D. C. Parenty, L. V. Smith, K. M. Guthrie, D. L. Long, J.
2008, 6676; (h) S. Díez-González, N. Marion and S. P Nolan,
Chem. Rev., 2009, 109, 3612; (i) T. Dröge and F. Glorius,
Angew. Chem., Int. Ed., 2010, 49, 6940; (j) S. Gaillard, C. S. J.
Cazin and S. P. Nolan, Acc. Chem. Res., 2012, 45, 778; (k) M.
N. Hopkinson, C. Richter, M. Schedler and F. Glorius, Nature,
2014, 510, 485.
D. S. McGuinness and K. J. Cavell, Organometallics, 1999, 18,
1596.
S. Gründemann, A. Kovacevic, M. Albrecht, J. W. Faller and R.
H. Crabtree, J. Am. Chem. Soc., 2002, 124, 10473.
Plumb, R. Brown and L. Cronin, J. Med. Chem., 2005, 48,
4504; (b) L. V. Smith, J. M. Fuente, K. M. Guthrie, A. D. C.
Parenty and L. Cronin, New J. Chem., 2005, 29, 1118; (c) L. V.
Smith, A. D. C. Parenty, K. M. Guthrie, J. Plumb, R. Brown and
L. Cronin, ChemBioChem., 2006, 7, 1757; (d) K. M. Guthrie, A.
D. C. Parenty, L. V. Smith, L. Cronin, A. Cooper and Biophys.
Chem., 2007, 126, 117; (e) N. McMillan, L. V. Smith, J. M.
Fuente, A. D. C. Parenty, N. Gadegaard, A. R. Pitt, K.
Thomson, C. MacKenzie, S. M. Kelly and L. Cronin, Chem.
Commun., 2007, 2581.
2
3
4
5
6
A. R. Chianese, A. Kovacevic, B. M. Zeglis, J. W. Faller and R. 13 (a) Y. Song, P. J. Kitson, D. Long, A. D. C. Parenty, R. J.
H. Crabtree, Organometallics, 2004, 23, 2461.
M. S. Jeletic, M. T. Jan, I. Ghiviriga, K. A. Abboud and A. S.
Veige, Dalton Trans. 2009, 2764.
(a) N. D. Clement and K. J Cavell, Angew. Chem., Int. Ed.,
2004, 43, 3845; (b) A. T. Normand, K. J. Hawkes, N.D.
Clemen, K. J. Cavell and B. F. Yates, Organometallics, 2007,
26, 5352; (c) A. T. Normand, A. Stasch, L. L. Ooi and K. J.
Cavel, Organometallics, 2008, 27, 6507.
Thatcher and L. Cronin, CrystEngComm, 2008, 10, 1243; (b)
C. J. Richmond, A. D. C. Parenty, Y. Song, G. Cooke and L.
Cronin, J. Am. Chem. Soc., 2008, 130, 13059; (c) P. J. Kitson,
Y. Song, P. Gamez, P. Hoog, D. Long, A. D. C. Parenty, J.
Reedijk and L. Cronin, Inorg. Chem., 2008, 47, 1883; (d) C.
Ritchie, G. J. T. Cooper, Y. Song, C. Streb, H. Yin, A. D. C.
Parenty, D. A. MacLaren and L. Cronin, Nat. Chem., 2009, 1,
47; (e) G. J. T. Cooper, A. G. Boulay, P. J. Kitson, C. Ritchie, C.
J. Richmond, J. Thiel, D. Gabb, R. Eadie, D. Long and L.
Cronin, J. Am. Chem. Soc., 2011, 133, 5947.
7
(a) D. S. McGuinness, M. J. Green, K. J. Cavell, B. W. Skelton
and A. H. White, J. Organomet. Chem., 1998, 565, 165; (b)
D. S. McGuinness and K. J. Cavell, Organometallics, 2000, 19
,
14 (a) S. Allard, M. Forster, B. Souharce, H. Thiem and U. Scherf,
Angew. Chem., Int. Ed., 2008, 47, 4070; (b) H.-H. Chou and
C.-H. Cheng, Adv. Mater., 2010, 22, 2468; (c) B. Park, Y. H.
Huh, H. G. Jeon, C. H. Park, T. K. Kang, B. H. Kim and J. Park, J.
Appl. Phys., 2010, 108, 094506; (d) A. Facchetti, Chem.
Mater., 2011, 23, 733; (e) C.-L. Wang, H.-L. Dong, W.-P. Hu,
Y.-Q. Liu and D.-B. Zhu, Chem. Rev., 2012, 112, 2208.
4918; (c) D. S. McGuinness, N. Saendig, B. F. Yates and K. J.
Cavell, J. Am. Chem. Soc., 2001, 123, 4029; (d) A. M. Magill,
D. S. McGuinness, K. J. Cavell, G. J. P. Britovsek, V. C. Gibson,
A. J. P. White, D. J. Williams, A. H. White and B. W. J. Skelton,
Organomet. Chem., 2001, 617−618, 546; (e) D. J. Nielsen, A.
M. Magill, B. F. Yates, K. J. Cavell, B. W. Skelton and A. H.
White, Chem. Commun., 2002, 2500; (f) D. S. McGuinness, 15 (a) C. Zhang, Y. Zhao, B. Li, H. Song, S. Xu and B. Wang,
W. Mueller, P. Wasserscheid, K. J. Cavell, B. W. Skelton, A. H.
White and U. Englert, Organometallics, 2002, 21, 175; (g) S.
Caddick, F. G. N. Cloke, P. B. Hitchcock, J. Leonard, A. K. K.
Lewis, D. McKerrecher and L. R. Titcomb, Organometallics,
2002, 21, 4318; (h) W. J. Marshall and V. V. Grushin,
Organometallics, 2003, 22, 1591; (i) D. Bacciu, K. J. Cavell, I.
Dalton Trans., 2009, 5182; (b) C. Zhang, F. Luo, B. Cheng, B.
Li, H. Song, S. Xu and B. Wang, Dalton Trans., 2009, 7230; (c)
Y. Kong, H. Ren, S. Xu, H. Song, B. Liu and B. Wang,
Organometallics, 2009, 28, 5934; (d) Y. Kong, L. Wen, H.
Song, S. Xu, M. Yang, B. Liu and B. Wang, Organometallics,
2011, 30, 153; (e) Y. Kong, M. Cheng, H. Ren, S. Xu, H. Song,
A. Fallis and L. L. Ooi, Angew. Chem., Int. Ed., 2005, 44
,
M. Yang, B. Liu and B. Wang, Organometallics, 2011, 30,
5282; (j) D. C. Graham, K. J. Cavell and B. F. Yates, Dalton
Trans., 2005, 1093; (k) L. C. Campeau, P. Thansandote and K.
Fagnou, Org. Lett., 2005, 7, 1857; (l) D. C. Graham, K. J. Cavell
1677; (f) C. Zhang, B. Li, H. Song, S. Xu and B. Wang,
Organometallics, 2011, 30, 3029; (g) Y. Kong, S. Xu, H. Song
and B. Wang, Organometallics, 2012, 31, 5527; (h) L. Dang, J.
and B. F. Yates, Dalton Trans., 2006, 1768. (m) A. M. Magill,
B. F. Yates, K. J. Cavell, B. W. Skelton and A. H. White, Dalton
Trans., 2007, 3398.
Guo, H. Song, B. Liu, and B. Wang, Dalton Trans., 2014, 43,
17177; (i) C. Ma, C. Ai, Z. Li, B. Li, H. Song, S. Xu and B. Wang,
Organometallics, 2014, 33, 5164; (j) L. Dang, H. Song and B.
Wang, Organometallics, 2014, 33, 6812.
8
9
(a) K. J. Cavell and D. S. McGuinness, Coord. Chem. Rev.,
2004, 248, 671; (b) C. M. Crudden and D. P. Allen, Coord. 16 (a) B. Li, H. Feng, S Xu and B. Wang, Chem. Eur. J., 2011, 17
Chem. Rev., 2004, 248, 2247.
,
12573; (b) B. Li, H. Feng, N. Wang, J. Ma, H. Song, S. Xu and
(a) K. L. Tan, R. G. Bergman and J. A. Ellman, J. Am. Chem.
Soc., 2002, 124, 3202; (b) A. T. Normand, S. K. Yen, H. V.
Huynh, T. S. A. Hor and K. J. Cavell, Organometallics, 2008,
27, 3153; (c) D. Ghorai and J. Choudhury, Chem. Commun.,
2014, 50, 15159.
B. Wang, Chem. Eur. J., 2012, 18, 12873; (c) X. Tan, B. Liu, X.
Li, B. Li, S. Xu, H. Song and B. Wang, J. Am. Chem. Soc., 2012,
134, 16163; (d) B. Li, J. Ma, N. Wang, H. Feng, S. Xu and B.
Wang, Org. Lett., 2012, 14, 736; (e) N. Wang, B. Li, H. Song, S.
Xu and B. Wang, Chem. Eur. J., 2013, 19, 358; (f) B. Li, J. Ma,
10 (a) N. Umeda, K. Hirano, T. Satoh, N. Shibata, H. Sato and M.
Miura, J. Org. Chem., 2011, 76, 13; (b) J.-R. Huang, L. Dong, B.
Han, C. Peng and Y.-C. Chen, Chem. Eur. J., 2012, 18, 8896;
(c) L. Dong, J.-R. Huang, C.-H. Qu, Q.-R. Zhang, W. Zhang, B.
Han andC. Peng, Org. Biomol. Chem., 2013, 11, 6142; (d) J.-R.
Huang, Q.-R. Zhang, C.-H. Qu, X.-H. Sun, L. Dong and Y.-C.
Chen, Org. Lett., 2013, 15, 1878; (e) T. Iitsuka, K. Hirano, T.
Satoh and M. Miura, Chem. Eur. J., 2014, 20, 385; (f) L.
Zhang, L.-Y. Zheng, B. Guo and R. Hua, J. Org. Chem., 2014,
W. Xie, H. Song, S. Xu and B. Wang, Chem. Eur. J., 2013, 19,
11863. (g) B. Li, J. Ma, W. Xie, H. Song, S. Xu and B. Wang, J.
Org. Chem., 2013, 78, 9345; (h) B. Li, N. Wang, Y. Liang, S. Xu,
B. Wang, Org. Lett., 2013, 15, 136; (i) B. Liu, T. Zhou, B. Li, S.
Xu, H. Song and B. Wang, Angew. Chem., Int. Ed., 2014, 53
,
4191; (j) Y. Liang, K. Yu, B. Li, S. Xu, H. Song and B. Wang,
Chem. Commun., 2014, 50, 6130; (k) N. Wang, R. Li, L. Li, S.
Xu, H. Song and B. Wang, J. Org. Chem., 2014, 79, 5379; (l)
W. Xie, J. Yang, B. Wang and B. Li, J. Org. Chem., 2014, 79
8278.
,
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ARTICLE
17 D. Ghorai and J. Choudhury, ACS Catal., 2015,
Journal Name
5
, 2692.
18 (a) Y. Wei, I. Deb and N. Yoshikai, J. Am. Chem. Soc., 2012,
134, 9098; (b) E. M. Simmons and J. F. Hartwig, Angew.
Chem., Int. Ed., 2012, 51, 3066.
19 (a) G. Z. Wu, S. J. Geib, A. L. Rheingold and R. F. Heck, J. Org.
Chem., 1988, 53, 3238; (b) H. C. L. Abbenhuis, M. Pfeffer, J.-
P. Sutter, A. Cian, J. Fischer, H. L. Ji and J. H. Nelson,
Organometallics, 1993, 12, 4464; (c) W. Ferstl, I. K.
Sakodinskaya, N. Beydoun-Sutter, G. L. Borgne, M. Pfeffer
and A. D. Ryabov, Organometallics, 1997, 16, 411; (d) L. Li,
W. W. Brennessel and W. D. Jones, J. Am. Chem. Soc., 2008,
130, 12414; (e) J. Albert, M. Crespo, J. Granell, R. Judit, J.
Zafrilla, T. Calvet, M. Font-Bardia and X. Solans,
Organometallics, 2010, 29, 214; (f) D. L. Davies, O. Al-Duaij, J.
Fawcett and S. Kuldip, Organometallics, 2010, 29, 1413; (g)
D. Aguilar, R. Bielsa, T. Soler and E. P. Urriolabeitia,
Organometallics, 2011, 30, 642; (h) L. Cuesta, T. Soler and E.
P. Urriolabeitia, Chem. Eur. J., 2012, 18, 15178.
20 (a) R. P. Koriv, Y.-C. Wu and C.-H. Cheng, Chem. Eur. J., 2009,
15, 10727; (b) J. Jayakumar, K. Parthasarathy and C.-H.
Cheng, Angew. Chem. Int. Ed., 2012, 51, 197; (c) K.
Parthasarathy, N. Senthilkumar, J. Jayakumar and C.-H.
Cheng, Org. Lett., 2012, 14, 3478; (d) C.-Z. Luo, P. Gandeepan
and C.-H. Cheng, Chem. Commun., 2013, 49, 8528; (e) K.
Muralirajan and C.-H. Cheng, Chem. Eur. J., 2013, 19, 6198;
(f) D. Zhao, Q. Wu, X. Huang, F. Song, T. Lv and J. You, Chem.
Eur. J., 2013, 19, 6239; (g) C.-Z. Luo, P. Gandeepan, J.
Jayakumar, K. Parthasarathy, Y.-W. Chang and C.-H. Cheng,
Chem. Eur. J., 2013, 19, 14181; (h) G. Zhang, L. Yang, Y.
Wang, Y. Xie and H. Huang, J. Am. Chem. Soc., 2013, 135,
8850; (i) N. Senthilkumar, P. Gandeepan, J. Jayakumar and
C.-H. Cheng, Chem. Commun. 2014, 50, 3106.
21 C. White, A. Yates and P. M. Maitlis, Inorg. Synth., 1992, 29
,
228.
22 L. Zhu, P. Guo, G. Li, J. Lan, R. Xie and J. You, J. Org. Chem.,
2007, 72, 8535.
23 H. Clavier, A. Correa, L. Cavallo, E. C. Escudero-Adán, J.
Benet-Buchholz, A. M. Z. Slawin and S. P. Nolan, Eur. J. Inorg.
Chem., 2009, 1767.
24 J. Berding, J. A. van Paridon, V. H. S. van Rixel and E.
Bouwnman, Eur. J. Inorg. Chem., 2011, 2450.
25 C.-Z. Luo, J. Jayakumar, P. Gandeepan, Y.-C. Wu and C.-H.
Cheng, Org. Lett., 2015, 17, 924.
26 G. K. Mulholland and Q.-H. Zheng, Synth. Commun., 2001,
31, 3059.
18 | J. Name., 2015, 00, 1-18
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