Rh(iii)-catalyzed relay carbenoid functionalization of aromatic C-H bonds: Access to π-conjugated fused heteroarenes

Article abstract of DOI:10.1039/c6cc00254d

A novel Rh(iii)-catalyzed relay cross-coupling/cyclization cascade between arylketoimines and diazoesters is described. This transformation provides a concise access to unique π-conjugated 1-azaphenalenes (1-APLEs) via a double aryl Csp²-H bond

Full text of DOI:10.1039/c6cc00254d

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Chemical Communication
EDGE ARTICLE
Rh(III)-Catalyzed Relay Carbenoid Functionalization of Aromatic
C-H Bonds: Access to π-Conjugated Fused Heteroarenes
Ying Xie, a, c, ‡ Xun Chen, a, ‡ Xin Liu, b Shi-Jian Su,*, b Jianzhang Li, c and Wei Zeng*, a
†
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A novel Rh(III)-catalyzed relay cross-coupling/cyclization cascade between arylketoimines and diazoesters is described.
This transformation provides a concise access to unique π-conjugated 1-azaphenalenes (1-APLEs) via a double aryl Csp2-H
bond carbenoid functionalization process. As illustrative examples, the 1-APLE-based π-conjugated molecules which
possess low-lying HOMO levels could be converted to promising organic optoelectronic materials.
www.rsc.org/
H bonds with carbenoids provides a very powerful tool to form
C-X bonds (X = C, N, and O, etc.). In this regards, various
directing groups have been successively explored to allow for
Introduction
Fused polycyclic heteroarenes (FPHAs) are commonly
encountered in natural products, biologically-active molecules
and organic functional materials. Among them, π-conjugated
hetero atom-fused polycyclic backbones have aroused growing
concerns for their potential application in the field of organic
photovoltaic and organic field-effect transistor materials. For
examples, various nitrogen-containing FPHAs such as indole-
based FPHAs,
triarylamine-based FPHAs (SAT-FPHAs) and others have
been well evaluated for their optoelectronic applications
(Figure 1). However, the material property explorations derive-
regioselectively introducing particular single functional group
into aryl ring system via C-H activation process.8 However, in
contrast to these moncarbenoid functionalization of Csp2-H
bonds, the double cross-coupling of aryl C-H bonds with
carbenoids would possibly provide an attractive and
sustainable approach to more complex compounds due to that
neither of the two aryl C-H bonds need to be
prefunctionalized. Our recent work about the trapping of six-
1
2
3
4
carbazole-based FPHAs,
spiro-annulated
5
6
membered metallacycle species which derived from N-(2-
pyridyl)-ketoimines A (Scheme 1a) by unsaturated alkynes
9
10
and CO, inspired us to successfully realize Rh(III)-catalyzed
chelation-assisted intermolecular carbenoid functionalization
of Csp3-H bonds, in which insertion of carbenoids
Figure 1. Selected Examples of N-Fused Polycylic Heteroarenes
Ar
N
NH
1
2
5
4
regioselectively occurred at α
-imino alkyl Csp3-H bond instead
R
R
MeO
C
2
N
of phenyl Csp2-H bonds (Scheme 1a). 11 Owing to the synthetic
importance of 1-APLEs, these results stimulated us to further
envision that Rh(III) catalysts could doubly activate C-imino
aryl Csp2-H bonds employing imine as chelating group once
2
R
R
N
R
1
N
R
R
R
R
O
1
2
1
3
R
R
R
Novel muscarinic allosteric agents
1-APLE
SAT-FPHAs
Indole-based FPHAs
d from 1-azaphenalenes (1-APLEs) are rarely reported owning
to the restriction of efficient synthetic access to 1-APLE library,
even though these compounds are gradually attracting
remarkable attention because of their potential material
switching the pyridyl group from N-(2-pyridyl)-ketoimines
A
to
-acyl
G and I) to furnish multisubstituted
phenyl group ( ), followed by the cross-coupling with
E
α
diazocarbonyl compounds (
1-APLE deriv-
7
properties. Therefore, the development of concise methods
3
for rapidly assembling 1-APLE derivatives has been an
important goal for synthetic chemists.
In the past decade, metal-catalyzed cross-coupling of aryl C-
a) Our Recent Work: Pyridine-directed Rh(III)-catalyzed Csp -H functionalization with diazo compounds
3
O
R
O
3
R
2
3
R
R
Rh
2
2
R
R
Ar
N
N
N
Rh
1
R
N
N
Rh(III)
2
N
Ar
N
N
Ar
N
A
B
D
C
b) This Work: Ketoimine-directed Rh(III)-catalyzed Relay aryl C-H functionalization with diazo compounds
Ph
O
O
O
a.School of Chemistry and Chemical Engineering, South China Unversity of
Technology,381 Wushan Road, Guangzhou, 510641, China. E-mail:
zengwei@scut.edu.cn
2
4
5
3
R
R
N
R
3
R
5
R
R
2
2
R
4
R
1
R
Ph
1
R
R
Ph
3
N
Rh(III)
N
2
G
I
N
2
N
R
N
1
R
Rh(III)
b.School Key Laboratory of Luminescent Materials and Devices Institute of
Polymer Optoelectronic Materials and Devices, South China Universtiy of
Technology, Guangzhou 510641, China
F
Rh(III)
1
E
H
3
R
Scheme 1 Rh(III)-Catalyzed C-C Coupling Cascade Involving Imines and Diazo
compounds
c.
School of Chemistry and Pharmaceutical Engineering, Sichuan University of
Science & Engineering, Zigong 643000, China
† These authors contributed equally.
Electronic Supplementary Information (ESI) available: CCDC 1443747. For ESI
and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c000000x
atives (Scheme 1b). To identify this hypothesis, herein we
report
a
novel
Rh(III)ꢀcatalyzed
relay
carbenoid
functionalization of aryl CꢀH bonds to rapidly establish 1ꢀ
APLE library through a singleꢀstep chemical process from basic
This journal is © The Royal Society of Chemistry 20xx
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1a/2a is 1:1. f The ratio of 1a/2a is 1:2 and the reaction time is 4 h.
reagents. The existing synthetic methods about 1ꢀAPLE
derivatives generally suffer from tedious reaction procedure,
harsh reaction conditions and poor substrate generality. 12
Substrate scope
Having established the optimized reaction conditions that
enable the relay aryl Csp2-H bond carbenoid functionalization
of 1a with 2a, we next investigated its scope with regard to the
Results and discussion
substituted N-phenyl-ketoimines (
1). As illustrated in Scheme
1
2, the substitution on the iminobenzene ring (R1) of
showed
Optimization studies
In the light of the fact that Pd(II), Cu(II) and Ir(III) catalysts, etc
could easily react with diazo compounds to generate metal
carbene intermediates,13 our early investigation began with
the cross-coupling/cyclization cascade of N-phenyl-ketoimine
no significant electronic effects, the ketoimine derivatives with
para-electron-donating group or halide (4-Me, 4-MeO, 4-Cl, 4-
Br, 4-F) on the phenyl ring afforded the 1-APLE derivatives in
good to excellent yields (68‒92%, 3a‒3f), and electron-poor
(1a) and α -acyldiazoacetate (2a) using various catalytic
transition-metal salts in the presence of AgBF4 (10 mol %) in 1,
substrates with nitro group, ethoxylcarbonyl group and nitrile
group on the phenyl ring could also underwent smoothly
o
2-dichloroethane (DCE) at 80 C under Ar atmosphere for 8 h
conversion to provide 65‒72% yields of the desired products
3j 3l. Compared with the para-substituted arylketoimines,
(Table 1, entries 1‒8). After an extensive catalyst screening, we
‒
introducing a methoxy group or chloride to the meta-position
of the C-iminobenzene ring led to poor reaction conversions
soon found catalysts [Cp*IrCl2]2 and [Cp*RhCl2]2 could afford
the desired polysubstituted 1-APLE 3a in 7% and 64% yields
(entries 5 and 8), respectively; and (Cp*RhCl2)2 proved to be
optimal (entry 8). Subsequently, the investigation of the effect
of different silver additives towards the reaction was carried
out, it showed that the reaction yield could be moderately
increased to 85% by using AgSbF6 as additive (compare entries
due to steric hindrance (3g
group- or halogen-substituted phenylamine moieties gave the
1-APLEs (3m 3s, 3u) in 65-82% yields, but electron-poor N-(4-
‒3i). Of note, electron-donating
‒
ethoxylcarbonyl-substituted phenyl)ketoimine and hydroxyl-
containing ketoimine were not allowed for this transformation
8
‒
11 with 12). The further solvent screening demonstrated
that DCE belongs to the most suitable solvent for this reaction
(compare entries 13 17 with 12). Notably, extending the
(
3t and 3v), and the starting materials were completely
recovered. The scope of the present procedure with regard to
diazo compound coupling partners has also been established,
‒
reaction time or increasing the reaction temperature led to a
decreased conversion of 1a to some degree (entries 18 and 19
vs 12). Finally, changing the ratio of 1a/2a from 1:3 to 1:1 or
1:2 decreased the reaction yields (entries 20-21), and also no
mono-aryl Csp2-H bond functionalization product was
observed.
and a wide scope of
alkoxyl, aryl, alkenyl and halogen groups could easily enable
assembling the desried 1-APLEs 3u 3z-2 in 52 72% yields.
Unfortunately, -benzoyl substituted diazoacetate was not
applicable to this transformation (3z
α -alkylacyl substituted diazoacetates with
‒
‒
α
‒3). Finally, the Rh(III)-
catalyzed cascade aryl Csp2-H bond carbenoid functionalization
of 1a (2.0 equiv) with different diazoacetates via one-pot
process was performed. As expected, we got the
Table 1. Optimization of Reaction Conditions a
Me
corresponding cross-coupling cyclization products 3aa
32% yields.14
‒
3ad in
EtO2
C
the overall 20
‒
Catalyst (2. 5 mol %)
additives (10 mol %)
solvent, 80 oC, 8 h
N
O
O
N
+
Table 2. Substrate scope a
OEt
Me
CO2Et
N2
3a
1a
2a
3
R
yield
(%) b
0
0
0
0
7
0
0
64
38
81
69
85
trace
58
62
31
26
71c
82d
24 e
69 f
EtO C
2
entry
catalysts
additives
solvent
2
2
R
R
[Cp*RhCl ] (2.5 mol %)
2 2
N
O
O
N
1
2
3
4
5
6
7
8
Pd(OAc)2
Cu(OAc)2
CuI
[Ru(pꢀcymene)Cl2]
[Cp*IrCl2]2
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgClO4
AgNTf2
AgOAc
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DMF
THF
toluene
CH3CN
DMSO
DCE
DCE
DCE
DCE
AgSbF (10 mol %)
6
+
3
o
3
R
OEt
C
DCE, 80 C, 8 h
1
R
1
R
R
N
2
2
CO Et
2
1
3
EtO2
EtO2C
EtO2C
N
N
N
RhCl3
Rh2(COD)2Cl2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
[Cp*RhCl2]2
MeO
Me
CO2Et
CO2Et
3a, 85%
CO2Et
3c, 89%
EtO2
3b, 92%
9
EtO2
C
C
EtO2C
10
11
12
13
14
15
16
17
18
19
20
21
N
N
N
Br
F
Cl
CO2Et
CO2Et
CO2Et
3d, 71%
3f, 68%
3e, 75%
EtO C
2
EtO C
2
EtO C
2
MeO
N
N
N
CO Et
2
Cl
CO Et
2
OMe CO Et
2
3g
3h
c
3i, 45% (66%)
3g + 3h = 49% (3g / 3h = 1:3)
a
Unless otherwise noted, all the reactions were carried out using
ketoimine (1a) (0.10 mmol) and diazocompound (2a) (0.30 mmol) with
metal catalysts (2.5 mol %) in the presence of silver salts additives (10 mol
%) in solvent (2.0 mL) at 80 ˚C for 8 h under Ar in a sealed reaction tube,
EtO2C
EtO
C
2
N
N
O
N
2
MeO2C
3k, 72%
b
c
CO Et
2
followed by flash chromatography on SiO2. Isolated yield. The reaction
CO2Et
3j, 65%
crystal structure of 3k
temperature is 60 oC. The reaction temperature is 100 oC. The ratio of
d
e
2 | Chem. Commun., 2016, 00, 1-3
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that the low-lying HOMO levels of the small donor molecules
are essential to higher open-circuit voltage (Voc) of the organic
solar cells (OSCs),17 so the combination of 1-APLEs and
carbazole-(Cz) or 1,5-dithia-s-indacene (BDT) units provided
promising precursors with the lower HOMO energy level to
assemble high-performance organic optoelectronic materials.
EtO2
C
EtO2
C
OMe
EtO2C
N
N
N
NC
CO2Et
CO2Et
CO2Et
3l, 70%
EtO2
3m, 82%
3n, 84%
EtO2
EtO2C
F
C
C
N
N
F
N
CO2Et
CO2Et
3p, 72%
3q, 65%
CO2Et
3o, 80%
Scheme 3. Product Transformations
EtO2
C
Cl
EtO2C
Br
EtO2C
CO2Me
R4
R4
N
CO2Et
EtO2
EtO2
C
C
N
N
N
N
N
Ph
(HO)2
B
B(OH)2
4
CO2Et
CO2Et
3s, 79%
CO2Et
3t, 0%
Pd(PPh3
K
)
4 (5 mol %)
Ph N
3r, 73%
2CO3 aq. (2.0 equiv)
toluene, 120 oC, 12 h
CO2Et
Ph
N
R4 = -CH(C8H17
)
2
EtO2
C
5 (70% yield)
EtO2
C
NHAc EtO2C
OH
OR5
EtO
2C
CO2Et
N
N
N
S
CO2Et
EtO2C
OR5
Sn
Sn
3e Br
S
CO2Et
2
CO2Et
CO2Et
O
3w, 72%
3u, 80%
3v, 0%
N Ph
S
OR5
)4 (5 mol %)
6
S
Ph
N
Pd(PPh3
cycohexyl
OR5
K2CO3 aq. (2.0 equiv)
toluene, 120 oC, 12 h
CO2Et
7 (88% yield)
MeO2
C
EtO2C
EtO2C
EtO2C
CH2CH2CH2CH3
CH
CH2CH3
Ph
N
N
R5 = -CH2
N
O
cyclohexyl
CO2Et
2
CO2Me
CO2Et
Ph
3y, 63%
3z, 72%
3x, 70%
Ph
Mechanistic insights
Cl
3
2
EtO
C
2
EtO C
2
EtO
C
2
Several control experiments were designed to elucidate the
aryl Csp2-H bond carbenoid functionalization process (Scheme
4). First, the parallel kinetic isotope effect from monodeuterat-
Ph
Ph
Ph
Ph
N
N
N
Ph
Cl
2
3
CO Et
2
CO Et
3z-1, 52%
CO Et
3z-2, 70%
2
3z-3, 0%
2
O
EtO2C
Ph
Ph
N
D
N
EtO2C
[Cp*RhCl2]2 (2.5 mol %)
AgSbF6 (10 mol %)
EtO2C
MeO2C
EtO2C
Ph
N
or
88% D
Ph
Ph
N
Ph
Ph
(1)
(2)
2a (2.0 equiv)
N
N
N
DCE (2.0 mL), 80 oC, 15 min
O
1a
3a
d-1a-a
CO2Et
KIE = 1.6
CO2Me
3ac
CO2Et
3ad
CO2Et
CO2Et
3aa
3ab
EtO2C
Ph
Ph
N
[Cp*RhCl2]2 (2.5 mol %)
AgSbF6 (10 mol %)
N
(D)H
(D)H
Ph
3a = 28%; 3w = 23%
3aa + 3ab = 32% (3aa/3ab = 0.6:1)
3a = 32%; 3y = 30%
3ac + 3ad = 20% (3ac/3ad = 3.5:1)
N
or
2a (2.0 equiv)
d5
DCE (2.0 mL), 80 oC, 30 min
a
All the reactions were carried out using ketoimines (1) (0.10 mmol) and
98% D
H(D) CO2Et
KIE = 2.0
1a
d-1a-b
3a or d-3a
diazocompounds (2) (0.3 mmol) with [Cp*RhCl2]2 (2.5 mol %) in the
presence of AgSbF6 (10 mol %) in DCE (2.0 mL) at 80 ˚C for 8 h under Ar in a
sealed reaction tube, followed by flash chromatography on SiO2. b Isolated
yield. c The reaction conversion determined by crude 1H NMR spectrum.
[Cp*RhCl2]2 (2.5 mol %)
AgSbF6 (10 mol %)
DCE (2.0 mL), 80 oC, 8 h
85% yield
Ph
Ph
N
O
O
N
(3)
+
OEt
N2
2a
O
8
OEt
1v
O
Synthetic application
Ph
OEt
N
O
O
[Cp*RhCl2]2 (2.5 mol %)
AgSbF6 (10 mol %)
DCE (2.0 mL), 80 oC, 8 h
Ph
(4)
To evaluate the potentiality of the 1-APLEs as an electron
donor in organic photovoltaic devices, we prepared carbazole-
(Cz) or 1,5-dithia-s-indacene (BDT)-containing APLE-based π-
+
N
OEt
H
N2
2a
( 78% yield)
CO2Et
1w
Ph
9
Ph Ac
NH
conjugated organic small molecules
5 (70% yield) and 7 (88%
Ph
N
HN
[Cp*RhCl2]2 (2.5 mol %)
AgSbF6 (10 mol %)
O
O
yield) through traditional Pd-catalyzed cross-coupling strategy
(Scheme 3). The photophysical properties of these organic
small molecules were investigated by UV-vis absorption and
+
+
(5)
OEt
DCE (2.0 mL), 80 oC, 8 h
( 8 and 10 not observed)
N2
1x
2a
10
O
OEt
8
Scheme 4 Preliminary Mechanism Studies
photoluminescence spectroscopy. The small molecule
the absorption ranges from 320 to 380 nm, while the small
molecule exhibits the wider absorption ranges from 340 to
430 nm (Figure S1), and the photoluminescence spectra of
and show maximum emission peaks at 530 and 520 nm,
respectively (Figure S2). The highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital
(LUMO) energy levels of these organic small molecules are
important parameters in the design of optoelectronic
devices.15 To our delight, the cyclic voltammogram (CV) curves
5 shows
ed ketoimine d-1a-a (kH/kD = 1.6) and its pentadeuterate
analogue d-1a-b (kH/kD = 2.0) demonstrated that double aryl
Csp2-H bond activations were involved in this transformation
(eq. 1 and eq. 2), and the second Csp2-H cleavage is a major
contributor to the overall rate of the reaction. 18 Subsequently,
when ortho-substituted arylcycloketoimine 1v was subjected
7
5
7
to the same reaction system, 1-APLE
8 was obtained in 85%
yield (eq. 3). Meanwhile, the ortho-methyl ketoimine 1w
afforded
functionalization/cyclization arylamine product
(eq. 4). On the contrary,
phenyl)naphthalenamine 1x as starting material could not lead
the
mono-aryl
Csp2-H
bond
from compounds
5 and 7 demonstrated that their HOMO
9
in 78% yield
energy level are up to -5.76 eV and -5.57 eV (Figure S3 and
Table S5), respectively. These energy levels were lower-lying
compared with the benzothiadiazole-based polymers.16 Given
employing
2-(N-
to the formation of 1-APLE
8
and amine product 10 (eq. 5),
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these results suggested that the cyclization process would
possibly occur after the second ary Csp2-H carbenoid
functionalization was done, and aryl amine intermediates was
also not involved in this transformation.
The
authors thank
the
NSFC (No.
Science and Technology Program of Guangzhou
21372085),
(No.
156300075) for financial support.
Based on the aforementioned results, a plausible reaction
mechanism is proposed as shown in Scheme 5. Initially,
Notes and references
(Cp*RhCl2)2 dedimerizes and produces
A
a
rhodacycle
intermediate by an imino “nitrogen”-assisted concerted
1 For selected reviews, see: (a) W. Jiang, Y. Li, Z. Wang. Chem. Soc. Rev. 2013,
42, 6113; (b) C. Beemelmanns, H. U. Reissig. Chem. Soc. Rev. 2011, 40,
2199 and reference therein.
metalation/deprotonation (CMD) process. Subsequently, the
coordination of the diazoestate (2a) to the rhodium center is
followed by the denitrogenation/ migratory insertion/
protonolysis to afford monofuctionalized ketoimine
2 For selected examples, see: (a) Y. Park, B. Kim, C. Lee, A. Hyun, S. Jang, J.
H. Lee, Y. S. Gal, T. H. Kim, K. S. Kim, J. Park. J. Phys. Chem. C. 2011, 115,
4843; (b) K. Takimiya, S. Shinamura, I. Osaka, E. Miyazaki. Adv. Mater. 2011,
23, 4347; (c) R. Li, W. Hu, Y. Liu, D. Zhu. Acc. Chem. Res. 2010, 43, 529; (d)
K. Takimiya, Y. Kunugi, Y. Konda, N. Niihara, T. Otsubo, J. Am. Chem. Soc.
2004, 126, 5084; (e) L. Huo, J. Hou, S. Zhang, H. Y. Chen, Y. Yang, Angew.
Chem., Int. Ed. 2010, 49, 1500.
intermediate
1x) could not lead to ortho-aryl Csp2-H bond carbenoid
functionalization (see Scheme 4, eq. 5), the possibility of an
alternative catalytic pathway was excluded. Finally, the
secondary Rh(III)-catalyzed imine-directed Csp2-H bond
carbenoid functionalization/cyclization cascade of furnished
the desired 1-APLE 3a with release of Rh(III) catalyst.
D. In the process herein, given that aryl amine
(
B
3 For selected examples, see: (a) T. Mitsumori, M. Bendikov, O. Dautel, F. Wudl,
T. Shioya, H. Sato, Y. Sato. J. Am. Chem. Soc. 2004, 126, 16793; (b) M. S.
Park, J. Y. Lee. Chem. Mater. 2011, 23, 4338; (c) M. Kim, J. Y. Less. Org.
Electron. 2012, 13, 1245; (d) M. S. Park, D. H. Choi, B. S. Lee, J. Y. Lee. J.
Mater. Chem. 2012, 22, 3099.
D
Ac
CO Et
2
Ph
Ph
4 For selected examples, see: (a) B. Wei, J. Z. Liu, Y. Zhang, J. H. Zhang, H. N.
Peng, H. L. Fan, Y. B. He, X. C. Gao. Adv. Funct. Mater. 2010, 20, 2448; (b) J.
Simokaitiene, E. Stanislovaityte, J. V. Grazulevicius, V. Jankauskas, R. Gu, W.
Dehaen, Y. C. Huang, C. P. Hsu. J. Org. Chem. 2012, 77, 49243.
5 Z. Q. Jiang, Z. Y. Liu, C. L. Yang, C. Zhong, J. G. Qin, G. Yu, Y. Q. Liu. Adv.
Funct. Mater. 2009, 19, 3987.
1/2[Cp*RhCl
]
N
2
2
N
AgSbF
Ac
6
AgCl
G
1a
CO Et
2
cascade cyclization
Cp*Rh(SbF
)
2
6
Ac
CO Et
2
Ph
Rh
Ph
N
N
6 For selected examples, see: (a) P. Liu, S. Dong, F. Liu, X. Hu, L. Liu, Y. Jin, S.
Liu, X. Gong, T. P. Russell, F. Huang, Y. Cao. Adv. Funct. Mater. 2015, 25,
6458; (b) X. F. Wu, W. F. Fu, Z. Xu, M. Shi, F. Liu, H. Z. Chen, J. H. Wan, T.
P. Russell. Adv. Funct. Mater. 2015, 25, 5954; (c) C. C. Lai, M. J. Huang, H. H.
Chou, C. Y. Liao, P. Rajamalli, C. H. Cheng. Adv. Funct. Mater. 2015, 25,
5548; (d) C. Ji, Y. Zheng, J. Li, J. Shen, W. Yang, M. Yin. J. Mater. Chem. B.
2015, 3, 7494.
Rh
Ac
Ph
N
A
CO Et
2
F
EtO C
2
Ac
2a
CO Et
2
2a
N
2
3a
CO Et
2
Ac
Ac
CO Et
2
Ph
Rh CO Et
2
Ph
N
N
cascade cyclization
Rh
E
B
Rh(III)
7 (a) A. Yu, X. Xue, J. Wang, H. Wang, Y. Wang. J. Phys. Org. Chem. 2012, 25,
92; (b) G. Y. Eom, Y. H. Choi, J. H. Byun, J. H. Park, H. Y. Lee. KR Patent
2014100766A, 2014.
Ac
Rh CO Et
Ph
Ac
CO Et
2
2
N
protonolysis
Path A
1, 1-aryl shift
Ph
-Rh(III) salts
N
EtO
C
2
Ac
HN
Ph
EtO C
2
D
Ph
N
C
Rh
8 For selected examples, see: (a) W. W. Chan, S. F. Lo, Z. Zhou, W. Y. Yu. J.
Am. Chem. Soc. 2012, 134, 13565; (b) T. K. Hyster, K. E. Ruhl, T. Rovis. J.
Am. Chem. Soc. 2013, 135, 5364; (c) B. Ye, N. Cramer. Angew. Chem., Int.
Ed. 2014, 53, 7896; (d) S. Yu, S. Liu, Y. Lan, B. Wan, X. Li. J. Am. Chem. Soc.
2015, 137, 1623; (e) F. Hu, Y. Xia, F. Ye, Z. Liu, C. Ma, Y. Zhang, J. Wang.
Angew. Chem. Int. Ed. 2014, 53, 1364; (f) D. Zhao, H. Kim. L. Stegemann, C.
A. Strassert, F. Glorius. Angew. Chem., Int. Ed. 2015, 54, 4508; (g) Z. Shi, D.
C. Koester, M. Boultadakis-Arapinis, F. Glorius, J. Am. Chem. Soc. 2013, 135,
12204.
Path B
Ph
Ac
HN
-Rh(III)
K
CO Et
2
J
CO Et
2
H
CO Et
2
2a
Ph
Rh(III)
Rh
N
I
CO Et
2
Scheme 5. Possible Mechanism for the Transformation
9 Y. Xie, T. F. Chen, S. M. Fu, X. S. Li, Y. Deng, H. F. Jiang, W. Zeng. Chem.
Commun. 2014, 50, 10699.
10 Y. Xie, T. Chen, S. M. Fu, H. F. Jiang, W. Zeng. Chem. Commun. 2015, 51,
9377.
Conclusions
11 X. Chen, Y. Xie, X. Xiao, G. Li, Y. Deng, H. F. Jiang, W. Zeng. Chem.
Commun. 2015, 51, 15328.
In conclusion, we have developed a novel Rh(III)-catalyzed
relay aryl Csp2-H bond carbenoid functionalization between
arylketoimines and diazoesters. This reaction can serve as a
concise method for rapidly assemblying unique π-conjugated
1-APLEs with wide reactive functional group tolerance. The
primary exploration about photovoltaic performance of 1-
APLE-based π-conjugated molecules demonstrated that these
compounds could be further converted to promising organic
optoelectronic materials.
12 (a) P. Flowerday, M. J. Perkins. J. Am. Chem. Soc. 1969, 91, 1035; (b) T.
Gottlieb, J. L. Neumeyer. J. Am. Chem. Soc. 1976, 98, 7108; (c) S. O’Brien,
D. C. C. Smith. J. Chem. Soc. 1963, 2907.
13 For selected reviews, (a) Q. Xiao, Y. Zhang, J. Wang, Acc. Chem. Res. 2013,
46, 236; (b) (c) A. Archambeau, A.; F. Meige, C. Meyer.; J. Cossy. Acc.
Chem. Res. 2015, 48, 1021.
14 It is difficult for isolating the corresponding cross-coupling mixture (3aa and
3ab, 3ac and 3ad), their ratio data was determined by 1H NMR spectrum.
15 M. C. Scharber, D. Muhlbacher, M. Koppe, P. Denk, C. Waldauf, A. J.
Heeger, C. Brabec. J. Adv. Mater. 2006, 18, 789.
16 L. Dou, J. Gao, E. Richard, J. You, C. C. Chen, K. C. Cha, Y. He, G. Li, Y.
Yang. J. Am. Chem. Soc. 2012, 134, 10071.
Acknowledgements
17 H. Zhou, L. Yang, W. You. Macromolecules 2012, 45, 607.
18 E. M. Simmons, J. F. Hartwig. Angew. Chem., Int. Ed. 2012, 51, 3066.
4 | Chem. Commun., 2016, 00, 1-3
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